PRELIMINARY STUDY OF
SELECTED POTENTIAL
ENVIRONMENTAL CONTAMINANTS -
OPTICAL BRIGHTENERS, METHYL
CHLOROFORM, TRICHLOROETHYLENE,
TETRACHLOROETHYLENE, ION
EXCHANGE RESINS
JULY 1975
FINAL REPORT
U.S. Environmental Protection Agency
Office of Toxic Substances
Washington, D.C. 2046O
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EPA-560/2-75-002
Final Report
PRELIMINARY STUDY OF
SELECTED POTENTIAL ENVIRONMENTAL CONTAMINANTS
OPTICAL BRIGHTENERS
METHYL CHLOROFORM
.TRICHLOROETHYLENE
TETRACHLOROETHYLENE
ION EXCHANGE RESINS
Contract No. 68-01-2657
Project Officer
Frank D. Kover
Prepared for
Office of Toxic Substances
Environmental Protection Agency
Washington, D.C. 20160
July 1975
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NOTICE
This repor.t. has been reviewed by the
Office of Toxic Substances, EPA,,and
approved for publication. Approval
does not signify that the contents
necessarily reflect the views and
policies of the Environmental Pro-
tection agency, nor does mention of.
trade names or commercial products
constitute endorsement or recommenda-
tion for use.
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TABLE OP- -CONTENTS
OPTICAL BRIGHTENERS
Summary and Conclusions 1
I. Physical Properties U
II. Uses . U
III. Production and Importation lU
IV. Current Practice l6
V. Enviornmental Contamination 17
VI. Monitoring and Analysis 18
VII. Chemical Reactivity ' "22
VIII. Biology . . 25
A. Absorption 25
B. Excretion/Elimination 26
C. Transport and Distribution 26
D. Metabolism and Metabolic Effects . 29
IX. Enviornmental Transport and Fate 29
A. Persistence and/or Degradation . . 29
B. Enviornmental Transport . ' , 30
C. Bioaccumulation 30
X. Toxicity 30
A. Human Toxicity 30
B. Toxicity to Non-human Mammals 32
1. Acute, Subacute, and Chronic Toxicity 32
2. Sensitization 36
3. Teratogenicity 37
k. Carcinogenicity 38
5. Mutagenicity Uo
6. Behavioral Effects Ul
C. Toxicity to Lower Animals Ul
D. Toxicity to Plants U2
E. Toxicity to Microorganisms ^3
Appendix . . UU.
Literature Cited ^5
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TABLE. OF CONTENTS (Cont'd)
CHLORINATED HYDROCARBON SOLVENTS .. .
METHYL .CHLOROFORM, TRICHLOROETHYLENE, -TETRACHLOROETHYLENE
Summary and Conclusions U8
I, Physical Properties . 50
II. Production ' . 6h
A. Methyl Chloroform 6k
B. Trichloroethylene 66
C. Tetrachloroethylene 69
III. Uses . -'.... ..- ,. 72
IV. Current Practices 76
V. Enviornmental Contamination " " .81
VI. Monitoring and'Analysis . . . 83
A. Analysis of Mixtures . . 83
B. Trichloroethylene . 85
C. Tetrachloroethylene . 86
VII. Chemical Reactivity 87
A. Methyl Chloroform 87
B. Trichloroethylene ' 88
C. Tetrachloroethylene ' 89
VIII. Biology . ' ' 90
A. Absorption '. . . 90
B. Excretion . ' 90
1. Methyl Chloroform 90
2.- Trichloroethylene . . -..-. . -92.
3.. Tetrachloroethylene .93
11
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TABLE OF CONTENTS (Cont'd)
CHLORINATED HYDROCARBON SOLVENTS
METHYL CHLOROFORM, TRICHLOROETHYLENE, TETRACHLOROETHYLENE
C. Transport and Distribution 9^
1. Methyl Chloroform 9k
2. Trichloroethylene 9^
3. Tetrachloroethylene 95
D. Metabolism and Metabolic Effects 96
IX. Enviornmental Transport and Fate 99
A. Persistence and/or degradation 99
B. Enviornmental Transport 100
C. Bioaccumulation 100
X. Toxicity .. ..... ... 101
A. Human Toxicity 101
1. Inhalation of Methyl Chloroform 101
2. Ingestion of Methyl Chloroform 103
3. Skin Contact with Methyl Chloroform 10U
h. Behavioral Effects of Methyl Chloroform IQk
5. Inhalation of Trichloroethylene 10U
6. Ingestion of Trichloroethylene 107
7. Skin Contact with Trichloroethylene ' 108
8. Behavioral Effects of Trichloroethylene 108
9. Inhalation of Tetrachloroethylene 109
10. Ingestion of Tetrachloroethylene 112
11. Skin Contact with Tetrachloroethylene 112
12. Behavioral Effects of Tetrachloroethylene 112
B. Toxicity to Non-human Mammals 115
1. Acute, Subacute, and Chronic Toxicity 115
a. Inhalation 115
b. Ingestion . . 119
c. Intraperitoneal Administration 119
2. Sensitization 120
3. Teratogenicity 120
U. Carcinogenicity 120
5. Mutagenicity 121
6. Behavioral Effects 121
C. Toxicity to Lower Animals and Insects 121
D. Toxicity to Plants 122
E. Toxicity to Microorganisms 122
Literature Cited 123
iii
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TABLE OF CONTENTS (Cont'd)
'-....- Page
ION-EXCHANGE RESINS / :
Summary and Conclusions 131
I. Physical Properties , 133
II. Production ' 136.
III. Uses 136
IV. . Current, Practice .138
V. Environmental Contamination 138
VI. . Monitoring and Analysis 138
VII. Chemical Reactivity .
VIII. Biology .;/..
A. Absorption ,
B. Excretion/Elimination .
C. Transport and Distribution .
D. Metabolism and Metabolic Effects
IX. Environmental Transport and Fate
A. Persistence and/or Degradation
B. Environmental Transport
C. Bioaccumulation
X.' Toxicity
.A. Human Toxicity .
1. Inhalation
2. Ingestion
B. Toxicity to Non-Human Mammals
1. Acute, Subacute and Chronic Toxicity
2. Sensitization ' .
3. Teratogenicity - Reproductive Effects
4. Carcinogenicity -
. 5. Mutagenicity
6. Behavioral Effects
C. Toxicity to Lower Animals .
D. Toxicity to Plants
E. Toxicity to Microorganisms
Literature Cited . .
iv . .. -:.' . ;..
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OPTICAL BRIGHTENERS: Summary and Conclusions
The "optical brighteners" constitute a unique class of chemicals, not
onjy because of their wide structural variety but also because of their
wide application range.
In recent years, optical brighteners have become one of the more im-
portant components of laundering products in the United .States. Millions
of pounds are used yearly for this purpose. Virtually all clothing con-
tains brighteners; they are used extensively for the mass whitening of
synthetic polymer fibers, during which the optical brightener is added to
the spinning solution or melt. They are also used in the finishing of
textiles, including "wash-wear" cottons, where they are applied to the
fabric along with a finishing agent. In paper manufacture, the brighteners
can be applied to the pulp in the dipping process or during the coating
operation. Most of the vast numbers of articles which are manufactured
from plastics contain brighteners, including wrappers and containers for
foodstuffs.
Although the production of optical brighteners in the United States
has declined somewhat, this cannot be taken as an indication of the pre-
valence of these agents without reference to import statistics: available
figures show that approximately 2,000,000 pounds of brighteners were im-
ported in 1972. These import figures are broken down to the amount of
each brightener by trade name. No such breakdown was found for the brigh-
teners which are manufactured in the United States.
Identification of the individual structures of the molecules which
are employed as brightening agents has become increasingly difficult because
of their growing numbers and tremendous structural varieties. Each agent,
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of course, has a characteristic spectral-absorption curve of minimum
transmittance or maximum absorption. Reliable identification, however,
would depend on a detailed examination by chroma tography, absorption spec-
troscopy, and comparison of the infrared spectra to determine the parent
structure and the substituents.
Nothing is reported on the fate of these compounds when their sub-
strates decompose, i.e., deterioration from use or gradual decomposition
after being discarded, or following incineration of the substrate. They
certainly have a direct route into the water supply, being carried in the
effluent from manufacturing plants and in household laundry waste water.
The stilbenedisulfonic acid salts are water soluble when released as the
free molecule (not attached to a substrate) into aquatic systems.
Considering the inertness of the optical brighteners towards other
chemicals which they .contact during application, and their stability under
rigorous processing conditions, it would seem that they should remain
stable in the environment. Those brighteners which are incorporated into
enzyme-containing detergent formulations would probably resist biodegradi-
bility becuase of their enzyme-stability. This would certainly raise the
question of bioaccumulation, on which no specific studies under natural
conditions (accumulation in fish, for instance) have been reported. The
few tissue-affinity studies which have been published report a rapid
excretion of the brighteners into the bile or the urine. Long-term studies
showed no changes in the organs of the test animals. These results, of
course, are valid only for those compounds which were selected for the
studies.
All studies reported in the literature on the toxicity of the optical
brighteners toward humans and the lower animals- gave negative results. The
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studies on animal reporduction, including teratogenicity and mutagenicity
studies, also gave negative results.
One specious report of the carcinogenic interaction of the optical
brighteners and ultraviolet light appeared in the recent literature and
reported positive results. However, this work has been highly criticized
because it was conducted under unrealistic conditions and thus had no
practical value. The authors of this report have conceded to their critics
and have announced that further work is in progress. All other studies
on carcinogenesis have reported negative results.
In summary, it would seem that introduction into environmental waters
would be the most probable source of pollution by the optical brightening
agents. There are no data in the literature reporting on the fat-solubility
of any brightener molecules. This property would have bearing on bioaccu-
mulation. While these compounds may be chemically inert in vitro, no
conclusions can be drawn from the information in the literature as to what
biological activity they might exhibit if they gained entrance into human
systems to any extent.
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Optical Brighteners
1. PROPERTIES AtiD USES
The literature abounds with synonyms alluding to the properties of
the optical brighteners: optical whiteners, fluorescent white dyes, or-
ganic fluorescent dyes, fluorescent whitening agents, fluorescent brighten-
ers, and optical bleaching agents. Optical brighteners, however, are in
no way comparable with bleaching agents; their only common property is
the improvement of the whiteness of the substrate; even in this they
differ in the means by which the desired effect is attained.
In all other properties the optical brighteners are closely related
to dyes. They are dyes, in fact, in the sense that they change the visual
appearance of the substrate to which they adhere, although they differ
from dyes in the way that the desired effect is produced. A dye molecule
absorbs visible light and reflects the unabsorbed portion. A fluorescent
molecule absorbs invisible ultraviolet light and emits visible blue
fluorescent light. It is this property that lends special status to the
optical brighteners.
A variety of theories have been developed to explain dye-fiber inter-
action. These same theories serve to explain brightener-fiber interac-
tion. The main theories pertaining to brightening cellulose are the theor-
ies of direct dye mechanisms:
(1). Hydrogen Bonding. The brightener molecule must be capable of
forming hydrogen bonds. It should be linear, should have aromatic nuclei
capable of coplanar configuration, and should cont.ain conjugated double
bonds.
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(2). Van der Waal's Forces. The brightener molecule should be planar to
allow the closest possible contact with the fiber. The attraction is by
interaction of dipoles, between nonionic portions of the molecules. The
attractive forces depend on the size and the mobility of the electron
clouds. Substantivity increases with the number of conjugated double
bonds.
(3). Aggregation Theory. The brightener molecule must be planar to penetrate
the cellulose and enhance aggregation. The molecules pass singly into
the fiber and then aggregate after losing their water of hydration. Van
der Waal's forces between the dye molecules increase in strength with
increasing numbers of double bonds (Stensby, 1967).
The main theories pertaining to brightening synthetic fibers, such
as nylon, polyester, and acetate, are the theories of dispersed dye mechan-
isms: (1). The solid brightener dissolves into the solid fiber, or:
(2). The brightener molecules penetrate into "canals" between the fiber
molecules, or:
(3). The water-insoluble brighteners may be soluble to a small extent.
The small amount of dissolved brightener, then, would be adsorbed by the
fiber, permitting more brightener to dissolve until equilibrium is reached
(Stensby, 1968).
Further discussion on brightener-fiber interaction is given in Sec-
tion VII, CHEMICAL REACTIVITY.
Raw textiles, papers, and plastics have a yellow tint attributable
not only to the wavelength of light which they naturally absorb, but also
to the colored impurities associated with the raw goods. It is well known
that materials with a yellow cast can be made to look whiter by adding a blue
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tint, as evidenced by the success of the laundering "bluing agents" which
fluorished until recently. Optical brighteners correct any off-white
appearance by reason of the blue-to-violet fluorescence which they exhi-
bit under ultraviolet light as it is present in ordinary daylight.
To qualify as an additive in laundry products, a brightener must
be stable to heat, water, and bleaching agents (Figs. 1, 2, and 3).
For use in the textile industry, a brightener'must be light-fast and
possess certain properties of fiber affinity (Figs. 4, 5, and 6).
In the plastics industry, the main areas of brightener application
today are in PVC films, boards, injection mouldings, and plastisols; poly-
styrene boards and injection mouldings; polypropylene films and injection
mouldings; polyethylene paper coatings, polyurethane coatings, thermo-
setting pressings and resins (Fig. 7).
Following are the basic chemical structures of some optical brighten-
ers with the most important fields of application of their derivatives, as
given in Review 1973/1, by Ciba-Geigy.
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Fields of application
and substrates
Textiles, detergents
spinning solutions/
melts, plastics
polyamide (T, W)
polyester (T, W, S)
polyvinylchloride (K)
polystyrene (K)
polypropylene (K)
secondary acetate (T. S)
triacetate (T, S)
Textiles, detergents
spinning
solutions/melts
cotton (W)
polyamide (W)
polyacrylonitrile (T, S)
Textiles, detergents
spinning solutions/
melts, plastics
polyamide (T, W)
polyester (S)
polyacrylonitrile (T)
polyvinylchloride (K)
polystyrene (K)
silk (T)
secondary acetate (T)
triacetate (T)
Textiles, detergents
! wool (T)
silk (T)
triacetate (T)
secondary acetate (T)
polyacrylonitrile (T)
polyamide (T, W)
Textiles
polyester (T)
polyacrylonitrile (T)
secondary acetate (T)
triacetate (T)
Textiles
polyester (T)
secondary acetate (T)
triacetate (T)
Textiles, detergents
polyamide (T, W)
polyester (T, W)
General basic structures
R R
R R
bis- (benzoxazol-2-yl) -derivatives
£^x_£r^
R2 R,
bis- (benzimidazol-2-yl) -derivatives
i1
Coumarins
R5
"3 "4
pyrazolins
o >r~\
RK1 \i . /
1 / \
naphthalimides
OR
^^^ OR
triazinyl-pyrenes
1 U
1 H ^
2-styryl-benzoxazoles and naphthoxazoles
Subsmuetiut
ii H
W
H H
1 1 f~\.
c=c c=c-< y-
i i \ /
H H
CM,
-R--H.-C(CH,)» C-/ N . CH,
CH,
-COOsIM
~ *L. / . c=c
H
_R = _H, -CH,. -CH2CH2OH
-R, -.-H.-CH,.-CH1COOH
-R,.-H.-/^.-|T~J ^-COOCH,
-M' ^T J| -,O*»»«. -N (*»*),.- "-CO-CM
-R, =-H,-CI.-N: * *
_R3,_R4__H, -alkyl. -^^
-R2 = -CI.-SO3H,-SO2NH2,-H
-SO2NH-. -COO alkyl
-S02CH^
-SO2 NH CH2 CH2 CH2 N (CH,),
R U f*t
5 H. - U
RI ~ alkyl CH2CH2CH2N(CH,),
-R2 = - O alkyl, - SO3H. - NH CQCH3
R - alkyl
-R, = -CN, -COO alkyl. -Cl
- R4 = -H, -alkyl. /^N
Fiel«te of application. Textiles (T). Detergents (W), Paper (P), Spinning Solutions/melts (S), Plastics (K)
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Textiles, detergents
paper, spinning
solutions/melts
cotton (T, W)
polyamide (T. W, S)
cellulose (T. W. P. S)
SOjH " R4
4.4' -bis- (triazinylamino)-stilbene-2,2'-disulfonic acids
SO3H
-N(CH2CH2OH)2. -NCH2CH2OH. -NH2
-N(alkyl)2,-OCH3.-Cr
-N-CH2CH2S03H,-NHCH2CH2OH
H
Textiles, detergents
H03S
cotton (T, W)
polyamide (T, W)
4,4'-bis-(v-triazpl-2-yl)-stilbene-2,2'-disulfonic acids
Spinning
solutions/melts
polyester (S)
_R = -H,-OCH3,-aikyl
4,4'-bis-(diphenyltriazinyl)-stilbenes
Textiles, detergents
paper
spinning solutions/
melts, plastics
cotton (T, W)
cellulose (T, W, P)
polyamide (T, W, S)
polyester (T, S)
polyvinylchloride (K)
polystyrene (K)
polyurethane (K)
H
4.4' - distyryl - biphenyls
-R = -H,-SO3H.-SO2N(3lkyl)2
-OCH3. -CN, -C(, -COQCHj
-6oN(alkyi)2
Textiles, spinning
solutions/melts
polyester (T)
polyamide (S)
H
C=C
H
4-phenyl-4'-benzoxazolyl-stilbenes
-R =-H,-GI.-alkyl,-SO2CH3
Textiles, detergents
spinning solutions/
melts, plastics
cotton (W)
polyamide (W)
polyacrylonitrile (S)
oolyester (T, W, S)
polyvinylchloride (K)
polystyrene (K)
-R, =_H,-CI
-R2 =-SO3H,-SO2NC,-SO2OC6HS
-CN
-R3 = -H,-SO3H
stilbenyl - naphthotriazoles
Textiles, spinning
solutions/melts
polyester (T)
polyamide (S)
-R = -CN,-CONc
4-styryl-stilbenes
Fields of application Textiles ^T). Detergents (W), Paper (P), Spinning Solutions/melts (S). Plastics (K)
8
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Fig. 1. OPTICAL BRIGHTENERS (FLUORESCENT WHITENING AGENTS) IN DETERGENTS
FLUORESCENT BRIGHTENER 9
"v
NH
CH = CH
SOjNa
SOjNa
NH
FLUORESCENT BRIGHTENER 28
E
CH,
N^ J?
NH-fT ~^t-NH ('
SO,H
SO,H
i CHJ
II
OH OH
OH
NH-C' ^VCHsaCH-C' ^>-NH-j^ "^St- NH
,, CH, ^C CH,
H,
OH
HjC
\ x'
O
SO,Na
SOjNa
NH^*|NH-
SOURCE: Stensby, 1965
SOjNa
CH, CH,
CH, CH,
OH OH
CH, CH,
r i
CH, CH,
OH OH
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Fig. 2. COTTON BRIGHTENERS
i
R=
" r01' r- MO- or
" ' r i ' f' ' MOR'NH
M Oil M
TA DM DMEA DDEA MEO
Fig. 3. BLEACH STABLE BRIGHTENERS
BRIGHTENER BS BRI6HTENER NTS
f
BRIGHTENER BBI
SOURCE: Stensby, 1967 a
10
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Fig. 4. POLYAMIDE BRIGHTENERS
R'
7
BRI6HTENER AC BRI6HTENER DP
Fig. 5. POLYESTER AND POLYAMIDE BRIGHTENERS
\
,C-CH=CH-R
BRIGHTENER BBO
BRI6HTENER BOS
N N
BRIGHTENER NTSA
Fig. 6.
The most important properties
of some polyester whiteners
in relation to their chemical
structure.
X
.0-
-o
naphthyl
naphthyl
stilbyl
stilbyl
R
-C(CH3)3
-E©
-H
-COOR
-H
-COOC4H9
Thermal
stability
good
good
poor
good
poor
good
Glycol
vapour
volatil-
ity
high
moder-
ate
high
none
moder-
ate
none
Subli-
mation
high
none
high
none
moder-
ate
none
Shade
greenish
greenish
bluish
bluish-
green
bluish
bluish
SOURCES: Figs. 4 and 5 - Stensby, 1967a
Fig. 6 - Review, 1973/1
11
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Fig. .7. PROPERTIES OF VARIOUS OPTICAL BRIGHTENERS FOR USE IN PLASTICS
Structure
@CC
f^Wl
Fields
of
applica-
tion
PVC. PS.
PP. PE
PVC, PS,
PP. PE
PVC, PS,
PS
PVC, PS,
PP, PE
Migra-
tion
stability
very
good
very
good
good
moder-
ate
Light
fastness
good
good
moder-
are
good
White
build-
up
good
very
good
very
good
moder-
ate ;
SOURCE: Review. 1973/1
12
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The optical brighteners are very versatile chemical compounds; most
of them have more than one major application, as is shown in the
tables and figures in the appendix.
There is a lack of sufficient data in the literature to establish
which of the brighteners are most commonly used (the U. S. Tariff Commission
does not publish individual production figures for the brighteners). Figures
1 through 7 are indicative of the major volume compounds; however, these
are all based on data from Ciba-Geigy Corp. The amount of information
which is published on an individual brightener (compiled in the tables
given in the appendix) may be indicative of its competitive status.
According to Chemical Economics Handbook, the following figures are
1965
1966
1967
1968
1969
: percent of
Detergents
63.6%
67.6
73.3
73.0
72.6
sales value
Paper
13.0%
9.8
7.7
7.8
8.2
by application:
Textiles
18 . 3%
16.0
13.0
13.1
12.8
Fibers/Plastics
. 5.1%
6.6
6.0
6.1
6.4
These figures indicate that, in 1969, approximately 29,000,000 pounds
of the brighteners produced in the United States went into detergents;
3,000,000 pounds went into paper; 4,000,000 pounds went into textiles;
and 2,000,000 pounds went into synthetic fibers and plastics.
Sandoz, Inc. (Technical Bulletin I-C-2009 No. 5) recommends its
Aclarat 8678 as a shampoo additive0.01% to brighten hair and 0.05% to
whiten off-white hair. This is the only direct reference to cosmetic appli-
cation found in the literature. Since no C. I. -Fluorescent Brightener num-
13-
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her was found for this product, its properties are listed under the trade
name at the end of the appendix. .,
III. PRODUCTION AND IMPORTATION .
While dye production gained by 8.0% in 1972 over 1971, the production
of optical brighteners fell by 8.4%. Of the total 1972 production of all
compounds classified as dyes, the optical brighteners accounted for 10.4%.
The United States' manufacturers of brighteners as reported to the
U. S. Tariff Commission in 1972, are: American Cyanamid Co.; Ciba- Geigy
Corp.; Cincinnati Malacron Chemicals, Inc.; E. I. duPont de Nemours and
Co., Inc.; GAF Corp. (Chemical Div.); Pfister Chemical Works; Sandoz, Inc.
(Sandoz Color and Chemicals Div.); Hilton-Davis Division of Sterling Drug
Co., Inc.; and Verona Corp.
Production figures are as follows, in pounds, as published by the
U. S. Tariff Commission:
YEAR SPECIFIC FLUORESCENT BRIGHTENERS . ALL OTHERS TOTAL
1958
1959
1960
1961
1962
1963
1964
1965
1966
1967
1968
F.
F.
F.
B.
B.
B.
68
68
68
Fluorescent
F.
F.
F.
F.
F.
F.
F.
F.
B.
B.
B.
B.
B.
B.
B.
B.
68
9
28
28
9
28
9
28
63
72
100
,000
,000
,000
7,
9,
11,
429
684
746
,000
,000
,000
Brighteners are included under "ALL
31
3,749
1,515
1,240
318
1
234
1,420
,000
,000
,000
,000
,000
,410
,000
,000
16,
14,
2.1.
25,
29,
644
156
972
894
643
,000
,000
,000
,000
,000
5
7
7
9
11
OTHER
16
19
23
26
30
,900,
,000,
,492,
,756,
,846,
DYES
,675,
,420,
,212,
,213,
,297,
000
000
000
000
000
it
000
000
000
410
000
-------
254,000
1,676,000
1,593,000
1,574,000
1,604,000
37,844,000
29,731,000
28,238,000
25,717,000
39,774,000
31,324,000
29,812,000
27,321,000
YEAR SPECIFIC FLUORESCENT BRIGHTENERS ALL OTHERS TOTAL
1969 F. B. 9
F. B. 28
1970 F. B. 28
1971 F. B. 28
1972 F. B. 28
Although the production of optical brighteners in the United States
has declined somewhat, this cannot be taken as an indication of the pre-
valence of these agents without reference to import statistics. Import
figures for 1972 (in pounds) are listed below. This information was
taken from the U. S. Tariff Commission Reports.
OPTICAL BRIGHTENER AMOUNT IMPORTED OPTICAL BRIGHTENER AMOUNT IMPORTED
F. B. 28 4,180 Ecophan 240,302
F. B. 32 5,181 Fluorescent Red 5B 110
F. B. 47 33,951 Hostalux NR 26,978
F. B. 48 5,570 Hostalux PR 1,980
F. B. 52 3,527 Leucophor PC 16,534
J*. B. 55 220 Phorwite BHC 167,090
F. B. 75 1,200 Phorwite DCR 5,885
F. B. 103 220 Phorwite K 50
F. B. 112 250 Phorwite MAN . 100
F. B. 119 125,040 Tinopal CH-3511 1,875
F. B. 121 79,210 Tinopal MSP 220
F. B. 134 25,792 Tinopal SFG 7,883
F. B. 140 441 Tinopal 3751 112
F. B. 148 5,250 Tuyacol 61F 11,023
F. B. 184 551 Uvitex AT 2,006
F. B. 191 77,975 Uvitex CK 22,484
F. B. 200 46,250 Uvitex EFT 496
F. B. 205 490,665 Uvitex MA 1,058
F. B. 229 77,160 Uvitex MES . 2,249
F. B. 238 1,587 Uvitex NFW .220
15 '
-------
OPTICAL BRIGHTENER AMOUNT IMPORTED OPTICAL BRIGHTENER AMOUNT IMPORTED
F. B. 251 220 Uvltex 3257 332,782
F. B. 254 1,102 Uvitex 5660 1,433
F. B. 257 1,050 Other optical
F. B. 265 450 brighteners 3,747
TOTAL 1,833,659
IV. CURRENT PRACTICE
There seem to be no particular problems in the storage, transport,
or handling of the optical brighteners.
The Hilton-Davis Division of Sterling Drug Co. advises that if Hilta-
mine Arctic White products come into contact with the skin, it should be
rinsed thoroughly with water. Precautions should be taken against entry
of these products into the eyes or respiratory tract. By following these
precautions, the fluorescent whitening agents should offer no health
hazards in industrial handling (Hilton-Davis Technical Bulletin B-17-4/73).
Data on these Hiltamines can be found in the tables in the appendix
tinder C. I. Fluorescent Brighteners 9.1, 28, 126, 127, 128, 129,
130, 130:1, 131, and 132. Those Hiltamines with which no Fluorescent
Brightener number was correlated are listed separately at the end of the
tables.
American Cyanamid Co. (Technical Sales Bulletin 1056.) states that
all shipments of Calcofluor White RW Solution bear the following warning
label:
CAUTION! May Cause Irritation.
Avoid contact with skin or eyes.
In case of contact, flush skin or eyes with plenty of water.
Further data on Calcofluor White RW can be found in the tables under
C. I. Fluorescent Brightener 61.
\6
-------
No other directives for special handling of the optical brighteners
was found in the literature.
V. ENVIRONMENTAL CONTAMINATION
The wide range of applications of the optical brighteners would make
environmental contamination a distinct possibility.
Their incorporation into laundry products would suggest a transport
route into surface and ground waters. During industrial production or
application, brighteners may get into the effluent. Ciba-Geigy reports
(Review, 1973/1) that the amounts measured in domestic effluent in densely
populated areas vary between about 0.01 and 0.1 ppm (Stensby, 1968, states
that the total concentration of birghtener in the liquor of the modern
American home laundry would be only 3-10 mg/liter). Efficient purifica-
tion plants retain more than 90% of the brighteners from industrial ef-
fluents. In very badly polluted rivers with few adjacent purification
plants, doses can be of the order of 0.000001 grams per liter, while no
demonstrable amounts can be found in rivers with sufficient purification
plants.
Skin contact is inevitable, largely from wearing textiles that have
been treated with these agents. According to Ciba-Geigy Corp. (Review,
1973/1), the high affinity for natural fibers and firm fixation in synthetic
fibers do not permit the transfer of measurable amounts of FWA to the skin.
The same holds true for plastics and paper which contain amounts of brigh-
tener similar to the amounts contained in textiles (0.05% and 0.15% of ...
optical brightener). .
Transference into food from brightener-treated containers and wrapping
paper may lead to unintended ingestion. Low levels of brighteners persisting
17
-------
in potable water would be another source of unintended ingestion. If some
amount of brightener were ingested from these sources, the amount would be
10,000 times smaller than the amounts tolerated in long-term animal experi-
ments without toxic effects (Ciba-Geigy, Review. 1973/1).
VI. MONITORING AND ANALYSIS
A comprehensive presentation of the analysis of optical brighteners
is given by Kiger and Bbn (1960). The following brighteners were studied
in this work:
TRADE NAME
Tinopal AN
Tinopal 2B
Tinopal BV
Tinopal 4BM
Tinopal GS
Tinopal RBN
*Tinopal SP
*Uvitex BT
Uvitex GS
Uvitex RBS
Uvitex RS
Uvitex RT
Uvitex VR
Celumyl BW
FLUORESCENT BRIGHTENER
' 55' "'."
24
1
28
47
59
18
;.. 19
42
41
37
142
TRADENAME
Celumyl R
Celumyl S
Blankophor BA
Blankophor BBV
Leucophor B
Leucophor 2B
Leucophor BS
Leucophor R
Leucophor RG
Fluotex CBL
Fluotex CDC
Blankit 1A
*Ultraphor GPB
Pontamine White G
FLUORESCENT BRIGHTENER
17
113
114
32
49
30
14
21
114
*These brighteners are not being currently manufactured.
The most suitable solvent for these brighteners was a mixture of 95
parts of pyridine to 5 parts of ammonium hydroxide. To extract the brigh-
teners from cotton fabric for assay, 2 gm of fabric (approximately 10 x 10
cm) was placed in a 100 ml flask with 30 ml of a 5% solution of ammonium
18
-------
hydroxide in pyridine and was shaken for two hours. The extract was con-:
centrated to 3-5 ml on a water bath.
Detection methods are summarized as follows:
Circular Paper Chromatography; Results were obtained within two hours,
but were not satisfactory enough to merit further study. No migration
took place with dichloroethane, cyclohexanone, ethyl acetylacetate or
methylcyclohexanone. Spots were displayed with butyl acetate and isobutanol.
Migration was quite variable with neutral or acidic acetone, with neutral
or acidic acetone, methanol, with propanol, and with dimethylformamide.
Column Chromatography: A 5 mm alumina column was used and development took
place in approximately two hours per ml of solution. The differences in
the fluorescence of the chromatograms were too weak to allow definite
identification of the-brighteners.
Ascending Paper^ Chromatography; The brighteners in a pyridine-ammonia
solution were run in a mixture of butanol, acetic acid, and water in the
ratio of 80:20:100. It was possible to classify a certain number of groups ;
from the chromatograms, but individual brighteners within the groups could
not be identified because of identical migrations. The author gives a
tabulation of the Rf values obtained in this study.
Electrophoresis; Microelectrophoresis under high voltage was applied
for five hours. An exact pH of 8.6 was attained by using the following
mixture: 29.428 g of sodium veronal, 19.428 g of sodium acetate, 180 ml
of 0.1 N hydrochloric acid, and 3 L of distilled water. The author gives
a tabulation of the Rf values obtained in this study, both of the pure
products and of the products extracted from fabric.
Spot Fluorescence on Textiles: One drop of a mixture of 10% sulfuric
19
-------
acid, 4% sodium hydroxide, sodium hypochlorite, and hydrogen peroxide
was applied to samples of fabric and of paper which had been treated
with brighteners: The results obtained from the fabric samples differed
from those of the paper samples. The brighteners could be differentia-
ted by groups. All results are' tabulated by the author.
O'Hare (1966) gives a simple test method which is accurate to ±5%,
in which anionic brighteners are titrated with cationic Methylene Blue
G to give a water-insoluble complex which does not fluoresce. The end-
point is observed under ultraviolet light.
Spectrophotometric analysis of optical brighteners is described
by Weeks, Harris, and Lewis (1959).
A 0.2500 g sample of brightener was transferred to a foil-wrapped
Erlenmeyer flask and the weighing pan was washed with 200 ml of absolute
methanol. One ml of 40% aqueous sodium hydroxide was added to aid dis-
solution. The mixture was heated at 55-60°C for several minutes, after
which it was transferred to a 1000 ml flask. The Erlenmeyer flask was
rinsed with 200 ml of -water and then by 200 ml of methanol. The flask con-
tents were diluted to 1000 ml with 67% aqueous methanol. The resulting
solution contained 0.0250% brightener and was used as the stock solution.
It is important that non-ionic, actinic glassware be used throughout,
and that the solution be absolutely protected from any ultraviolet radia-
tion.
Test solutions were prepared by diluting 5, 10, 15, 20, and 25 ml
aliquots of the stock solution with 67% aqueous methanol to the mark in
250 ml actinic volumetric flasks to yield brightener concentrations of
0.0005%, 0.0010%, 0.0015%, 0.0020%, and 0.0025%.
20
-------
A Cary spectrophotometer was calibrated to zero absorbancy over
the range of 300 mu to 400 mu with 67% aqueous methanol in both the
blank cells and test cells. It was operated at 0.6 mu per second. The
ultraviolet absorption spectra were determined for the brightener test
solutions at 0.0010% concentration.
Once the absorbancy characteristics of a brightener were known, the
other solution concentrations were analyzed at the wavelength providing
maximum absorbency. After a concentration vs. maximum absorbancy curve
is made for a standard of reference brightener, it is then possible to
analyze other samples of the same type for relative purity.
Some idea of the brightener present in an unknown detergent composi-
tion may be gained by: 1) Determination of stability of the brightener
to hypochlorite bleach; 2) Washing a spectrum of fibers to determine af-
finity characteristics of a brightener; and 3) Fluorescence spectrum of
the washed fabric.
Functional properties of brighteners are suggested as a means to
characterize them. It should be possible to identify unknown brighteners
by comparing their functional properties with those for knowns.
Colorimetry in the visible range is described by Taylor (1955), using
a Spekker fluorimeter (Hilger and Watts). This work is limited to com-
parative strength determination of chemically identical samples. The
following brighteners were studied:
TRADE NAMES FLUORESCENT BRIGHTENER TRADE NAMES FLUORESCENT BRIGHTENER
Uvitex RS
Uvitex GS
Uvitex RBS
Uvites RT
*Uvitex W
41
42
37
57
Uvitex WGS
Uvitex RSW
*Uvitex NA
Uvitex WS
61
:
58
*These brighteners are not being currently manufactured.
21
-------
Transmission vs. concentration values and reflectance vs. concentra-
tion values were obtained and used as standard curves. Ethyl alcohol or
Cellusolve were the preferred solvents.
Taylor states that no attempt should be made to obtain even a rough
comparison of the fluorescence of brightening agents which are not chemi-
cally similar, in water or in any other solvent. Also, the fluorescence
of a product in solution gives no reliable indication of its fluorescence
when adsorbed on the substrate for which it is intended.
i .
A major difficulty encountered in the fluorimetry of brighteners
in solution is the appreciably differing absorptions for ultraviolet
radiation between the cis and trans isomers of the stilbene series.
In certain cases, no steady state of equilibrium was attained and the
test had to be abandoned.
VII. CHEMICAL REACTIVITY
It is physical fluorescence and not chemical reactivity that is the
primary characteristic of an optical brightener. In fact, a highly reac-
tive molecule would be disqualified as a brightener, as it must remain
stable to the rigorous conditions to which it is submitted during appli-
cation and use.
A brightener must have certain structural features: a series of con-
jugated double bonds to give it fluorescence; one or more solubilizing
groups (such as sulfonic acid groups); NHCO groups, or sufficiently
high molecular weight, to have affinity for the fiber (Adams, 1954).
Brightener-fiber interactions are discussed briefly in Section I,
PROPERTIES AND USES, and are discussed here in greater detail.
Cellulosic fibers absorb water and swell when in contact with water.
22.
-------
Brightener molecules are then admitted to the fibers and pass through
water-filled channels by diffusion. These brightener molecules may
interact with the fiber by either of two bonding mechanisms:
(a) A brightener molecule which is capable of forming a hydrogen bond
with the substrate will do so. A hydrogen bond is formed when a hydrogen
atom on one molecule forms an addition bond to an electronegative atom on
another molecule, thereby creating an attractive force which holds these
interacting molecules together. The energies of hydrogen bonds are
5 kcal/mole, well below normal bond energies, and too weak to be con-
sidered as true chemical bonds.
(b) Van der Waal's forces result in a weak attractive force between
the brightener molecules and the fibrous substrate, by dipole moment in-
teraction. Although these forces are electrical in nature, their bonding
energies are far less than the energies of hydrogen bonds, and so are
too weak to be considered as true chemical bonds.
Van der Waal's forces are the principal forces which bind dispersed
brightener molecules to hydrophobic synthetic fibers, such as nylon,
polyester,--and acetate. The dispersed dyestuff .particles are relatively
small in size, have low solubility, and are neutral in character. These
particles may either dissolve into the solid fiber, penetrate the fiber
between the fiber, molecules, or simply deposit onto the fiber. Van der
Waal's forces then establish the attraction between the fiber and the
brightener molecules.
Individual optical brighteners exhibit different fastness properties
and different stabilities, depending on individual chemical constitutions.
and the reactive strength of other chemicals presentduring application
23
-------
and use. The fastness and stability characteristics of the individual
brighteners are given in the tables in the appendix.
For application in the textile industry, the brighteners, after
incorporation into the fibers, must have fastness, to light; must with-
stand frequent washings in detergents or dry-cleaning; must be inert to
atmospheric gases; and must remain fast to ironing, perspiration, deo-
dorants, and friction in use (Stensby, 1967).
To be suitable as a detergent additive, a brightener must be stable
to severe processing conditions in a strongly alkali medium at high tem-
peratures. It must remain stable during storage of the product, re-
main stable in solution, and be inert to bleach and to other detergent
additives (Stensby, 1968; Siegrist, 1955).
The optical brighteners selected for use in the paper industry
must be compatible with the chemicals used in paper making, including
chlorite bleach. They must have good storage stability arid affinity
for pulps and fillers, and they should have good tolerance to sizes,
bonding agents, wet strength resins, and retention agents. They must be
fast to alum, alkalies, and acids, and must be insensitive to hard
water (Review, 1973/1).
Whiteners for incorporation into polymers have great demands made
on their thermal and chemical behavior during addition at the polyester
or polymerization stage with polyamide. The whiteners must be so stable
thermally that they withstand the high temperatures necessary for polymer-
ization or polycondensation, without any noticeable degradation. They must
not be volatile, nor must they sublime from the melt in a vacuum (Review,
1973/1).
2U.
-------
Those brighteners which are incorporated into pigmented coatings
must have outdoor durability and thermal stability.
VIII. BIOLOGY
A. ABSORPTION
Experiments with three strains of bacteria, three strains of fungi,
and three strains of yeast show that some optical brighteners are absorbed
by microorganisms and transported to new cells. Specific names for the
brighteners tested are not given, except for 4,4'-bis[4-anilino-6-bis(2-
hydroxyethyl)amino-s-triazin-2-ylamino]-2,2'-stilbenedisulfonic acid
(Darken, 1962). Complete data on this brightener is compiled
in the tables in the appendix, under C. I. Fluorescent Brightener 28.
In those investigations during which brighteners were topically
applied to skin and mucous membrane, no toxic effects were noted. Snyder
(1963) applied stilbene disulfonates and other common brighteners used
in detergents to the skin of mice, rats, guinea pigs, and rabbits over
a two-year period without any development of toxic symptoms from absorp-
tion. Alexander (1964) recommends further study on the possibility of
incorporating brighteners into cosmetics, since his review of the liter-
ature indicated no toxicity from topical application. The only direct
reference to brighteners which are actually recommended for cosmetic use
is published in Sandoz, Inc. Technical Bulletin I-C-2009 No. 5. Aclarat
8678 is recommended for use as a shampoo additive. Other information on
this brightener is listed under the trade name at the end of the tables
in the appendix. ,
The stilbene character of most optical brighteners might have an
-------
estrogenic effect after accumulation and resorption through the skin.
Brighteners were injected subcutaneously in doses of,100-600 mg/kg into
rats, and for three weeks brighteners were applied to the skin. The
conclusion was drawn that the stilbenedisulfonic brighteners do not
resorb, as evidenced by a lack of estrogenic effect. In this same ex-
periment a 1% solution of Blankophor brighteners was applied to the skin
of post-menopausal women for a period of three weeks. No stilbene
groups were found in the urine, and Papanicolaou smears indicated no
estrogenic activity (Schneider, 1955). Schneider does not indicate
which specific brighteners were used in this study.
B. EXCRETION/ELIMINATION
Diaminostilbenedisulfonic acid derivatives of the Blankophor series
were administered intraperitoneally to cats in doses of 50 mg/kg. The
largest amount of brightener was initially excreted in the urine, with
subsequent smaller amounts being detected over a period of time until
the total amount of brightener had been eliminated. After an oral ad-
ministration of the same dosage, brightener could be detected for 2 days
in the urine of the cats by qualitative fluorescence, but could not be
determined quantitatively (Gloxhuber, 1962).
A common brightener, 4-methyl-7-diethylaminocoumarin, was given
orally and intravenously to rabbits, after which the route of elimina-
tion was determined to be in the bile and in the urine. (Gouaze, 1963).
Other data on this brightener are listed at the end of the tables in
the appendix, under the trade name Advabrite MDAC.
C. TRANSPORT AND DISTRIBUTION
The tissue affinity of one hundred forty-eight optical brighteners
26
-------
for the tissues of lower animals was studied by Gbuaze (1963). Soluble
compounds were administered both intravenously and orally while insoluble
compounds were administered only orally to mice, rats, rabbits, and dogs.
The di-sodium salt of (2-oxo-4-imidazoline-4,5-diyl)dibenzenesul-
fonic acid, a non-toxic, soluble compound, had no affinity for the spleen
or nervous system. It gave a general fluorescence to the skin, mucosa,
intestinal tract and muscles.
4,4'-Bis[4-anilino-6-(bis(2-hydroxyethyl)amino-s-triazin-2-yl)ami-
no]-2,2'-stilbenedisulfonic acid, anon-toxic, soluble compound, gave
general fluorescence to the skin, mucosa, intestinal tract and muscles.
It showed affinity for the spleen, fatty tissue, nervous system, pan-
creas, and glandular system. Complete data on this compound are listed
in the tables in the appendix under C. I. Fluorescent Brightener 28.
7-(Diethylamino)-^-methylcoumarin, a soluble compound having
a slight toxicity, had an affinity for the nervous system. Other data
on this compound are listed in the tables at the end of the appendix, under
Advabrite MDAC.
l~[p~[(2-Hydroxypropyl)sulfonyl]phenyl]-3-phenyl-2-pyrazoline also
had an affinity for the nervous system.
Derivatives of diaminostilbenetriazine had an affinity for the spleen
and for the nervous system.
Derivatives of bis-benzoxazole had an affinity for the pancreas,
salivary glands, thyroid, adrenals, pituitary, ovaries, and testes.
Gouaze (1963) administered 7-(diethylamino)-4-methylcoumarin and
several pyrazole derivatives, such as l-[p-[(2-hydroxypropyl)sulfonyl[phe-
nyl]-3-phenyl-2-pyrazoline, to rabbits, both orally and intravenously.
27
-------
He found that these compounds were taken up by the brain and nervous
system.
The distribution of 7-hydroxy-4-methylcoumarin was investigated in
the rats. Male Sprague-Dawley JCL strain rats, weighing 200 to 250 g,
were given 50 mg of methylhydroxycoumarin (1% suspension in 0.5% carboxy-
methylcellulose solution) per kg of body weight, by means of a stomach
tube.
The cumulative amounts of free methylhydroxycoumarin recovered from
urine after 24, 48, and 72 hours were 2.96%, 3.04%, and 3.12%, respectively,
I
*
of the administered dose.
Following are the tissue and plasma concentrations of total (con-
jugated + free) and free methylhydroxycoumarin in the rat. A vertical
line indicates a standard error.. .
Source: Tomura, 1971
The distribution of free methylhydroxycoumarin was markedly different
from that of total methylhydroxycoumarin. The level of the free form in
28
-------
the brain was not statistically different from those in cardiac muscle,
lung, and skeletal muscle and was 20% to 30% of that in the plasma.
The free form of the drug was predominant in the brain.
D. METABOLISM AND METABOLIC EFFECTS
The di-sodium salt of diaminostilbenedisulfonic acid inhibited the
respiration of rabbit liver homogenate 41.0% at 1.5 X 10~6 M and 62.2%
at 1.5 X 10~5 M. Subcutaneous injection of 200 mg/kg of the di--sodium
salt of 4,4'-bis(l,3,5-triazin-6-ylamino)stilbene-2,2'-disulfonic acid
into rabbits increased urinary excretion of lactic and pyruvic acids
but did not affect excretion of citric acid (Ukita, 1960).
The major metabolic pathway for 7-hydroxy-4-methylcoumarin is as a
sulfate conjugation (Tomura, 1971). This was demonstrated by sulfatase
hydrolysis of the conjugated form in plasma, diluted urine, or in 10%
water homogenate of tissue after a 50 mg oral administration of methyl-
hydroxycoumarin to rats. The free compound was determined in the
urine at levels of 2.96%, 3.04%, and 3.12% of the administered dose.
After the sulfatase hydrolysis these values increased to 85.7%, 87.0%,
and 94.6%.
The free form of the compound was predominant in the brain, demon-
strating that free methylhydroxycoumarin, which is low in liposolubility,
penetrates through the blood brain barrier very easily. Its lipid in-
soluble metabolite, the conjugated form, does not gain access to the brain.
IX. ENVIRONMENTAL TRANSPORT AND FATE
A. PERSISTENCE AND/OR DEGRADATION
From the information gathered on the chemical properties of molecules
which qualify them for use as optical brighteners, it would seem that -
29
-------
they would persist in the environment. Their inertness to the various
other chemicals with which they come into contact during application,
and their stability under the severe conditions to which they are sub-
jected during processing and use, would support this assumption.
No information on the decomposition products of the brighteners
is published. Individual stabilities to various agents are listed under
the individual compounds in the appendix.
B. ENVIRONMENTAL TRANSPORT
The brighteners are carried both on and in the tremendous variety
of substrates to which they are applied. However, water-transport would
be the main area of concern related to environmental significance.
C. BIOACCUMULATION
No information was uncovered concerning the bioaccumulation of the
optical brighteners. It would seem, however, that fat-soluble molecules
might accumulate in animal tissues.
X. TOXICITY
A. HUMAN TOXICITY
Contact or accidental ingestion would be the major pathways by which
the optical brighteners could demonstrate toxicity toward humans. Textile
materials which are worn contain between 0.05%-0.15% of optical brighten-
ing agents. Their fastness on the fiber substrate would argue against
transference to the skin. The amount of brightener that might be acciden-
tally ingested, as from an .agent transferring into food from a brightener-
treated container would be negligible. The amount of brightener persisting
in potable water, if ingested, would be approximately 1 micrdgram per
liter; this amount is 10,000 times smaller than the amounts tolerated in
30
-------
long-term animal experiments without the slightest effect (Review, 1973/1).
Ten derivatives of 4,4'-diamino-2,2'-stilbenedisulfonic acid were
used in patch tests (1%) on eight human subjects. Seven subjects revealed
no reactions, but a transient hyperemia occurred in one case. Intra-
cutaneous injection of the brighteners in a 1% aqueous solution caused
necrosis and infiltration. These compounds showed no photosensitizing
effect (Gloxhuber, Hecht, and Kimmerle, 1962). In similar patch tests,
Schneider (1955) noted no reaction unless ultraviolet light or abrasive
action was employed. Alexander (1964) conducted patch tests on 2000
subjects, using dilutions of optical brighteners from 10 mg/L to .100
mg/L. Readings were taken after 24 and 48 hours, and repeat applications '
were made at two-month intervals; 53 of the 2000 subjects showed weakly V
positive sensitization reactions after 24 hrs; 87 of the 2000 subjects
displayed erythema. Glashoff (1963) applied washing powders and soaps. .
containing optical brighteners to human skin in a 5% solution. The !
solution was reapplied for 6 days. No sensitization was noted. In
further investigations, 87 dermatology patients were tested, with similar
results.
Keplinger, Fencher, Lyman, and Calandra (1974) tested the following
optical brighteners for sensitization induction in human subjects:
(I) 4-(2H-naphtho[i,2-d]triazol-2-yl)-2-stilbenesulfonic acid, sodium
salt
Tinopal RBS (Ciba-Geigy Corp.)
Fluorescent Brightener 46
(II) 4,4'-Bis[[[4~anilino-6-(2-hydroxyethyl)(methyl)amino]-s-triazin-2-
yl]amino]-2,2'-stilbenedisulfonic acid, disodium salt ,
Tinopal'AMS (Ciba-Geigy Corp.)
31 " , -.- ..-" '-.' '
-------
(Ill) 4,4I-Bis[[[4-anilino-6-(2-hydroxyethyl)(methyl)amino]-s-triazin-2-
yl]amlno]-2,2'-stilbenedisulfonic acid, disodium salt
Tlnopal 5BM (Ciba-Geigy Corp.)
(IV) 2,2'-(4,4'-biphenylylenedivinylene)dibenzenesulfonic acid,
disodium salt
Patches containing these brightening agents were applied to human
skin, three times a weekj with a. total of ten patches being applied to
the same site. After a rest period of 10-14 days, a challenge patch
was applied. Examinations 24 hours and 48 hours later revealed neither
irritation nor sensitization in 50 human subjects.
According to American Cyanamid Co. (Technical Sales Bulletin 1056),
Calcofluor White RW (C. I. Fluorescent Brightener 61) shipments bear a
warning label which states that this compound is a skin and eye irritant.
B. TOXICITY TO NON-HUMAN MAMMALS
1. Acute, Subacute, and Chronic Toxicity
Gloxhuber, Hecht, and Kimmerle (1962) studied the following brigh-
teners in relation to animal toxicity:
TRADE NAME FLUORESCENT BRIGHTENER
Blankophor R 30
Blankophor G 40 (not presently manufactured)
Blankophor B
Blankophor BE 115
Blankophor BH
Blankophor BBH 121
Blankophor BGH
Blankophor BUP
Blankophor HZN ~
Blankophor PM
Blankophor H type B
32
-------
ACUTE TOXICITY, SINGLE ORAL ADMINISTRATION, LD50 (g/kg)
Blankophor Rats Guinea Pigs
B > 5.0 >2.0
BH 3.0 0.25
BBH > 2.0 >1.0
BGH > 2.0 >1.0
G > 5.0 , 2.0
H type B > 5.0 1.0
R > 5.0 0.5
BUP >10.0 >2.5
HZN '' > 2.5 >2.5
PM >10.0
Doses higher than 1.0 g/kg were not administered to rabbits nor
cats. At this level, these animals survived with no toxic reactions.
ACUTE TOXICITY, SINGLE PARENTERAL ADMINISTRATION, LD50 (g/kg)
Blankophor Mice (iv) Rats (ip) Mice (sc)
B 0.1
BH 0.3
BBH
BGH
G
H type B 0.35
R 0.35
BUP 0.9
HZN
PM 0.8
After intraperitoneal injection of 50 mg/kg of Blankophor B to cats,
the brightener was excreted in the urine over a two-day period without
any toxic effect.
1.0
0.5
0.35
0.75
0.5
0.35
0.35
1.75
0.4
1.75
0.5
1.0
1.5
1.0
1.0
1.0
1-5
.
33
-------
REPEATED ORAL ADMINISTRATION
Rats, rabbits, and cats were given oral doses of Blankophors B,
BH, BBH, BGH, G, H type B, R, BUP and HZN, over a 2-4 week period, at
levels of 0.1-0.5 g/kg. No recognizable toxic effects were noted.
CHRONIC FEEDING STUDY
Male rats, weighing 50 g, were given optical brighteners in their
drinking water. Results are given as follows:
Test Time Total Amount
Blankophor Concentration % (days) Administered
R 0.2 498 20.3
BH 0.5 464 35.5
BBH 0.2 362 18.0
BGH 0.2 362 12.0
One animal from the R group expired after 7 days; one animal from
the BGH group expired after 269 days; and one animal from the BBH group
expired after 330 days. The weight of the survivors did not differ from
that of the controls. During the time period of the experiment, the
survivors showed no toxic symptoms. The average life-span of the survivors
was 700 days, calculated from the beginning of the test period.
EFFECT ON MUCOUS MEMBRANES
Aqueous solutions of the Blankophor brighteners produced no particular
irritation of animal mucous membranes. A 1% solution of Blankophor BUP
produced a transient hyperemia of the rabbit conjunctival sac. Blankophor
"BBH and BE showed no such effect.
INTRACUTANEOUS ADMINISTRATION :
The intracutaneous administration of 1 ml ,of a 1% solution of the
Blankophor brighteners to rabbits resulted in infiltration and localized
-------
necrosis. Blankophors BUP and PM were exceptions; they produced no
adverse effects.
CHRONIC PARENTERAL ADMINISTRATION
Male rats were given parenteral injections of 0.5 ml of 1% solutions
of the Blankophor brighteners twice weekly for one year. Any ulcerations
which formed healed normally after interruption of the treatment.
PHOTOSENSITIZATION
Control mice were given subcutaneous injections of"Hypericin in
doses of 25 mg/kg. A rapid onset of toxic symptoms appeared when these
animals were placed in sunlight, and 4 of the 5 animals treated expired
within 12 hours. Similarly treated control animals survived in the dark.
The test mice were given doses of 0.25 g/kg of Blankophors R and BH,
subcutaneously. No difference was found between those mice which were
kept in sunlight and those which were kept in darkness.
ACUTE DUST INHALATION
Keplinger, Fancher, Lyman, and Calandra (1973) exposed rats for
four hours to the highest dust concentration achievable (2900-5500
mg/m3) of the following optical brighteners:
(I) 4-(2H-naphtho[l,2-d]triazol-2-yl)-2-stilbenesulfonic acid, sodium
salt
Tinopal RBS (Ciba-Geigy Corp.) .
Fluorescent Brightener 46
(II) 4,4'-Bis[(4-anilino-6-morpholino-s-triazin-2-yl)aminb]-2,2'-s til-
benedisulfonic acid, disodium salt
Tinopal AMS (Ciba-Geigy Corp.)
v "* H.
(Ill) 4,4'-Bis[[[4-anilino-6-(2-hydroxyethyl)(methyl)amino]-s-triaziri-
35
-------
2-yl]amlno]-2,2'-stilbenediaulfonic acid, disodium salt
Tinopal 5BM (Ciba-Geigy Corp.)
(IV) 2,2'-(4,4t-biphenylybenedivinylene)dibenzenesulfonic acid, disodium
salt
Compounds II and IV caused grooming, sneezing, inactivity, and weak-
ness on inhalation by the rats, but induced no pathological changes. Lung
hyperemia was found in two out of ten rats which inhaled compound I.
Lung consolidation was found in four out of ten rats, and one rat expired;
Compound III induced inactivity in the animals inhaling it. Slight lung hy-
peremia was found in three put of ten rats and lung consolidation was found
in 2 out of ten rats.
Fontaine (1968) investigated the oral, intraperitoneal, and intra-
venous LDso values of 4-methylumbelliferone (7-hydroxy-4-methylcoumarin)
in male mice. These values were 7500, 325, and 250 mg/kg, respectively.
In male rats, the oral and intraperitoneal LDso values were 6200 and
750 mg/kg respectively. This compound caused ataxia and tranquilization
in both mice and rats. The i.v. LDioo was 251 mg/kg (respiratory arrest)
and 292 mg/kg (cessation of the QRS complex), following infusion of 5
mg/ml/min into anesthetized rats. A three month oral administration of
doses of 200 or 40 mg/kg/day to young rats did not affect growth, food
intake, mortality, blood picture, or organ histology. No blood, acetone,
bile salts, or bile pigments appeared in the urine.
2. Sensitization
No sensitizatipn is reported in any of the published articles studied
irrespective of the type of animal studied, amount of optical brightener
i
administered, route of administration, or duration of experiment
36
-------
(Gloxhuber, Hecht, and Kimmerle, 1962; Schneider, 1955; Alexander, 1964;
Glashoff, 1963; Keplinger, Fancher, Lyman, and Calandra, 1974).
3. Teratogenicity
Fontaine (1968) studied the teratological effects of 7-hydroxy-4-
methylcoumarin in rats. This brightener demonstrated no teratological
effects when administered orally to pregnant rats in doses of 15-1200
mg/kg/day from the 6th to 15th days of gestation; to mice at 50, 200, or
800 mg/kg/day for 15 days before mating; nor to rabbits at 50, 200, or
800 mg/kg/day from days 6 through 15 of gestation.
Keplinger, Fancher, Lyman, and Calandra (1974) studied the teratogenic
activity of four optical brighteners in rabbits. The brighteners were
administered at dose levels of 10 and 30 mg/kg. Results are tabulated as
follows:
SUMMARY OF TERATOGENIC EFFECTS OF FOUR FLUORESCENT WHITENING AGENTS
IN ALBINO RABBITS
Test material
None
Thalidomide
Compound Is
Compound II
Compound III
Compound IV
'
Dose
(mg/kg)
'
37.5
37.5
75
10
30
10
30
10
30
10
30
No. of
pregnant
females
12
12
10
10
7
14
13
' 17
16
16
11
13
16
No. of
implantations
99
112
70
124
55
118
105
147
140
117
90
91
132'
-No. of
resorptions
8 (8.1%)
9 (8.0%)
13 (18.6%)
24 (19.3%)
15 (27.2%)
10 (8.5%)
10 (9.5%)
16 (10.9%)
19 (13.6%)
20 (17.1%)
24»(26.7%)
17 (18.7%)
15 (11.3%)
No. of
normal
fetuses
91
99
54
85
26
108
95
131
121
97
65
74
107
No. of
abnormal
fetuses
0
4
3
15
14
0
0
0
0
0
1
0
1
Test material neutralized to pH 7 with hydrochloric acid.
' 15 were from-2~fema1es only. .
* 9 were aborted from 1 female.
37
-------
(I) 4-(2H-naphtho[l,2-d]triazol-2-yl)-2-stilbenesulfonic acid, sodium
salt
Tinopal RBS (Ciba-Geigy Corp.)
Fluorescent Brightener 46
(II) 4,4'-Bis[(4-anilino-6-morpiiolino-s-triazin-2-yl)amino]-2,2'-stil-
benedisulfonic acid, disodium salt
Tinopal AMS (Ciba-Geigy Corp.)
(Ill) 4,4'-Bis[[[4-anilino-6-(2-hydroxyethyl)(methyl)amino]-s-triaz in-
2-yl]amino]-2,2l-stilbenedisulfonic acid, disodium salt
Tinopal 5BM (Ciba-Geigy Corp.)
(IV) 2,2l-(4,4'-biphenylybenedivinylene)dibenzenesulfonic acid, disodium
salt
4. Carcinogenicity
No evidence was found in the literature to prove that the optical
brighteners are carcinogenic to either humans or animals.
Bingham and Falk (1970) attempted to demonstrate synergism between
the optical brighteners and ultraviolet light in malignant tumor develop-
ment. The compounds tested were: (I) 3-benzyl-4-methyl-7-hydroxycoumarin;
(II) 4,4'-bis(2,4-dimethoxybenzamido)-2,2'-stilbenedisulfonic acid,
disodium salt; and (III) 4,4l-bis(4,6-dianilino-s-triazin-2-yl)amino-
2,2'-stilbenesulfonic acid, disodium salt [Fluorescent Brightener 9].
Groups of 50 young adult C3H mice were treated with a 1% solution
of optical brightener in DMSO (dimethyl sulfoxide) or with DMSO alone
as a control. A dose of 50 mg of solution was applied 3 times weekly to
the skin of the intrascapular region, for the lifetime of the mouse or
until a tumour appeared.
38
-------
Tumours did not occur in any mice receiving topical applications of
the optical brightener alone, but a high incidence of tumors developed
in all three test groups with the addition of ultraviolet light (254 mu).
Histological examination of the tumors revealed that they were squamous
cell carcinomas.
Optical brightener II appeared to be slightly more active than either
I or III. Two carcinomas developed in the mice that were treated with
solvent and light. No tumors developed in the group receiving applica-
tions of solvent alone..
However, this work has been called irrelevant by Berth, Fischer, and
Gloxhuber (1972), since the wavelength of ultraviolet light used by Bingham
and Falk (254 mu) does not occur in natural light, making the results ob-
tained invalid in practice.
Neukomm and DeTrey (1961) studied the carcinogenic properties of
the following brighteners:
(I) 4,4l-bis[[4-anilino-6-[(2-hydroxyethyl)methylamino]-s-triazin-2-
yl]amino]-2,2'-stilbenedisulfonic acid, disodium salt;
(II) 4-(2H-naphtho[l,2-d]triazol-2-yl)-2-stilbenesulfonic acid, sodium
salt (Fluorescent Brightener 46); and
(III) 4-(7-sulfo-2H-naphtho[l,2-d]triazpl-2 yl)-2-stilbenesulfonic acid,
disodium salt.
A group of 50 female mice, aged 3 to 6 months were used as controls.
A second group of 50 mice of the same sex, age, and strain were
injected subcutaneously with a mixture of 0.2 ml of 8g of talc in 20
g of peanut oil. These were used as solvent controls.
"*-\_^
A third group of 50 mice of the same sex, age, and strain were in-
39
-------
jected with 0.5 mg of 3,4-benzopyrene in 0.2 ml of peanut oil. These
were used as comparison controls in .tumor formation. .
Fifty test mice, identical in sex, age, and strain to the control
mice, were injected subcutaneously with the optical brighteners at a
dose level of 5 mg of brightener in 0.2 ml of a mixture of talc and
peanut oil, 0.5 mg of brightener per day per animal in food.
The duration of the experiment was two years.
The lungs, heart, liver, spleen, and kidneys of each animal were
' ' ' !
examined both grossly and histologically after expiration.
No mice receiving the brightener test compounds presented tumors
at the injection site, nor did the talc-oil controls. The 3,4-benzopyrene
controls developed fibroblasts at the injection site.
Mammary tumors, ovarian cysts, and incidence of leukemia were not
accelerated by the brighteners when compared with the controls.
Although there were no general toxic effects noted during these
long-term studies, a few cases of splenic amyloidosis and liver damage
might be attributable to the long-term feeding of brighteners to the
affected animals (comparable doses for humans would amount to 20 tug/kg,
or.1.2 g per day).
5. Mutagenicity
The mutagenic effects of some optical brighteners toward microorgan-
isms are discussed in Section E, TOXICITY TO MICROORGANISMS.
Keplinger, Fancher, Lyman, and Calandra (1974) tested the following
brighteners for mutagenic effects toward mice:
(I) 4-(2H-naphtho[l,2-d]triazol-2-yl)-2-stilbenesulfonic acid, sodium
salt
-------
Tinopal RBS (Ciba-Geigy Corp.)
Fluorescent Brightener 46
(II) 4,4'-Bis[(4-anilino-6-morpholino-s-triazin-2-yl)amino]-2,2'-stil-
benedisulfonic acid, disodium salt
Tinopal AMS (Giba-Geigy Corp.)
(Ill) 4,4'-Bis[[[4-anilino-6-(2-hydroxyethyl)(methyl)amino]-s-triazin-2-
yl]amino]-2,2'-stilbenedisulfonic acid, disodium salt
Tinopal 5BM (Ciba-Geigy Corp.)
(IV) 2,2l-(4,4l-biphenylylenedivinylene)dibenzenesulfonic acid, disodium
salt
Compounds I,II, and III were administered in dosages of 25 and 50
m§/kg, and compound IV was administered in dosages of 5 and 10 mg/kg.
The ability of treated males to fertilize untreated females was not
impaired. The numbers of implantations, resorptions, viable embryos,
prelmplantation losses, and mutation frequencies did not differ from
those of the untreated animals. - .
6. Behavioral Effects
No relationships between optical brighteners and animal behavior
have been reported in the literature.
C. TOXICITY TO LOWER ANIMALS
Keplinger, Fancher, Lyman, and Calandra (1974) investigated the LCso
values of four different optical brighteners in fish. The brighteners
used in these studies were:
(I) 4-(2H-naphtholl,2-d]triazol-2-yl)-2-stilbenesulfonic acid, sodium
salt
Tinopal RBS (Ciba-Geigy Corp.)
Fluorescent Brightener U6
Ul
-------
(II) 4,4'-Bis[4-anilino-6-morpholino-s-triazin-2-yl)amino]-2,2'-
stilbenedisulfonic acid, disodium salt
Tinopal AMS (Ciba-Geigy Corp.)
(Ill) 4,4'-Bis[[[4-anillno-6-(2-hydroxyethyl)(methyl)amino]-s-triazin-2-
yl]amino]-2,2'-stilbenedisulfonic acid, disodium salt
Tinopal 5BM (Ciba-Geigy Corp.)
(IV) 2,2'-(4,4t-biphenylylenedivinylene)dibenzenesulfonic acid, disodium
salt
_
Compound III appeared to be the most toxic, with a twenty-four hour
LCso value of 120 ppm trout and 105 ppm for catfish. The twenty-four hour
LCso values for compound IV were 160 ppm in trout and 105 ppm for catfish.
Compounds I and II showed equal activity; the twenty-four hour LCso values
for both trout and catfish amounted to 2000 ppm.
Ciba-Geigy Corp. (Review, 1973/1) reports that the amounts of
optical brighteners which have been measured in domestic effluent in
densely populated areas vary between 0.01 and 0.1 ppm. Furthermore,
efficient purification plants retain more than 90% of this, so that the
amounts of brightener reaching surface or ground waters would be approxi-
mately .001 to .010 ppm.
D. TOXICITY TO PLANTS
f
Sharma (1963) reports on chromosome breakage in alluim roots after
the roots were treated with natural coumarin and some of its derivatives.
Quereioli (1957) tested twenty-one derivatives of coumarin to study any
toxic effects these might have toward the roots of yellow onion bulbs. A
considerable degree of fragmentation of the chromosomes was noted.
-------
Although none of the compounds used in these studies can be designated .. .
as specific optical brighteners, these studies are mentioned here because
coumarin is the parent structure of several commonly used brighteners.
E. TOXICITY TO MICROORGANISMS
Blankophor FBO (Fluorescent Brightener 206), Uvitex SOF (Fluorescent
Brightener 190), and Uvitex SWN (Fluorescent Brightener 140) were tested for
their ability to induce petite mutants in a diphloid strain of Saccharomyces
cerevisiae. Fluorescent Brightener 206 induced a high frequency of mutants
when the yeast was incubated for 48 hours in its presence in darkness.
Fluorescent Brighteners 140 and 190 induced photosensitization and a
marked increase in petite mutants after a one-hour treatment with the
brighteners in the presence of light (Gillberg, 1971).
Gillberg has since admitted that his results are irreproducible
(Kilbey and Zetterberg, 1974). Kilbey and Zetterberg used the same genetic
system and the same compounds as those used by Gillberg, but were unable
to confirm that the suspected agents acted positively when incorporated
in the growth medium of the organism. None of their several trials
produced a positive result.
Darken (1964) determined that ten species of microorganisms showed
increased spore germination of 159%-848% after a two-hour exposure of a
12% solution of 4,4'-bis[4-anilino-6-bis(2-hydroxyethyl)amino-s-triazin-2-
ylamino]-2,2'-stilbenedisulfonic acid, disodium salt (Fluorescent Brigh-
tener 28), in 42% aqueous ethylene glycol monomethy1 ether.
-------
APPENDIX'
Starting on page A-l (follows 148), a compilation of optical
brighteners has been drawn from the Colour Index, from the indices of
Chemical Abstracts, and from manufacturers' data sheets. The optical
brighteners are listed according to the "C.I. Fluorescent Brightener"
numbers. All other information with which a correlation with the C.I.
numbers could be established is included.
44
-------
LITERATURE CITED
Adams, D. A. W. (1954), "Optical Whitening Agents for Detergents",
Perfumery Essent. Oil Record 45, 303-7 10621
Alexander, P. (1964), "Effect on Skin of Optical Brighteners", Mgf.
Chemist 35_ (9), 72 12114
Berth, P., Fischer, W. K., and Gloxhuber, C. (1972), "The Development
of Laundry Aids with Consideration for the Human Toxicity and
Ecological Requirements", Tenside Det. 9. (5)» 260-267
Bingham, E. and Falk, H. L. (1970), "Combined Action of Optical Brigh-
teners and Ultraviolet Light in the Production of Tumours", Food
Cosmet Toxicol 8^, 173-176
Chemical Economics Handbook, Stanford Research Institute, Menlo Park,
Calif.
Colour Index, Third Edition, 1971, The Society of Dyers and Colourists
Darken, M. A. (1962), "Absorption and Transport of Fluorescent Brigh-
teners by Microorganisms", Appl. Microbiol 10, 387-93 12620
Darken, M. A., and Swift, M. E. (1964), "Effect of Brightener on Spore
Germination, Mycologie _56_ (62), 158 12330
Fontaine, L., Grand, M., Chabert, J., Molho, D., Boschetti, E. ."(1968) ,
"Toxicologies! and Teratological Study of 4-Methylumbelliferone",
Therapie 23_ (2), 359-71 (Fr.) 12071
Gillberg, B. 0., and Aman, J. (1971), "Petite Mutants Induced in Yeast
by Optical Brighteners", Mutat, Res. 13_ (2), 149-154 10521
Glashoff, E., Stegmann, W., and Schroeder, E. (1963), "The Biological
Action of Optical Bleaches Used in Detergents and Soaps", Fette,
Seifen, Anstrich. 65. 42-6 (Ger.) 12244
Gloxhuber, C., Hecht, G., and Kimmerle, G. (1962), "Toxicological In-
vestigations with Brighteners (Blankophor(R) Series)", Archiv. Toxi-
kol. 19_, 302-12 (Ger.) 12242
Gouaze, A., and Castaing, J. (1963), "The Tissue Affinity of One Hun-
dred Forty-Eight Fluorescent Compounds", Compt. Rend. 257 (26),
4230-4 (Fr.) 12233
Keplinger, M. L., Fancher, 0. E., Lyman, F. L., and Calandra, J. C.
(1974), "Toxicologic Studies of Four Fluorescent Whitening Agents",
Tox. Appl. Pharm. 27, 494-506
Kiger, J. and Bon, R. (I960),. "The Problems of Identification Posed by
Optical Bleaching Agents", Ann. Pharm. Franc., 18, 853-72 (Fr.) 12211
-------
Kilbey, B. J., and Zetterberg, G. (1974), "Optical Brighteners",
Science 183, 798 16064
Neukomm, P. S. and De Trey M. (1961), "Study of Some textile Optical
Bleaching Agents from the Point of View of Their Carcinogenic
Activity", Med. Exptl. 4_, 298-306 (Fr.) 10557
O'Hare, R. J. (1966), "Optical Brightening Agents", Chem. Ind. (Lon-
don), 28, 1220-4 10648
Quercioli, E. (1957), "Molecular Constitution of Coumarins and their
Effect on Vegetable Cells", Pubbl. Centra. Studio Citogenet.
Vegetale Consiglio Nazi. Ricerche No. 206 12396
Review 1973/1 CIBA-GEIGY
Schneider, W. (1955) "Optical Whitening Agents and Their Influence on
the Skin and Body Functions", Berufsdermatosen _3_, 201-6 (Ger.)
10581
Sharma, A. K., Chandhuri, M., Chahraborti, D. T. (1963), "Chemical
Basis of the Action of Natural Coumarin and its Derivatives on
Chromosome Breakage", Acta. Biol. Med. Ger. 31 (3), 433-44
12495
Siegrist, A. E. (1955), "Optical Brighteners in Detergents", Soap.
Chem. Spec. .31 (11), 44; 31 (12), 58 10592
Snyder, F. H., Opdvke, L., and Rubenkoenig, H. L., (1963), "Toxicolo-
gic Studies on Brighteners", Toxicol. Appl. Pharmacol. .5, 176-83
12601
Stensby, P. S. (1968), "Optical Brighteners as Detergent Additives",
J. Amer. Oil. Chem. Soc. 45_(7), 497-504 12067
Stensby, P. S. (1967), "Optical Brighteners in Laundry Products",
Detergent Age, 3_ (9), 20-7 10446
Stensby, P. S. (1967a), "Optical Brighteners and Their Evaluation",
Sopa. Chem. Spec. 43_(4), 41; (5), 84; (7), 80; (8), 94; (9),
96 14167
Stensby, P. S. (1965), "Optical Brighteners in Fabric Softeners",
Soap. Cham. Spec., May 16498
Taylor, G. G. (1955), "Estimation of Fluorescent Brightening Agents",
J. Soc. Dyers Colour., 2I» 697-704 10593
Tomura, M., and Akera, T., (1971), "Blood Brain Barrier; Implication
of Drug Metabolism in the Penetration of Methylhydroxycoumarin
in the Rat", Jap. J. Pharmacol., 2J, (5) , 683-5 10505
1*6
-------
Ukita, C. (1960), "Triazinylstilbene Optical Bleaching Agents: I. Tox-
icity and Change in Urinary Constituents after Administration of
the Dye. Shokukin Eiseizaku Zasshi 1 (1), 69-73 10539
United States Tariff Commission, Synthetic Organic Chemicals, United
States Production and Sales
Weeks, L. E., Harris, J. C., and Lewis, J. T. (1959), "Methods for
Analysis of Fluorescent Brighteners", Soap. Chem. Spec., May,
66-70
U7"
-------
METHYL CHLOROFORM, TRICHLOROETHYLENE, AND TETRACHLOROETHYLENE:
SUMMARY AND CONCLUSIONS
The status of these three chlorinated hydrocarbon solvents is undergoing
a change at the present time. The use of trichloroethylene is declining in
industry because of the stringent regulations which are being enforced to
control its use. This means that there will be bigger markets for methyl
chloroform and tetrachloroethylene. They will become prominant in those
areas of industrial application where trichloroethyiene was formerly the
solvent of choice. Tetrachloroethylene is also expected to find continuously
wider application in textile manufacturing and dyeing as these industries
convert from aqueous to non-aqueous systems to avoid water pollution.
The volatility of these chlorinated hydrocarbons presents a dual
hazard: they are readily absorbed through the lungs and digestive tract,
and they are easily transported through the air. In the literature on hand,
there was little or no information specifically reporting on monitoring that
is actually being carried out at the sites where these solvents are used.
Very few figures are reported on actual concentrations of these compounds
found during enviornmental field tests. One complete study that has been
reported was done in Europe.
While methyl chloroform is considered to be the most stable and least
toxic of the three solvents discussed here, it may not be considered innocuous.
In fact, a system for grading these compounds according to stability or
toxicity can only be valid when related to specific applications and application
conditions - amount evaporating into the air during use, temperature and press-
ure variables, composition of contact surfaces, and duration of exposure time.
U8
-------
The danger of toxicity from the inhalation of these solvents is of
fundamental concern. Their decomposition into toxic products, such as
ph >sgene, occurring under use-related conditions, also presents a hazard.
The toxicity of the chlorinated hydrocarbon solvents has been est-
ablished from experiments on animals and from observations of exposed
humans. Acute, heavy exposures result in a depression of the central
nervous system. Death may occur from respiratory and cardiac failure,
although there is a wide difference between the minimum narcotic dose and
the fatal dose.
All three solvents discussed in this study induce liver and kidney
dysfunction following repeated, long-term exposures. However, the function-
ing of these organs returns to normal when the affected subjects no longer
have contact with the solvents.
The metabolites of these solvents and their excretion have been care-
fully studied. However, the intermediate breakdown products within the
body, as well as the metabolic sites, seem to remain uncertain. Since no
information is available, the toxicity of the intermediates in the met-
abolism of these solvents cannot be assessed.
-------
CHLORINATED HYDROCARBON SOLVENTS
(METHYL CHLORFORM, TRICHLOROETHYLENE AND TETRACHLOROETHYLENE)
I. Physical Properties
The physical and chemical properties of the chlorinated solvents
methyl chloroform (1,1,1-trichloroethane), trichloroethylene, and tetra-
chloroethylene (perchloroethylene) qualify_j:hem for continually increasing
use in industry. Their characteristic non-flammability in air, volatility,
and poor solubility in water make them very useful solvents. The relatively
low toxicity of methyl chloroform is a special advantage and makes it the
solvent of choice in instances where another solvent might be otherwise more
suitable.
All three solvents are clear, colorless liquids with the chloroform
odor characteristic of the group of compounds to which they belong.
The following composite tables give the properties reported from various
sources, while the single tables give data on the pure compound.
-------
TABLE I. Chlorinated Solvents, Properties
Methyl chloroform Trichloroethylene
Tetrachlbroethylene
,Formula
Molecular weight
Melting Point °C
Boiling Point °C
Freezing Point °C
Decomposition Temp
Density
Flash Point
Relative Rate of
vaporization
:Solvent Power
Surface tension
(dyne/cm2, 20°C)
Refractive Index
Vapor Pressure
Vapor Specific
Gravity (Air
Viscosity (cps, 25°C)
Autooxidation
Hydrolysis
Thermal Stability
(without stabilizers)
C2H3C13
133.41
-50° (1)
74-76° (1)
74.1° (2)
-42° (2)
p. °C 360-440° (4)
1.437 (1)
None
5.0 (3)
124(3)
25.56 (3)
2° 1.4370 (1)
"C mmHg °C mmHg
0 :j7 50 340
10 62 60 470.
20 100 70 600
.".0 150 SO 000
-------
TABLE 1. Cont'd.
Methyl Chloroform Trichloroethylene Tetrachloroethylene
Solubility ^ ^ .4420 .-, O.ll25 0.01525
water g/lOOg H20
0.12560(4)
(1) Aldrich Chem. Co. (97% with 3% p-dioxane)
(la) (98%)
(Ib) (Spectrophotometric grade)
(2) Hooker Chem. Co.
(3) Dyrenfurth (1972)
(4) Klrk-Othmer Encyclopedia of Chemical Technology, 5^ (1964)
-------
Table 1A - PHYSICAL AND CHEMICAL PROPERTIES OF METHYL CHLOROFORM
NAJ^E Methyl chloroform
Mole Ref. Molecular r ., r. Molecular
% Pur. 99.92 1 Formula <-i"3^13 Weight 133.425
F.P. °C
F.P. 10051
3. P. °C
760 mm
100
30
10
1
Pressure
mm 25°C
«e
Denaity
g/ml 20'C
dt 25
d4 30
a
b
Ref. Index
»D 20.C
50
»C"
MR (Obs.)
MR (Calc.)
(nD-d/2) .
Dielectric
A 1 -3 to
B 1 1 3 1 "C
c
A*| -3 to
B«i_ 91 -C
K
tk | to"
'xi 'c
A' | to
B'U !£
C'
A'* to
B'» 'C
Ac | It I to
Bc._
-------
Table IB - PHYSICAL AND CHEMICAL PROPERTIES OF TRICHLOROETHYLENE
NAME 1, 1, 2-Trichloroethylene
Mole Ref. Molecular r Hrl Molecular ..
%Pur. Formula C2HO13 Weight 131.399
_F.P. °C
F. P. 100%
B. P. *C ,
760 mm
100
30
10
1
Pressure
mm 25*C
'e
Density
g/ml 20-C
d* 25
"4 60
b
Kef. Index
DD ,«
50
»C"
MR (Obs.)
MR(Calc.)
(nD-d/2)
Dielectric
A 1 7 to
B 1 155 *C
C
A*| 7 to
B*|_1 *
c
*k 1 to
?! -c
A< | to
B' i_ "C
c-
A1* to
B'* *C
Ac| 155 to
Be it,. 'C
Cc l
CryoB. A*
consta. B"
*e'C
- 87.08
31.54
6.90
-11.85
-42. 89
74.31
975.52
1.46422
1.45541
1.39501
1.49948
-0.00174
1.47734
1.47457
1.46056
0.4302
25.37
25.57
0.74523
7.02808
1315.0
230.
1 . 54642
1230.2
7.4675
1675.
280.
95.60
Re I
1
4
5
5
5
5
5
1
1
1
4
4
1
1
1
4
4
5
4
4
4
4.
5
5
5
5
5
5
dt/dP
C/mm
Z5*C
BP
*.
30 mm
AHm cal/g
oHv cal/g
25'C
30 mm
BP
t'(d.e)
AHv/Te
d 1 7 to
-o.-H6-;f
e' ! 'C
d, g/ml
v£ ml/g
tcc -c
P mm
PV/RT
25'C
30 mm
BP
»e
*c
aHc kcal/m
AHf
AFf
Viscosity
certi stokes
V 20 "C
' 40
60
80
Bv 1 10 to
Av | 70 'C
lB^T| ^
(Av)| .C
«p »q. °K
cp vap. °K
<=v »»P-
0.2890"
d. 04369
0.0359
0.6178
62.33
64.02
56.43
55.61
55. 62
19.81
64.67
0.0946
0.513
1.950
298.
36876.
0.9957
1.0000
0.9578
0.9507
0.265
0. 3844
0.3Z91
0.2867
0.2553
311.03
T. 52395
Ref
5'
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
1
L
1
1
4
4
STRUCTURAL FORMULA
CC12=CHC1
f | j to
8 j ' ' IK.
h | .
f ' ' to
g' 1 L "K
h' |
, 1
ml 'to
n 1 -K
° !
m- I 1 to
n' , 1 -K
°' I
Surface tension
dynas/cm. 20*C
> . 30
40
Parachor [p]
20'C
30
40
Sugd.
Exp. L.l.%/wt.
u.
Dispersion
Flash Point "C
Fire Point
M Spec.
Ultra V.
X-Ray Dif.
Infrared
Solubility in +
Acetone
Carbon tet.
Benzene
Ether
n-Heptan*
Ethanol
Water
Water in
29.28
27.94
26.76
208.7
208.8
209.0
212.8
Ref.
1
1
1
4
4
4
5
TR = 0.75TC * Krarn3/ioo crams solvent
REFERENCES: 1 -Dow 2 -API 3 -Lit. 4-Calc. from det. data 5-Calc. by formula
SOURCE: ' Dow .
PURIFICATION: Distillation
Source: ADVANCES IN CHEMISTRY SERIES NUMBER 22
-------
Table 1C - PHYSICAL AND CHEMICAL PROPERTIES OF TETRACHLOROETHYLENE
NAME Perchloroethylene
Mol« Ref. Molecular r _. Molecular
% Pur. Formula ^2^*4 Weight 165.848
P.P. *C
F.P. 100%
B.P. 'C
760 mm
100
30
10
1
Pressure
mm 25°C
«<,
Density
g/ml 20'C
^ 2S
d4 30
a
b
Ref. Index
"D ««
30
"C"
MR (Obs.)
MR (Calc..)
(nD-d/2)
Dielectric
A 1 34 to
B (_187'C
C
A*l 34 to
B*|144'C
K
tk | to"
'x| 'C
A'| 25 to
B'| 34 -C
C'
A1* 25 to
B'* 34 'C
Acl 167 to
-L.'c_-
-------
-10 0 10 20
40 60 80 100 120 140 180 220240
IOOO
800
800
4OO
200 £
100
80
60
40
20 *
10 ^
8
I
.8
.6
..T-
±7
X:
+
_j
<::
*f
vapor pressure over a range of 20° G to +240* C.
Source: GALLANT, 1966
-56
-------
-150
-140
-130 -120 -110 -100 -80 -SO -40 -20 0 20 50
1000
vapor pressure over a range of 90° C to +50° C.
Source: GALLANT, 1966
-------
120
100
-6O
-20
20 60 100 140 180 220 260
0 CENTIGRADE
heat of vaporization over a range of 60° G lo | 300° C.
3OO
O 100 20O 3OO 40O 500 600 TOO 800 900 IOOO
0 CENTIGRADE
Source: GALLANT, 1966 vapor heat capacity over a range of 0° C to +1,000° C.
-------
50 70
0 CENTIGRADE
liquid heat capacity over a range of 30° C to'+150° C.
-60 -20 20 60 100 I4O ISO 220 26O 300
0 CENTIGRADE
Source: GALLANT, 1966
liquid density over a range of 60° C to +300° C.
59
-------
210
190
170
ISO
130
-6O
-20
2O 60 100 I4O ISO 220
. ° CENTIGRADE
vapor viscosity over a range of 60° C to +300° C.
260
300
2.8 EH
-6O -2O 20 60 100 140 180 22O 260 30O
CENTIGRADE
Source: GALLANT, 1966 liquid viscosity over a range of 60° C to +300° C.
-------
60
-60
-20
20 60 100 140 180 220
0 CENTIGRADE
surface tension over a range of 60° C to + 300° C.
260 300
-30
-10 10 30 50 70 90 110 I3O
0 CENTIGRADE
liquid thermal conductivity over a range of 30° C to +150° C.
150
Source: GALLANT, 1966
61
-------
TRICHLOROETHYLENE
U.S. Federal Specification 0-T-634a. Technical Grade Dated April 17. 1956
Chemical and Physical Requirements
General (Type I and II)
Appearance
Specific Gravity 20°/20°C
Acidity as HC1:
Alkalinity as NaOH:
Water Content:
Copper Corrosion and
. Free Chlorine:
Color:
Odor:
Non-Volatile:
Spot Test:
Distillation Range:
Initial Boiling Point
At Least 95%
End Point:
Acidity as HC1:
Clear and free of suspended natter
or sediment.
1.450 - 1.475
0.01% Max.
0.01% Max.
No cloud at 0°C
Must pass government test
Shall not be darker than a solution
containing 0.0045 gm potassium
dichromate in one liter of distilled
water.
Type I
Type II
No residual odor
0.004 gm/100 ml Max. 0.020 gm/100 ml Max,
No spot or staia
86.0°C
90.0°C
Faintly discernible
spot or stain
85.0°C
Below 90.0°C
95.0°C
0.02% Max.
Source: Chemical Economics Handbook
62
-------
TETRACHLOROETHYLENE
U.S. Federal Specification 0-P191a Technical Grade, Dated September 23, 1959, and
Amendment 1, Dated February 21, 1961:
Appearance:
Color:
Odor:
Specific Gravity 20°/20°C:
Non-Volatile Matter:
pH at 25°C:
Distillation Range:
Acid Acceptance:
Amine
Non-amine
Spot Test:
Water Content:
Copper Corrosion and
Free Chlorine:
Clear and free of suspended matter or
sediment.
Shall not be darker than a solution
containing 0.0045 gm. potassium
dichromate in one liter of distilled
water.
Characteristic, no residual odor.
1.615 - 1.630
0.016 gm/100 ml. max.
5.0 min.
118 - 124°C
0.01 max.
0.08 - 0.12
No spot or stain
No cloud at 0°C
Must pass government tests
Source: Chemical Economics Handbook
-------
II. PRODUCTION
A. Methyl Chloroform
The following are the largest reported manufacturers of methyl chloroform in
the U.S.
Company and Location
Dow Chemical U.S.A.
Freeport, Texas
Ethyl Corporation
Industrial Chemicals Division
Baton Rouge, Louisiana
PPG Industries, Inc.
Industrial Chemicals Division
Lake Charles, Louisiana
Vulcan Materials Company
Chemicals Division
Geismar, Louisiana
Total
Annual Capacity
As of September 1972
(Millions of Pounds)
340
50
175
65
630
Raw Material
vinyl chloride
vinyl chloride
vinylideiie chloride
ethane
Source: Chemical Economics Handbook
The overall reactions for methyl chloroform production may be represented as follows:
CH2.= CHC1 + C12 + CH3CC13
and
CH2 = CC12 + HC1 -> CH3CC13
-------
No figures on methyl chloroform production are available prior to .1966.
. - . « "
Methyl Chloroform (Millions of Pounds)
' Production . Sales
1966 242.9 249.7
1967 269.7
1968 299.4 288.1
1969 324.3 298.9
1970 366.3 , 327.4
1971 374.6 341.3
1972 .
1973 (p) 537.3
Jan. 1974 (p) 45.2 ; ^ :
Source: United States Tariff Commission
United States Production and Sales of. Miscellaneous Chemicals
(p) Preliminary Report S.O.C. Series C/P-74-1
Rule 66 which went into effect in Los Angeles County in 1967 has had a
favorable impact on the methyl chloroform market. The restricting of trichloro
ethylene caused 50% of the vapor degreasing industry in Los Angeles to switch
to other chlorinated solvents. Also, late in 1971, Dow announced that it was
producing vinylidene chloride directly from methyl chloroform, a change which
adds approximately 8-10 million pounds per month to reported methyl chloroform
production (Chemical Economics Handbook).
65
-------
The Dow Chemical Co. states that methyl chloroform has the best health
and safety picture and is also more readily recovered than other chlorinated
solvents. It could introduce a savings in consumption of 20-30%. Dow expects
methyl chloroform to grow by 9-10% per year through 1975, and 5-8% per year after
that (Chemical Week, November 15, 1972).
' ''.':
B. Trichloroethylene
During the first part of 1972, the Detrex Chemical Industries, Inc.
closed their plant at Ashtabula, Ohio, which had a production of 100 million
pounds per year of trichloroethylene. In Mayj 1972, du Pont closed its
Electrochemicals Department plant at Niagara Falls, N.Y., where 250 million
pounds of trichloroethylene were produced per year.
i
The overall reactions for trichloroethylene manufacture may be
represented as follows:
HC 2 CH + 2C12 -» CHC12-+CHC12
2CHC12 CHC12 + Ca(OH)2 -» 2CHC1 = CC12 + CaCl2 + 2H20
CHC12 CHC12 »- CHC1 = CC12 + HCl
Pyrolysis
CH2C1CH2C1 + 2C12 -» CHC1 = CC12 + 3HC1
66
-------
As of September, 1972, the following five companies were reported
.as producers of trichloroethylene in the United States:
Company and Location
Annual Capacity
As of September 1972
(Millions of Pounds)
150
b.
a.
Dow Chemical U.S.A.
Freeport, Texas
Diamond Shamrock Chemical
Company
Electric Chemicals
Division
Deer Park, Texas 60
Ethyl Corporation
Industrial Chemicals
Division
Baton Rouge, Louisiana 50
^
Hooker Chemical Corporation
Industrial Chemicals
Division
Tacoma, Washington 30
Taft, Louisiana 40
PPG Industries, Inc.
Industrial Chemical
Division
Lake Charles, Louisiana 200
Total 530
Raw Material
Ethylene
Ethylene
Ethylene
Acetylene
Acetylene
Ethylene
a. An additional 50 million pounds per year unit was closed in late 1971.
b. Believed to be producing only small quantities (production was not reported
to the U.S. Tariff Commission in 1971 or in the first six months of 1972).
Capacity of the plant will be expanded by April 1973.
c. A 60 million pounds per year acetylene-based trichloroethylene plant at
Niagara Falls, New York, was closed in early 1972.
d. Expanding to 280 million pounds per year by the end of 1973.
Source: Chemical Economics Handbook.
67
-------
Tfio fn11rnj-fn£ Hat A on production ana SHJ.KS »av^ »«.*... -
Economics
Handbook and from the United States Tariff Commission TC Publication
C/A for 1971 and Preliminary Report S.O.C Series
for 1973.
1935
1936
1937
1938
1939
1940
1941
1942
1943
1944
1945
1946
1947
-1948
1949
1950
1951
1952
1953
1954
Preliminary figures are indicated "by
Trichloroethylerie (Millions
. Production Siles
12
21 - '
33 . ; ' : .-_ .- .
27
34
»
55
(82) '
130
(150) .
' (170)
185 ~
(186) ,-
(188)
190
(205) ~
(215) ' x
'(250) 233.2
270.5 241.8
323.3 287.7
296.8 252.4
C/P-74-1 Of
(p).
of Pounds)
1955
1956
1957
1958
1959
I960
1961
1962
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972
1973 '(p)
Jan. 1974 (p)
the same
Production
316.2
346.1
337.7
295.1
360.2
352.8
309.2
356.1
368.2
370.5
434.5
480.2
490.0
519.1
596.8
610.8
514.8
(438.0)
450.5
38.6
source
Sales
284.5
303.2
292.2
243.5
302.2
298.8
325.8
347.9
362^6
370.1
428.1
' 462.9
472.7
527.6
561.5
568.9
532.4
. ~~ .
*"
fc
68
-------
Producers are curtailing any expansions in trichloroethylene production
since Los Angeles' Rule 66 placed trichloroethylene on the list of restricted
solvents. Similar types of legislation have been passed in several states.
Diamond Shamrock sees a gradual drop in trichloroethylene volume,
conceding it could decline as much as 25-30% by 1975 if all agencies decide
on'rigorous enforcement. Dow sees trichloroethylene volume going from 600
million pounds per year in 1970 to 400 million pounds per year in 1975, with
the drop continuing (Chemical Week, November 15, 1972).
C. Tetrachloroethylene
Of the companies reported as producers of tetrachloroethylene in the United
States as of September, 1972, Diamond Shamrock, du Pont, and PPG expected to
have undergone considerable expansion in tetrachloroethylene production by the
end of 1973. .
It is estimated that about 20% of the tetrachloroethylene produced is from
the acetylene-chlorine method. The majority, however, is produced as follows:
CH2C1CH2C1 + 3C12 -» C12C = CC12 + 4HC1
C3H8 + 8C12 -» CCli* '+ C12C = CClz + 8HC1
2C3H6 + 16 C12 * 4CClk + C12C = CC12 + 12 HC1
Following is a list of the major producers in the United States.
69
-------
Tetrachloroethylene Capacity
Company and Location
Diamond Shamrock Chemical
Company
Electro Chemicals Division
Deer Park, Texas
Dow Chemical U.S.A.
Freeport, Texas
Pittsburg, California
Plaquemine, Louisiana
As of September 1972
(Millions of Pounds)
100
120
20
105
Raw Material
E. I. du Pont de Nemours & Co.,
Inc.
Electrochemicals Department
Corpus Christi, Texas 0
Ethyl Corporation
Industrial Chemicals Division
. Baton Rouge, Louisiana 75
Hooker Chemical Corporation
Industrial Chemicals Division
Tacoma, Washington 10
Taft, Louisiana 35
PPG Industries, Inc.
Industrial Chemical Division
Lake Charles, Louisiana 160
Stauffer Chemical Company
Industrial Chemical Division
Louisville, Kentucky 70
Vulcan Materials Company
Chemicals Division
Geismar, Louisiana 150
Wichita, Kansas 40
Total 885
Ethylene dichloride
Various
Various
Various
Ethylene dichloride
Calcium carbide acetylene
generated by Hooker
Acetylene generated by
Union Carbide Corporation
Ethylene dichloride
Various
Various
Various
Source: Chemical Economics Handbook
TO
-------
The following data have been taken from the Chemical Economics Handbook,
from the United States Tariff Commission TC Publication 614
Preliminary Report S.O.C. Series C/P-74-1 of the same source
figures are indicated by (p) .
; Tetrachloroethylene (Millions
1940
1941
1942
1943
1944
1945
1946
1947
1948
1949
1950
1951
1952
1953
1954
1955
1956
Production
12
(13)
15
53.0
75.1
60
(63)
(65)
70
(80)
(93)
109.8
105.7
152.9
158.0
177.9
185.6
* Sales
' : .
'
103.0
97.6
136.4
140.6
160.5
169.0
of Pounds)
for 1971
for 1973
Production
1957
1958
1959
1960
1961
1962
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972 (p)
1973 (p)
Jan. 1974
(p)
196.6
187.2
203.0
209.4
225.1
320.5
325.1
365.7
429.4
462.7
533.0
636.5
635.3
706.9
704.7
(745)
693.8
65.8
and from
Preliminary
Sales
168.6
162.3
186.0
187.2
225.4
307.7
278.1
335.6
385.0
424.8
468.7
567.0
611.6
640.2
653.9
Tetrachloroethylene profits from the restriction on trichlordethylene,
although methyl chloroform is favored in metal degreasing because of its lower
toxicity.
The dry cleaning market is expected to increase its consumption of
tetrachloroethylene at 4-5% per year through 1975. 'It is estimated that the
perchloroethylene consumption for industrial dry cleaning will increase
from about 90 million pounds in 1971 to 200 million pounds by 1975 (Chemical
Economics Handbook).
71
-------
III. USES
The chlorinated hydrocarbon solvents find their most widespread appli-
cations as alternatives to water-surfactant systems in drycleaning and metal
degreasing (Carbonnier, 1967; Streeb, 1972; Weitbrecht, 1965; Willard, 1972).
The use of organic solvents as substitutes for water as a medium for
dyeing fabric could eliminate much of the liquid dye wastes from textile
plants, since less actual waste remains after dyeing and this smaller
amount could be used in a variety of ways. This would have an immediate
effect on the water pollution problem. Tetrachloroethylene is the subject
of much research in this area (Byeland, 1971; Fielding, 1972; Furness,
1971; Gebert, 1971).
Methyl chloroform is the principal solvent in wet cleaning applications.
Its use as a vapor degreaser is expected to increase by 10% per year as
trichloroethylene undergoes further restrictions. The low toxicity of
methyl chloroform, its good evaporation rate, lack of flash and fire points (in air),
and moderately high vapor pressure qualify it as a solvent and carrier for
many of the active materials used in aerosols, specifically in spot removers.
It is used to raise the apparent flash point in-flammable petroleum solvents and
is used as a coolant in cutting oils, printing inks, and shoe polishes. It
is a resin solvent in adhesives and is used in the'textile industry for
processing and finishing. Dow Chemical produces vinylidine chloride directly
from methyl chloroform.
While trichloroethylene has incurred disfavor as a solvent in vapor
degreasing because of its escape into the atmosphere (Dale, 1972;
Greve, 1971), it may find wide application in non-aqueous textile processing
and finishing (Dyhrenfurth, 1972; Willard, 1972).
-------
Trichloroethylene is used as an inhalation anaesthetic during parturition
and in dentistry (Huff, 1971; Kloos, 1966). It is used in the extraction of
I <*
hops and of soybean oil meal (Kloos, 1966; Pritchard, 1956).
Tetrachloroethylene is the leading dry-cleaning solvent and is the subject
of much research in the dyeing industry (Byland, 1971; Fielding, 1972; Furners,
1971; Gebert, 1971). It is used in both cold-cleaning and -vapor degreasing of
metals, as a solvent for silicones, and as an intermediate-in the synthesis of
fluroocarbons 113, 114, 115, 116. .
In the past, tetrachloroethylene has been used in treating fresh and
dried fruits (Deshusses, 1955) and in controlling rot-producing mold on straw-
berries and on other fresh fruit (Mapers, 1954). More recently, the brominated
hydrocarbons have replaced tetrachloroethylene in these processes.
It has been applied medically as an antihelmetic (Jung, I960; Mackie, 1955)
There are no references to this application in the more recent literature,
73
-------
Representative Commercial Products Containing Trichloroethylene
Brush Top Spot Remover, Regular**
(Product Sales Co.)
Espersol 2530 (xylene) 87%
Trichloroethylene 10*
Perchloroethylene 1.5
Methylene chloride 1.5
Brush Top Spot Remover, Super**
(Product Sales Co.)
100% chlorinated solvents
Triethane (1,1,1 -trichloroethane) 50%
Trichloroethylene 25
Perchloroethylene 10
Methylene chloride 5
Carbona Cleaning Fluid
(Carbona Products Co.)
Trichloroethylene 44%
Petroleum hydrocarbons 56
Carbona No. 10 Special Spot Remover
(Carbona Products Co.)
1,1,1-trichloroethane 10%
Trichloroelhylene 40
Petroleum hydrocarbons 50
Carbona Spray Spot Remover
(Carbona Products Co.)
Trichloroethylene
1,1,1-Trichlorethane
Cab-O-Sil
Freonl2
Crater 2X and 5X Fluid
(Texaco, Inc.)
Petroleum lubricating oil
Trich'.oroethylene
Pine tat
DuPont Dry Clean
(du Pont)
Trichloroethylene
Dux
Water Repellent
(Detrex Corp.)
Piccotex 120 Solution 25%
(synthetic resin)
Wax (paraffin)
Trichloroethylene
Glamorene Dry Cleaner for Rugs
(Formerly Glamorene Wool Rug Qeaner)
(Glamorene Products Corp.)
Chlorinated hydrocarbon
(trichloroethylene)
Petroleum distillate '
Wool flour
Glamorene Rug Qeaner
(Glamorene Products Corp.) t
Trichloroethylene t
Ethylene dichloride
Heavy naphtha .
Helmac Spot Pic-Up ;
Aerosol spot remover
(Helmac Products Corp.). ' .
Perchlorethylene
Methylene chloride
Trichloroethylene
HH Tree Wound Healer
Protective seal for pruned and damaged
tree and shrubs
(Hubbard-Hall Chem. Co.)
Asphaltum ' . :
Petroleum oils ' v
Phenylmercury oleate . '. /:
Allantoin ; /:',',
Inert ingredients:
Dichlorodiiluoromethane .. . ,.
Trichloroethylene
Methylene chloride : ,
Instant Chimney Sweep -
Aerosol spray application
(Miracle Adhesives)
Trichloroethylene
Active chemicals
Propellant (Freon)
Joy Solvent**
(Joy Chem. Inc.)
Trichloroethylene
Kwik Kleen Drug Shampoo*
Dry Shampoo
(Royal Bond, Inc.)
Trichloroethylene
Lash Bath
Cleanser for false eyelashes
(Revlon)
Naphtha
Trichloroethylene
O'Cedar Sea-Spray**
(O'Cedar)
Methylene chloride
Trichloroethylene
%w/w
34
41
25
Cellbsolve acetate
Synthetic detergents
Wax
Freon propellent
Perm-A-Qor NA
(Detrex Corp.)
Trichloroethylene
Sears Air Freshener
Sears Odor Neutralizer
(Sears,'Roebuck, & Co.)
Essential oils
Perfume
Trichloroethylene
Spot Chief**
Aerosol ring-free spot remover
(White Frost, Inc.)
. Trichloroethylene
Perchlorethylene
Solvent 310 (petroleums
Solvent 310 (petroleum solvent)
Paradichlorobenzene
Lanolin
1,1,1-trichloroethane
Freon 12
Surfisan Spray*
Surface disinfection, preservation
and deodorizing .
(Koyal Bond, Inc.)
Chloroform
Kerosene
Camphor
Trichloroethylene
Triad Metal Cleaner
Trichloroe thy lene
Triad Metal Polish
Trichloroethylene
Trichlor
Solvent
(P.P.G. Industries, Chem. Div.)
Trichloroethylene 100%
Tri-Qene Dry Clean
Trichloroethylene
No longer contains trichloroethylene but listed since some products may still be in use.
No longct marketed, but some may still be in use.
The above product descriptions are not to be construed as current or accurate since changes in product composition are being made
continually by manufacturers.
Source: Huff, 1971
-------
The following are data on the consumption of the chlorinated hydro-
carbon solvents in 1971.
Methyl Chloroform Consumption
Millions of Pounds Percent
Cleaning solvent
Cold cleaning
Vapor degreasing
Exports
Vinylidene chloride
Miscellaneous
Total
200
50
250
50
35
40
375
67%
13
.*""'''
9
11
100%
Trichloroethylene Consumption
Millions of Pounds Percent
Metal Cleaning
Exports
Miscellaneous
Total
455
52
32
539
84
10
6
100
Estimated Perchloroethylene Consumption
Millions of Pounds Percent
Textile Industry 435
Exports 125
Metal Cleaning 110
Chemical Intermediate 70
Miscellaneous 8_
Total 748^
Source: Chemical Economics Handbook
58%
17
15
9
1
100%
75
-------
IV. CURRENT PRACTICE
Methyl chloroform Is substantially stable under usual handling conditions,
although it ±a sensitive to hydrolysis. The commercial product always contains
Small amounts of stabilizing substances, the most common of which are: glycol
diesters, solvent ketone mixtures, nitriles, dialkyl sulfoxides, imines, dialkyl
sulfides, dialkyl sulfites, tetraalkyllead, morpholine, nitroaliphatic hydro-
carbons, 2-methyl-3-butyn-2-ol, tertiary butyl alcohol, tetrahydrofuran, 1,4-
dioxane, sec-butyl alcohol, and monohydric acetylenic alcohols.
Stabilized methyl chloroform can be stored in mild steel tanks fitted with
a drier to prevent ingress of moisture. It is transported in lacquer-lined mild
steel drums (.Kirk-Othmer, 1964).
Hill (1962) investigated the possibility of non-flammable halohydrocafbons
forming explosive mixtures at elevated pressures. Methyl chloroform liquid
at 24°C pressured to 6 Ib/sq. in. gauge could not be ignited by fusing a
one-inch nichrome wire at 50 or 80 volts. When the system temperature was
raised to 36°C and the pressure to 26.5 Ib/sq. in. gauge, and fired at 80
volts, a moderate temperature increase and a pressure surge to 65 Ib/sq. in.
gauge occurred.
-------
The most exothermic combustion reaction which can be written for this
compound is: . . ,
CH3CC13 + 202-»2C02 + 3HC1
H = -218 Kcal.
Experimental results indicate that this reaction probably did not occur.
A more likely initial combustion reaction is:
CH3CC13 + 1.75 02 -» C02 + 1.5 H20 + CC13*
H = ca -33 Kcal.
This mildly exothermic reaction would be followed by exothermic reaction of
of the CC1 " radical such as: -
2 CC13* -> CjClif + C12
resulting in over-all heat release of about 75 Kcal. per mole of pxygen consumed.
Methyl chloroform will burn, although not energetically, at a tenperatmre
of 36 C and a pressure of 26 Ib/sq. in.
The flammability of trichloroethylene-air mixtures has been incorrectly
assessed in the literature. Several reported explosions led to an investigation
by the Bureau of Mines (Perlee, 1966) on the conditions under which such
explosions can occur. The results of these investigations show that if trich-
loroethylene is handled in the manner prescribed in Chemical Safety Data Sheet
No. 14, published by the Manufacturers and the Manufacturing Chemists'
Association, fires and explosions need not be encountered. Pertinent data
from these investigations are given here.
77
-------
£
CO
co
UJ
ec
Q.
1,000
800
600
1 400
300
200
100
80
60
40
30
20
10
10
TEMPERATURE, * C
20 30 : 40
60
80
100
KEY
Air
o Oxygen
O Nitrogen tetroxide
A 7-inch-diam tube
Experimental curve
Theoretical curve
Impossible mixtures
Nonflammable
11.8 pet
11 pet
7.9 pet
10.5 pet
-o
7.5 pet
Nonflammable
UJ
a:
O
100 eg
80 a. £
60 < eJ
LU
30 a~
ui .5?
O) X
»li
10
UJ
O
1
50 100
TEMPERATURE, ° F
150
200
250
Temperature Dependence of Vapor Pressure of TCE and Concentration Limits of
Flammability of TCE-Air, TGE-Oxygen, and TCE-Nitrogen Tetroxide Mixtures.
Source: PERLEE, 1966
T8
-------
1 2 3
ELAPSED TIME, seconds
typical Pressure History Curve for Gonstont Volume
Combustion of a 15 Volume-Percent TCE-Oxygen
Mixture at About 29° C.
TABLE 2. - Maximum pressure and burning time for constant
volume combustion of near limit mixtures
of TCE-air and TCE-oxygen.
Mixture composition
(volume percent)
TCE
13
14
15
16
15
15
Oxidant
Air
Air
Air
Oxygen
Oxygen
Oxygen
pmax
(psig)
49
50
51
96
138
129
T
(sec)
5.0
5.2
7.0
.9
.2
.3
Source: PEKLEE, 1966
79
-------
The United States Pharmacopeia (1970) states that trichloroethylene
should be preserved in tight, light-resistant containers. It should be
kept from prolonged exposure to excessive heat. The containers must
bear the statements "Caution - repeated use may cause liver damage" and
Warning - trichloroethylene must not be used in any closed-circuit rebreathing
system utilizing soda lime or other alkali because phosgene or other
toxic products may be formed."
The standard container of trichloroethylene is usually 300 ml. It
is stored and shipped in lined tin or galvanized mild steel drums, fitted
with screw caps or some other suitably tight method of closure. Lare quantities are
shipped in road or rail tank cars. Large-scale storage tanks should
be of mild steel, fitted with a dryer. Vents should, of course, lead to
a safe point outside the storage building.
Commercial trichloroethylene stabilizers cover a tremendous variety
of chemicals, some of which are: acetone, aniline, borate esters,
epoxy compounds, hydroxyanisole derivatives, hydrazones, isocyanates,
nitro compounds, phenol, pyrrolinic derivatives, stearates, tetrahydrofuran,
and thiazoles.
The methods and conditions for the storage and transport of tetra-
chloroethylene closely follow those for trichloroethylene. Tetrachloro-
ethylene, however, may also be stored in cast iron or galvanized iron
containers.
80
-------
V. ENVIRONMENTAL CONTAMINATION
Since the chlorinated hydrocarbons are employed chiefly as solvents,
particularly in metal degreasing and dry-cleaning, their primary escape route
into the atmosphere is by evaporation. A secondary source of contamination
is the presence of these solvents in effluents. It has been estimated
(Murray, 1973) that each year in the United States 2 x 105 tons of these
chemicals are lost to the environment.
There are three mechanisms by which solvent vapors escape from a vapor
degreasing plant: by external air currents, thermal convection currents,
and molecular diffusion (Greve, 1971).
Synthetic fibers retain a certain amount of solvent, holding as much
as 5% on the weight of the cloth. This solvent can volatize in a framing
oven, or in a storage room or warehouse from which it passes to the outside
atmosphere.
The efficiency of solvent recovery from a variety of sources has been
claimed to be on the order of 95%, which leaves room for pollution problems
in large-scale operations (Willard, 1972).
In the literature collected, surprisingly little information appeared on
the incidence of methyl chloroform, trichloroethylene, and tetrachloroethylene
in the air, in ground waters, or in surface waters. No information at all is
available about the levels in the environment of the United States.
In an introductory study on samples of surface waters collected from the
northeast Atlantic in August, 1972, an average of 7 ng per L of trichloroethylene
and 9.5 ng per 1 of tetrachloroethylene were found. Molluscs from the rela-
tively unpolluted water around the Isle of Man-had accumulted significant con-
v'- . ' ;.' . .
centrations of several chlorine compounds, none of which were specifically
81
-------
named in the published report of the studied conducted.
In air samples taken from over the northeast Atlantic and from the rural
areas of Britain, 6 ng m 3 of trichloroethylene and 5 ng m 3 of tetrachloro-
ethylene were found (Murray, 1973).
82
-------
VI. MONITORING AND ANALYSIS
Many of the classical analytical procedures which employ techniques such
as combustion, hydrolysis, and the Beilstein reaction are still used, although
these are nonspecific since they relate total chlorine to the desired com-
ponent. They are therefore quantitative when a dingle compound is being
tested, but are qualitative only, when a mixture is being tested.
The colors of the products obtained from the reaction of the chlorinated
hydrocarbon solvents with pyridine and sodium hydroxide (Fujiwara reaction)
are colorimetrically applicable. The reaction of tetrachloroethylene with
pyridine .aniline, and sodium methylate offers increased sensitivity and more
stable color than the Fujiwara , reaction. A comprehensive presentation of these
analytical methods is included in The Encyclopedia of Industrial Chemical Analysis.
Gas chromatography, infrared spectroscopy, and mass spectroscopy can dis-
tinguish between individual compounds and give qualitative and quantitative data
on those present.
A. Analysis of Mixtures
In the field sampling of air, Grupinski (1966) mentions the possibility of
error through loss of the higher-boiling solvents by condensation in the gas
sample container during transport. Drasche (1972) recommends Teflon bags to
store exhaust gases from motor vehicles (excepting methane and acetylene) for
several days duration. Initial volumes can be attained by heating the bags.
Saran bags are recommended for long-term storage in the presence of carbon mono-
xide, methane, or acetylene in the air samples.
However, the use of charcoal tubes for collecting air samples prior to
gas chromatography testing has been shown to be efficient and practical. The
air to be sampled is aspirated through a standard charcoal sampling tube at an
accurately measured rate of 1 to 2 liters per minute. The charcoal is trans-
83
-------
ferred to a glass-stoppered Erlenmeyer flask, 3 ml of carbon disulfide is added,
the flask Is stoppered, allowed to stand for 10 min, and gently swirled. A
10 ml aliquot is injected into the gas chromatograph. This method gives average
recovery values of 962, 102%, and 100% for methyl chloroform; 88%, 96%, and 100%
for trichloroethylene; and 92%, 95%, and 97% for perchloroethylene (Reid, 1968).
A rapid field sampling of halogenated hydrocarbons in crude oil is given
by Jordan (1967). Description of the distillation apparatus is given together
with the experimental details. Pyridine and NaOH are added to the distillate and
read colorimetrically against standards prepared with kerosene. The lower
detection limit of methyl chloroform is 90 ppm,' with 1 ppm for trichloroethylene,
and 500 ppm for tetrachloroethylene. ..._..
Methyl chloroform, trichloroethylene, and tetrachloroethylene can be
determined in sewage sludge by either of two methods: 1) the solvents are
isolated from the sample by steam distillation, dissolved in n-hexane or
in cyclohexane, reduced with sodium, and the free chloride ions are deter-
mined titrimetrically; this method has a detection limit of 0.1 mg of
chlorine per liter of sludge. 2) The solvents are dissolved in ethanol
or cyclohexane, purified with Na2SO^, and analyzed by gas chromatography
(Montgomery, 1967).
A rapid method for separating and identifying chlorinated solvents in paint
was developed by Crippen and Emmerling (1960). The volatile solvents are
separated from the paints either by conventional distillation or steam distilla-
tion. The condensate is injected into gas-phase chromatograph operating between
70-125°F, with a helium flow rate of approximately 75 ml/min in Perkin Elmer
packed columns. The identity of the peaks is determined by time of emergence
(retention time) of the peak under given to temperature, gas flow, and column
8U
-------
packing. If a peak is questionable, it may be trapped and examined on an infra-
red instrument for positive identity. These procedures are useful also in
examining blood and body fluids for inhalation or absorption of chlorinated
solvents.
Infrafed spectrophotometric methods for determing trichloroethylene and
tetrachloroethylene in various Pharmaceuticals are described by Carol (1955)
and Healton (1962).
B. Trichloroethylene
Campbell (1959) bubbled contaminated air through toluene at 1 L per min.
to test the applicability to air of the method of Seto and Schultze (1956),
which is a modified Fujiwara reaction developed for determining trichloroethylene
.in urine, This is a colorimetric prodedure in which the sample is mixed with
toluene, followed by addition of pyridina and ethanolic potassium hydroxide.
The results of this method.used on air were comparable to the results obtained
after dehalogenation with sodium biphenyl and subsequent determination of the
chloride ion by the mercuric thiocyanate method.
Gage (1959) describes an air sampling system for trichloroethylene deter-
mination, consisting of two tubes connected in series. The first tube contains
a layer of silica gel impregnated with potassium permanganate and orthophosphoric
acid. The second tube contains silica gel impregnated with o-toluidine hydro-
chloride and serves to measure chlorine liberated by the first tube by the depth-
of color development. The life of these tubes is nine months and their precision
is adequate for industrial hygiene air analysis.
Another application of active charcoal .for...the adsorption of chlorinated
hydrocarbon solvents is demonstrated by Herbolsheimer (1972). In this case air
-------
is sampled in work areas at the head level of workers. N-decane is used as
the desorption reagent and the determination is carried out on a gas chroraa-
tograph with a dual flame ionlzation detector. In testing for trichloroethy-
lene, this method gives reproducibility of 95-100% and is quantitative to
1 ppm.
To determine trichloroethylene residues in spice oleoresins after solvent
extraction, Roberts (1968) used a microcoulometric gas chromatograph and read
the results against reference standards.
Using activation analysis, Morgan and Duxbury (1965) developed a method
for determing trichloroethylene in air. The air sample is drawn through a
saall charcoal pack by means of a battery-operated air flux and the Cl38
formed is determined by y-spectrometry. The lower limit of detection on
the equipment used was about Img of chloride.
Versie, Dodinval-Versie, Heusghem, and Moreau (1962) used gas chromato-
graphy to determine the concentration of trichloroethylene in blood following
intoxication. A 210 ml sample of blood was drawn from 345 of brain tissue.
The sample was treated with distilled water and toluene, before being analyzed
for trichloroethylene under the following conditions: Instrument, Perken Elmer
vapor fractometer; stationary phase, 25% didecylphthalate on cellite 545;
mobile phase, hydrogen; temperature, 83°C; voltage, 6.5V; flow rate 3.3 1/hr;
pressure, 9.5 kg/cm2; sensitivity, 1 part of trichloroethylene .to 32 parts of
toluene.
C. Tetrachloroethylene
The Hygienic Guide Series (1960) recommends that air to be tested for
tetrachloroethylene should be collected on silica gel followed by hydrolysis
with metallic sodium and determination of halide content. The alternatives
86
-------
mentioned are expulsion from the silica gel by heat, followed by combustion,
trapping the chloride in sodium carbonate-sodium formate solution and titrating
the trapped chlorine, or a direct combustion method followed by chloride
titration.
Strawberries which have been fumigated with tetrachloroethylene can be
tested for residue nephelometrically after extracting the tetrachloroethylene
with ethyl ether and evaporating in the presence of ethyl benzene (Mapes, 1954).
Deshusses (1955) extracted the tetrachloroethylene from fruit by thermal
decpnposition and titrated the liberated HC1 with HgN03.
VII.. CHEMICAL REACTIVITY
Chlorinated solvents in vapor concentrations of a few ppm may decompose
if they contact open flames and/or hot surfaces. The decomposition products
are hydrogen chloride, carbon dioxide, carbon monoxide and phosgene.
A. Methyl Chloroform
Possessing no unsaturation, methyl chloroform is inert to atmospheric
oxidation under normal handling conditions. It is, however, easily hydrolysed
in an excess of free water, especially at elevated temperatures and in the gas
phase (Dyhrenfurth, 1972).
Heated at 75-160°C with water under pressure, methyl chloroform decom-
poses in the presence of sulfuric acid or metal chlorides, according to the
quantity of water present, to give acetyl chloride, acetic acid, or acetic
anhydride. At temperatures over 370°C methyl chloroform is subject to atmos-
pheric oxidation yielding phosgene as one of the decomposition products, with
1,1-dichloroethylene and HC1 also given off."
87
-------
In contact with iron at 402°Cj copper at 369°C, zinc at 338°C, aluminum
at 354°C, brass at 354°C, and steel at 354°C, the amounts of phosgene in the
decomposition products are respectively, 0.8, 0.4, 1.9, 0.3, and 0.3 mg of
phosgene per gm of methyl chloroform (Noweir, 1972).
Methyl chloroform reacts with chlorine in sunlight to give 1,1,1,2-
tetrachloroethane, along with small quantities of penta- and hexachloroethane.
Reaction with anhydrous hydrogen fluoride at 144°C in the absence of a cata-
lyst results in formation of 1,1-dichloro-l-fluoroethane and l-chloro-1,1-
difluoroethane (Kirk-Othmer, 1964).
B. Trichloroethylene
. The unsaturated bonding in trichloroethylene is sensitive to atmospheric
oxidation in light. However, in the presence of suitable stabilizers, it is
stable to air, moisture, light, and contact with common metals up to 130°C,
where it becomes corrosive to metal.
Trichloroethylene is not hydrolysed by water under normal conditions
(Dyhrenfurth, 1972). It reacts with alkaline hydroxides at 150°C to give
glycolic acid. Strong alkalies react readily with trichloroethylene to form
explosive chloroacetylehes. Sodium carbonate and aqueous ammonia do not
react. In the presence of soda lime at 37°C, trichloroethylene decomposes
readily to dichloroacetylene, which then oxidizes readily to phosgene and
carbon monoxide.
Trichloroethylene does not react with cold inorganic acids but decomposes
violently in hot nitric acid.
In the presence of catalysts such as finely divided aluminum, or on exposure
to light, thermal decomposition occurs at 120°C (Smith, 1966). -In contact
-------
with iron at 450°C, copper at 500°C, zinc at 450°C and aluminum at 425°C, -
the amount of phosgene in the decomposition products is. 19, 31, 69 and 35 mg
of phosgene, respectively, per gm of trichloroethylene (Noweir, 1972).
When trichloroethylene is heated to 700°C, the vapor decomposes to give
a mixture of dichloroethylene, perchloroethylene, carbon tetrachloride,
chloroform, and methyl chloride (Kirk-rOthmer). :
C. Tetrachloroethylene
Unstabilized tetrachloroethylene in contact with water for long periods
slowly decomposes to trichloroacetic acid and HC1. It is sensitive to atmos-
pheric oxidation on exposure to light, going to trichloroacetyl chloride.
Stabilized tetrachloroethylene is inert to air, water, light, and common
metals to 140°C. -
Strong inorganic acids will oxidize tetrachloroethylene to trichloro-
acetyl chloride and tetrachlorodinitroethane. With ozone; it is decomposed
to phosgene and trichloroacetyl chloride (Kirk-Ot timer ).
In contact with iron at 450°C, zinc at 400°C, and aluminum at 400°C,
the amount of phosgene given off in mg of phosgene per gm of tetrachloroethy-
lene is 37, 17, and 3, respectively (Noweir, 1972).
89
-------
VIII. BIOLOGY
A. ABSORPTION
Methyl chloroform, trichloroethylene, and tetrachloroethylene are
volatile compounds and inhalation is the dominant intake route into human
or animal systems. They are absorbed very rapidly through the lungs and
gastrointestinal tract. .
Skin absorption studies were performed on these three solvents using six
human subjects. The skin of the hands was exposed to the solvents and the
amount of the compounds in the alveolar air during the skin exposure and in the
post-exposure period was determined by gas-chromatography. While all the sol-
vents penetrated the skin, it was concluded that they would not be likely to be
absorbed in toxic quantities when in contact with the skin of the hands and
arms (Stewart and Dodd, 1964).
McBirney (1954) reports paralysis of the thumb and forefinger following
intermittent repeated immersion of the hands in trichloroethylene under industrial
conditions.
'-.'>." - " :
. B. EXCRETION
1. Methyl chloroform
Studies involving the inhalation of methyl chloroform by human subjects
shows that the excretion of unchanged methyl chloroform via expired air has
an inverse exponential relationship to the time after exposure.
90
-------
70
50
30
20
!*>
7
5
3
2
: ::^
_. ._._
X
t
S
1
\ I.I.I-TRICHLOROETHANE
i CONCENTRATION, PPM
1
.7
.5
.3
.2
.1
/
' ..-
s
N
s
j
)
S
.
s
1
. . i. i . ; i iii LI .. j..
1 500 ppm, 78 mm (Exp
_...- : o 496ppm,l86min,(E«p
0 ! ;
r\ ° ' j
\
L Xp
XN
: ->,
x_-
X
i
1
T
y
s
-
-ts
T
>l
TN
1 i.
^
s
i
s
^
--
si
s
S_ 0
V °
X
\
\
1)
2)
j
1
>
j
i
1
; o
^
2 3 5 .7 I 23 57 IO
HOURS AFTER EXPOSURE
2O 3O 4O
1,1,1-Tric-lilorocthane Expired Air Concentration. Humans were exposed to
atmospheric concentrations of 500 ppm for 78 minutes (Exp. 1) and 496 ppm for 186 minutes
(Exp.2).
SOURCE: Stewart and Gay, 1961 (1)
Following absorption of methyl chloroform^ most of the compound ±s excreted
unchanged in the expired air and the metabolites trichloroethanol and trichloro-
acetic acid appear in the urine (Stewart, 1968).
The concentrations of methyl chloroform in human urine samples taken during
exposure indicated that some samples possibly contained up to 2 ppm of the compound.
Samples obtained 15 minutes after exposure revealed the presence of a trace amount
in some, with none being detected in others (Stewart and Gay, 1961 (!)) .
91
-------
2. Trichloroethylene
The following data are given by Stewart and Dodd (1970), demonstrating the
excretion of trichlorbethylene in the expired air of human subjects after
exposure.
I
Q
a.
0
o
ul
z
ul
J
ul
0
I
O
CO
108 3ppm. 7hrj /Joy - S d
6 tubjeett
5 2OOppm, 7hr» - 5lubj»ct»
X 197 7opi>. 3lvi.2Omir> - 2 mbj
2O2 ppm/ 1 h' - 2 lubj«ctl
1OO. 1 ppm, 4hr».- 2 tubjoctt
2O 3O . : 4O 'SO (SO
TIME IN HOURS AFTER EXPOSURE
-Following exposure, concentration of trichloroethylene in the expired breath
decreased exponentially. Concentration mean and range are plotted. Amount of solvent
present related to both duration of exposure and concentration of solvent during exposure.
Bartonicek (1962) measured the excretion of trichloroethylene by 9 human
volunteers who inhaled 1 g/m3 of the compound for 5 hours. He found the retention
rate to be 51-64%. The greatest amount of the trichloroethylene which was
excreted via the lungs was exhaled on the 1st and 2nd days after exposure, and
in traces on the third day. Of the trichloroethylene retained, 38 to 49.7% was
excreted in the urine as trichloroethanol and 27.4 to 35.7% as trichloroacetic
acid. 8.4% was excreted in the feces in the form of metabolites. The
remainder was excreted in perspiration and in the saliva in the form of
metabolites >
92
-------
Ikeda (1972) calculated that only one-third of the trichloroethylene
absorbed through the lungs was excreted in the urine during working time. His
studies were performed on urine samples from 85 male workers from 17 workshops
where the vapor concentration in the air was relatively constant.
In an earlier experiment, the excretion of trichloroethylene was investigated
by Soucek (1959) using five human subjects. A 6% concentration of trichloro-
ethylene was administered to the subjects by continuous inhalation for five hours.
\
The subjects retained 630-1288 mg, representing 58-70% of the amount inhaled
during exposure. Metabolites were present in the urine immediately after the
beginning of inhalation. Excretion of these metabolites in the urine lasted
between 312 to 520 hours.
3. Tetrachloroethylene
Mice were exposed for 2 hours to tetrachloroethylene-C11* vapor. In 4 days
70% of the amount inhaled was excreted in the expired air, and 20% appeared in
the urine in the form of metabolites (Yllner, 1961).
Six human subjects were exposed to tetrachloroethylene vapor, 194 ppm for
187 minutes. No tetrachloroethylene was found in the urine. Following is a
plot of the exhalation of the compound in time./
TETRACHIOROETHYUENE EXPIRED AIR CONCENTRATION )
-Tetrachloro-
ethylene expired air con-
centrations following
vapor exposure. Mean
concentration and range
are plotted.
. lo.e
TIME in HOUII*
10009
SOURCE: Stewart and Gay, 1961 (2)
93
-------
C. TRANSPORT AND DISTRIBUTION ,
1. Methyl chloroform
Six subjects were exposed to methyl chloroform at 500 ppm for 78 minutes.
Analysis of serial blood samples obtained during the exposure revealed that the
average concentrations of methyl chloroform in the blood at 30, 60, and 75
minutes after the start of the exposure were all between 3 and 4 ppm (Stewart
and Gay, 1961 (1)).
No studies on the distribution of methyl chloroform or its metabolites in
the tissues are reported in the material at hand.
2. Trichloroethylene
Trichloroethylene tissue uptake after vapor exposure was investigated
on dogs. Exposures were both acute and chronic with exposure times varying from
25 minutes to 219 hours at trichloroethylene concentrations ranging from 7,000
ppm to 20,000 ppm. After sacrificing the animals, cardiac blood and cerebral
spinal fluid were removed for immediate extraction, and tissues were frozen until
ready for processing.
The trichloroethylene concentration was determined colorimetrically after
extraction from the various tissues. Known amounts of trichloroethylene were
added to various tissues of normal animals as extraction controls.
-------
TJUCHLOKUKTHYLKNK RECOVERED FROM TISSUE
(Correctedin milligram* per cent wet weight)
Animal
Number
12
15
1C.
17
20
25
14
2t
1'J
22
24
Anincil
Nuiiitvr
12
15.
10
17
20
2.5
Mtxlr ol Exposure
o Acute
Acute
Acuiu
.Adltl!
Acutu
Acute X3
Chronic-Acute
Chronic-Acute
Chronic
Chronic
Chronic
Moils of Kxpoaiire
Acute
Acute
Acute
Acute
Acute
Acute X3
14 i Chronic-Acute
21
10
22
24
Chronic-Acute
Chronic
Chronic
1 Chronic
Adrenal
22.4
6.24
22.5
13.S
60.0
2;u
0.94
1.06
Lung
2.8
2.2
0.02
0.92
0.40
10.4
2.0
1.3
0.53
0.20
0.13
Blood
72.5
4ti.O
,r>2.7
22.3
28.4
50.0
4ti.l
50.6
9.6
0.13
0.25
Muscle
2.7
0.15
3.3
5.1
9.3
3.8
4.1
0.45
0.30
Brain
17.0
15.1
19.7
8.2
' 20.9
.
23.6
2.7
0.22
0.22
Pancreas
3.2
9.8
6.4
14.1
43.8
8.1
16.0
2.5
<0.05
0.28
Fat
17.9
14.7
4.8
70.4
70.5
22.1
30.7
14.4
6.5
Spinal
. Cord
8.8
'
28.3
.
0.13
0.13
Heart.
8.0
5.0
5.4
4.2
18.9
13.9
7.5
12.U
1.2
0.11
0.11
Cerebro
Spinal
Fluid
3.8
1.5
0.61
1.7
0.15
1.8
0.15
0.15
O.io
Kidney
1.6
8.2
5.8
3.0
3.2
17.5
21.1
5.3
1.0
0.13
0.25
Spleen
0.71
3.U
1.2
5.4
1.3
5.1
8.5
0.71
<0.05
0.12
Liver
27.0
9.6
38.8
10.8
9.2
49.4
.20.6
9.7
3.2
0.12
0.25
Thyroid
2.0
6.6
3.9
14.1
5.8
7.4
1.1
<0.05
0.63
SOURCE: Cohen, 1958
3. Tetrachloroethylene
Human volunteers were subjected to exposures of tetrachloroethylene vapor
and the following amounts of the compound were found in the blood:
«.o
. ».s
J.O
TETRACHLOROETHYLENE CLOOO |
CONCENTRATION DURING EXPOSURE |
lie TBflCm.OBOt TMTLtME I
1 PP« 1
_ z.s
1.0
1.9
1.0
0.5
0
/
/
1
1
1
/
/
T/
/
/'
/
y
/
'
*._«
V
s
.s' -
^.
1*4 PPM. « HIM.
9i>« rm.ium*.
"^-
,
1.0 1.5 IO
TIME IN HOURS
SOURCE:
Stewart and Gay, 1961 (2)
95
-------
D. METABOLISM AND METABOLIC EFFECTS
Five male volunteers were exposed to 500 ppm of methyl chloroform, 7 hours
per day for 5 consecutive days. Nine months later the same subjects were exposed
to trichloroethylene vapor, 200 ppm, 7 hours per day for 5 days. Twenty-four
hour urine collections obtained before, during, and following these vapor exposures
. ' - :..' « .
were analyzed for trichloroethanol and trichloroacetic acid. Results were as
follows: -.-.- - . ._._.-... '..' ' . , .
URINARY EXCRFl'lON OF TRICHtOROACETIC ACID (TAC) AND TRICHLOROETHANOL (TCE)
IN FIVE SUBJECTS DURING AND FOLLOWING VAPOR EXPOSURES TO 1,1,1-TRICHLOROF.THANE AND
TRICHLOROETHYLENE . .
Control value (mean and range)
1,1,1-Trichloroethane,
.500 ppm .
7 hr/day for 5 days
TCA TCE
(mg/24 hr) (mg/24 hr)
14,2(8-22,8) < 1«1-1)
Trichloroethylene,
200 ppm
7 hr/day for 5 days
TCA TCE
(mg/24 hr) (mg/24 "hr)
2(1-4) <
1st Exposure day
2nd Exposure day
3rd Exposure day
4th Exposure day
5th Day following last exposure
12th Day following last exposure
7,5(2,6-10,5) 20,1 ,(7,9-49) 51(34-84) 308(179-430)
10,9 (8,2-19,3) 30,1 (14,8-66,5 175(113-238) 359(294-480)
12,3(5,6-27) 29,3(19,1-51) 229(148-416) 399(296-546)
14,1 (7,8-19,2) 46,6 (23,4-93,6) 306 (231-439) 538 (249-822)
18(13-26) 7(1-14,9) 50(35-61) I5(tf>-18)
17,5(8-22)
-------
chloroacetic acid appeared in the urine a few minutes after the beginning of
the inhalation of the trichloroethylene vapor. The total quantity excreted
represented an aver-age of 4% of the quantity of trichloroethylene retained.
Trichloroacetic acid appeared in the urine immediately after the beginning of
the exposure. The average of the quantities excreted represents 19% of the retained
trichloroethylene. Trichlbroethanol appeared in the urine very soon after the
start of the exposure, and its excretion corresponded to 50% of the retained
trichloroethylene. In the various subjects the excretion of monochloroacetic
acid continued for 48 to 168 hours, the excretion of trichloroacetic acid
continued for 312 to 520 hours, and the excretion of trichloroethanol continued
for 312 to 390 hours. The amount of trichloroethylene which was retained during
the exposure was calculated to be between 58% and 70% of the amount inhaled.
Bartonicek (1962) determined a retention rate for trichloroethylene to be
51% to 64% of the amount inhaled by nine human subjects. An average of 45.4% of
the amount retained was excreted as trichloroethanol and 31.9% as trichlbroacetlc
acid.
The comparison of trichloroacetic acid plus the trichloroethanol in the urine
and the feces (urine average 21.5 mg/100 ml; feces average 17.8 mg/100 ml)
demonstrates that both metabolites pass into the digestive system through bile
and saliva, and are secreted by liver cells and the salivary gland cells in amounts
approximating those found in the urine.
Excretion of trichloroethanol and trichloroacetic acid in sweat demonstrates
that trichloroethanol-glucuronide circulating in blood and trichloroacetic acid
present in blood in ion form can pass into the parenchyma of sweat glands, and
are not confined to the extracellular fluid.
Mikiskova (1966) reports that the known trichloroethylene metabolites
possess their own physiological effects. Trichloroethanol is a central nervous
system depressant, -even when it is conjugated with glucuronic acid. Monochloroacetic
97
-------
acid has choleretic and laxative action and is hepatotoxic at high doses.
The toxicity of trichloroacetic acid is low.
The effect of trichloroethylene on tryptophan metabolism was studied by
determining the 5-hydroxyindole content in the urine of exposed human and animal
0
subjects (Corsi, 1963). A reduction of 5-hydroxyindole in the urine was
determined after administration of trichloroethylene.
Little is reported on the metabolism of tetrachloroethylene. Yllner (1961)
submitted mice to tetrachloroethylene-C11* vapor inhalation and detected the
urinary metabolites: 52% trichloroacetic acid, 11% oxalic acid and traces of
dichloroacetic acid. An epoxide is postulated as a metabolic intermediate,
with further rearrangement to trichloroacetyl chloride and then to trichloro-
acetic acid.
Dmitrieva (1967) investigated the metabolism of tetrachloroethylene in rats
and found ethylene glycol to be the dominant-metabolite which was excreted in
the urine. Trichloroacetic acid and oxalic acid were also determined.
It is surprising that no follow-up work was found in the literature con-
cerning the presence of the ethylene glycol and oxalic acid in rat urine
following exposure to tetrachloroethylene. Since it is not justifiable to apply
to man the results from experiments on animals, it would be of prime concern
here to establish that ethylene glycol and oxalic acid actually are metabolites
of tetrachloroethylene in the rat, and to establish whether any specific analysis
for these compound has been run on human urine following exposure to tetra-
chloroethylene.
When taken internally, ethylene glycol is extremely toxic. In fatal cases
death has been due to renal failure, with crystals of oxalic acid deposited
in the renal tubules. In poisoning by any of the glycols or their derivatives,
the outstanding toxic effect is exerted on the kidneys (Browning, 1961).
98
-------
In studies of tetrachloroethylene metabolism in humans, Haag (1958) reports
trichloroacetic acid in the urine of two workers who had been exposed to
tetrachloroethylene. Ikeda (1972) discusses the quantitative relationship
!'' " '"''"
between exposure to tetrachloroethylene and the concentration of the
metabolites trichloroethanol and trichloroacetic acid.
ft
0
IX. ENVIRONMENTAL TRANSPORT AND FAT°E
A. PERSISTENCE AND/OR DEGRADATION
There are many reports in the literature describing analytical methods for
determining the concentrations of the chlorinated hydrocarbon solvents in air,
but very little is published giving figures obtained during actual field tests
or in monitoring the environment in the vicinity of industries in which these
solvents are used. .
Nothing was found in the literature concerning the persistence or degrada-
tion of the solvents under natural atmospheric conditions.
99
-------
B. ENVIRONMENTAL TRANSPORT
The volatility of the chlorinated hydrocarbon solvents would provide
the mechanism for their transport in air. Water transport would also
distribute the solvents in the environment if they should escape in
effluents from the cites where they are being used. Their specif ic^ gravity
0 «
would tend to maximize effects in the bottoms of water streams or bodies.
a
C. BIOACCUMULATION
Murray (1973) reports on a preliminary investigation which showed
that molluscs from the relatively unpolluted waters around Fort Erin, Isle
of Man, contain significant concentrations of several organic chlorine
compounds in their tissues. Specific compounds found in these molluscs
are not named in this paper and amounts of chlorine compounds detected
. ' 1
are not given.
100
-------
X. TOXICITY
A. HUMAN TOXICITY
1. Inhalation of Methyl Chloroform
The principle toxic action of a single vapor exposure of methyl
chloroform is a functional depression of the central nervous system,
proportional to the magnitude of exposure, and typical of an anesthetic
agent (Stewart, 1968). Humans exposed to 900-1000 ppm experienced tran-
sient, mild eye irritation, light-headedness, and impairment of coordi-
nation. At a peak of 2650 ppm two of the subjects were unable to
stand (Stewart, 1961 (1)). Below the current threshold limit value
of 350 ppm no physiological effects have been observed.
Exposure time Concentration
(min) in air (ppm) Expected effect in humans
60 100 Apparent odor threshold
500 No detectable effect, but
odor is obvious
1000 Very slight loss of equilibrium
2000 Loss of coordination
30 1000 Eye & nasal discomfort, slight
loss of equilibrium
2000 Loss of equilibrium :
15 1000 Beginning of loss of equilibrium
5 2000 . Disturbance of equilibrium
Source: Stewart, 1968
Investigating liver and kidney damage suffered by humans after
exposure to methyl chloroform, Stewart, Gay, Erley, Hake, and Schaffer
(1961 (1)) reported the following results:
101
-------
I, I, l-TriflilonM-tliiiiio I'rc- anil I'cwtoxixmuro Dalit
Normal Value
Experiment 1
500 ppm, 78 niin..
Experiment 2
496 ppm, 186 min.
Experiment 3
U5S ppm, 73 min.
Experiment 4
910 ppm, 35 min.
Experiment 5
900 ppm. 20 min.
Experiment 6
0-2650 ppm. 15
niin.
Sub-
ject
1
4
6
6
8
11
1
2
5
6
8
10
5
6
8
3
4
2
7
9.
1
2
3
4
6
6
7
'. SGO-T
exposure
I
20 hr.
Post
7 da.
Post
6-40
22
14
15
16
16
12
20
20
16
23
20
24
16
19
18
14
18
17
18
16
14
16
10
14
14
15
14
10
14
U
10
16
16
20
18
16
20
18
10
18
16
16
16
18
15
20
18
16
15
11
14
15
16
12
in
16
12
14
14
14
16
10
18
19
16
12
15
6
16
14
17
20
15
15
16
18
14
19
20
Urinary Uruhilinngrn
ST
.
.£
(. hr.
Pout
2(1 hr.
Post
7 Ha.
Post
'
l:40nrl«wi
:IO
:10
-.10
:IO
:IO
:IO
; JO
|0
:10
:IO
; |0
:10
: 10
:10
:10
1 10
:10
:tO
:10
:10
:IO
:IO
:IO
:IO
:10
:10
:IO
*
:10
:IO
:IO
:10
:IO
:10
:10
:10
:10
1:640
1:640
1:10
1:40
: 10
: 10
: 10
:10
:10
:10
:IO
:10
r 10
r 10
1 10
1 10
:10
:IO
:1U
|o
! 10
' 10
:IO
:10
:IO
:IU
:IO
:IO
! 10
'. 10
|Q
; JQ
1:10
1:10
1:10
1:10
1:10
1:10
1:10
1:10
1:40
1:10
1:10
1:10
1:10
1:10
1:20
Urin»ly»i»
Preeipoiure
Alb.
Micro.
'20 hr.
PostexfHMure
Alb.
Micro
0-* RUC/IIPK
neg
neg
neg
neg
nog
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
rare HOC
1-2 IlUC
rnro RBC
neg
0-2 RBC
neg
neg
rare RBC
ne«
rare RBC
neg
.neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
tmre
neg
run- HIIC
3-6 KBC
13 min. P.S.P.
Precx-
poture
211 hr.
I'lMt-
Greater tlmn 25%
nrg nire It IK' i
neg nire It TIC
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
neg
m-g
neg
rare RBC
neg
neg
rare RBC
neg
neg
neg
neg
neg
neg
rare RBC
rare RBC
0-2 RBC
I-S RBC
30%
38%
40%
43%
89%
44%
31.5%
39%
44%
24%
These data show that methyl chloroform has^the capacity to exert
adverse effects on the liver and kidneys. Although in Experiment 6, it
might seem that the liver dysfunction is transient, subject 1 and sub-
ject 7 exhibited increased urinary urobilinogen values on the seventh
day following the exposure. This would indicate the possibility of
liver damage in predisposed individuals who would be subjected to a
chronic exposure to methyl chloroform. While the serum glutamic oxalo-
acetic transaminase (SGO-T) values and the 15-minute phenolsulfonphalein
102.
-------
excretion values following exposure deviated somewhat from the preexposure
values, they remained within normal limits.
Death results from the absorption of a toxic quantity of methyl
chloroform, following functional depression of the central nervous
system with respiratory arrest, peripheral vascular collapse, or
aspiration pneumonitis. The deaths from these causes are reported to
have occurred in unventilated tanks where the concentration of methyl
chloroform was well in excess of 5000 ppm.
Severe hypotension may be induced by a combination of central
nervous system depression and myocardial anoxia, secondary to poor
oxygen uptake.
However, no injury to man following repeated exposures to vapor
concentrations of less than 500 ppm has been observed (Stewart, 1968).
2. Ingestion of Methyl Chloroform
Methyl .chloroform is rapidly absorbed from the gastrointestinal
tract and is rapidly excreted, unchanged, via the lungs. However, the
ingestion of a toxic amount produces the same central nervous system
sequel as does the inhalation of a toxic amount. If the amount inges-
ted is sufficient to produce loss of consciousness, liver dysfunction
may result.
One case of accidental ingestion of methyl chloroform has been
reported (Stewart, 1968). Thirty minutes after a man ingested one
ounce of this solvent, he became nauseated. One hour after ingestion,
he experienced vomiting and diarrhea; this continued for two and one-half
hours at which time the man became incapacitated. Laboratory studies
at this time showed a leucocytosis and proteinuria. A slight eleva-
103
-------
tion In the serum bilirubin level was noted forty-eight hours after
ingestion. Six months following the ingestion, no deviation from the
normal was noted in complete blood cell counts, urinalyses, serum glu-
tamlc oxaloacetic transaminase, serum glutamic pyruvic transaminase,
blood urea nitrogen and electrocardiograms.
The median lethal oral dose of methyl chloroform in four species
of experimental animals is reported to range from 8.6 to 14.3 gin/kg.
3. Skin Contact with Methyl Chloroform
Prolonged or repeated contact with the skin results in transient
erythema and slight irritation. Several drops of this solvent splashed
directly on the cornea may produce a mild conjunctivitis which subsides
within a few days (Stewart, 1968).
4. Behavioral Effects of Methyl Chloroform
The daily exposure of humans to gaseous methyl chloroform (350 ppm
or 450 ppm) did not impair performance in psychophysiological tests.
The subjects were tested for perception, memory, reaction time, and
dexterity.
Although there were some deviations from normal patterns, these
were either not statistically significant or could be attributed to
fatigue and mental strain (Salvini, 1971).
5. Inhalation of Trichloroethylene
Trichloroethylene is classified among the most toxic solvents.
The acute toxicity of trichloroethylene with its predominant effects on
the central nervous system was recognized during the First World War
when it was substituted into degreasing systems. Individual cases of
liver damage among industrial workers have been reported.
-------
At trichloroethylene vapor concentrations of 150-250 ppm, workmen
experienced neurologic symptoms, headaches, and fatigue. Hypoalbuminemia
and hyperglobulinemia were observed in workers exposed for 5-10 months.
When vapor concentrations were 50-100 ppm, the frequency of symptoms
was reduced (Takamatso, 1962). The maximum permissible level for
trichloroethylene in air was set at 100 ppm in the United States in
1961.
Ten experimental human exposures to trichloroethylene at a 200 ppm
level were carried out for five consecutive days. During the exposure
individual subjects complained of lightheadedness, headache, throat
irritation, and mild eye irritation. Fatigue and drowsiness were experi-
enced. All neurological tests were normal during exposure, but 50%
of the subjects stated that greater mental effort was required to per-
form a modified Romberg test. With the exception of the 24-hour urine
samples which contained solvent metabolites, none of the clinical labor-
atory tests performed during or following the vapor exposures were ab-
normal. Thus, there was no laboratory evidence that even transient
organ dysfunction had occurred. Urinary urobilinogen tests, a most
sensitive index of hepatic dysfunction, were normal (Stewart, 1970).
If excessive concentrations of trichloroethylene are inhaled over
extended periods of time, varying degrees of poisoning may result.
Workmen may become addicted to it. Deaths from acute exposures to
trichloroethylene vapors most frequently result from narcosis to the
point of respiratory arrest or from primary cardiac failure. Entry
into a degreaser with trichloroethylene present was the most important
single cause of serious injury or death (Morrill, 1963).
105
-------
Longley (1963) states that acute unconsciousness can result from
the inhalation of trichloroethylene in a concentration of 3000 ppm if
the subject has had an immediately earlier, exposure resulting in a mild
intoxication. The generally accepted level of trichloroethylene required
to cause unconsciousness is 10,000 ppm.
Capellini and Grisler (1958) studied the liver function in a group
of twelve women who had worked in contact with trichloroethylene for
at least two years. About one-half of the cases showed dyspeptic syn-
f
dromes, liver enlargement, and serum protein changes. All cases had a
slight hyperbilirubinemia. Serum total proteins, albumin, total and
esterified cholesterol, alkaline phosphatase, blood glucose, and
urea were within normal values.
A fatal addiction to trichloroethylene was reported by.James
(1963). A worker who showed evidence of addiction to the inhalation
of trichloroethylene .vapors developed paresis of the olfactory nerves
with intermittant gastric disturbances over a nine-year period. Sudden
death occurred seventeen hours after the last known exposure. On autop-
sy, fatty degeneration of the liver, and lung hemmorhage were found.
The concentrations of trichloroethylene in the body were: 2.25 mg/100
ml in the blood, 7.1 mg in the liver, 19.9 mg in the stomach and its
contents, and 14.9 mg in the small intestine and its contents. The
urine contained 55.5 mg of trichloroacetic acid per 100 ml of urine.
In another addiction problem, Baerg and Kimberg (1970) found
centrilobular hepatic necrosis and acute renal failure in trichloro-
ethylene "sniffers". Three cases were involved. All had been inhaling
fumes from cleaning fluid. The first patient was admitted to the hos-
106
-------
pital with icterus. Tests of hepatic function were abnormal, but
rapidly returned to normal. Biopsy of the liver revealed acute toxic
centrilobular necrosis superimposed upon, a previous centrilobular
injury. The patient had an uneventful recovery and was discharged
from the hospital on the thirteenth day after admission.
A second patient, who had also inhaled fumes from cleaning fluid
was admitted to the hospital because of anuria of three-days' duration.
The patient had acute tubular necrosis and toxic hepatitis, both secon-
dary to trichloroethylene inhalation.
6. Ingestion of Trichloroethylene
General anesthesia was the outstanding feature in the clinical
course of a human who ingested approximately 50 ml of trichloroethylene
(Fleischhacker, 1956).
Stentiford and Logan (1956) report that an adult male who swallowed
approximately 130 ml of trichloroethylene was comitose for two days.
The foremost toxic sumptoms were short intermittent periods of very
rapid heart action. The electrocardiogram showed prolongation of the
P-R interval to 0.26 seconds. Liver function tests showed no abnormality.
The urine contained no protein at any time during'the course of recovery.
There was no clinical evidence of residual damage to the cranial nerves.
Full recovery ensued.
Meyer (1965) reviewed fifteen cases of peroral trichloroethylene
intoxication, eight of which were fatal. All cases displayed central
nervous system disturbances with cerebral edema, central respiratory
paralysis, and psychosis. The ^electrocardiograms showed a pseudoinfarct
and cardiac arrythmia. The blood pictures showed a shift to the left,
107
-------
with anisocytosis, hypochromasia, polychromasia, and basophilic stip-
pling. Kidney function disturbances were reversible. Toxic liver
damage was not detected although degenerative changes were observed.
7. Skin Contact with Trichloroethylene
Although trichloroethylene is not absorbed through the intact skin
in toxic amounts, heavy industrial exposures to this solvent have pro-
duced generalized dermatitis. Paralysis of the thumb and forefinger
occurred in cases involving intermittent, repeated immersion of hands in
the liquid. This disability lasted for several months after cessation
of contact. There was no skin damage in any of the cases (McBirney,
1954).
8. Behavioral Effects of Trichloroethylene
Stopps and McLaughlin (1967) used manual dexterity tests (Craw-
ford Small Parts Dexterity Test), card sorting, and dial display in
measuring changes in psychophysiological function in human subjects
exposed to trichloroethylene vapors. Four concentrations of trichloro-
ethylene vapor were selected for the exposures: 100 ppm, 200 pp»,
300 ppm, and 400 ppm. Trichloroethylene showed no significant effect
on psychomotor performance at the 100 ppm level. There is a slight
decline in performance at the 200 ppm level, which becomes progressively
more pronounced at the 300 ppm and 500 ppm concentrations.
Salvini, Binaschi, and Riva (1971) conducted studies similar to
those immediately above, and reached similar conclusions. In these stu-
dies, the following tests were performed: perception test with tachisto-
scopic presentation, Wechsler Memory Scale, complex reaction time test,
and manual dexterity test. In all the tests performed, a statistically
108
-------
significant decrease in performance ability was seen with increasing
vapor concentration inhaled. These workers concluded that 100 ppra of
trichloroethylene is very close to the concentration capable of inter-
fering with psychophysiological efficiency.
9. Inhalation of Tetrachloroethylene
Tetrachloroethylene is rapidly absorbed through the lungs and
gastrointestinal tract and is rapidly excreted, unchanged, via the
lungs. The primary toxic effect of a single vapor exposure is a func-
tional depression of the central nervous system, proportional to the
magnitude of exposure, and typical of an anesthetic agent. The early
symptoms of acute overexposure (between 200 and 300 ppm) are light-
headedness, and mild eye, nose, and throat irritation. Below the
current threshold limit value of 100 ppm, no adverse physiological ef-
fects have been observed in man (Stewart, 1969).
Exposure time Concentration
(min) in air (ppm) Response
1-4 75-80 Very slight eye irritation
4-6 100-120 Soft palate irritation and
dryness
6-30 200 Odor not unpleasant
30+ 210-244 Light-headedness
Following are laboratory studies performed on human subjects
after experimental exposures to tetrachloroethylene:
109
-------
LABORATORY STUDIES ON HUMAN SUBJECTS
AFTER TETRACHLOROETHYLENE EXPOSURE
BOO-T
HOP-T
Urinary Uroblllnovn
Subject
Kormnl Value
Pro- 20 llr.
exposure Putt
6-40
7 Dny Pro- 20 llr.
Pout exposure Pott
6-30
7 Day Pro- 8 Hr.
Poet exposure Post
1:40
or Less
20 Hr. 7 Diy
Post Post
Exp. 1
194 ppm,
187 mln.
Kip. 2
194 ppm.
83 mln.
'
Exp. 3
101 ppm,
183 mln.
1
2
3
4
6
6
2
3
6
7
8
9
1
2
3
4
6
7
12
18
16 '
16
15
10
16
12
6
16
17
18
16
14
16
14
16
16
18
20
18
23
16
13
16
14
10
17
19
16
12
18
14
10
12
14
18 .... '
14
18 ' '
.
14
12
18
12
12
16
20
18
14 16 14 14
14 13 16 -, 14
13 17 16 16
18 20 14 18
16 16 12 14
.17 ,17 12 20
:10
:10
:10
:10
:10
:IO
:10 1:10
:10. 1:10
-.10 1:10
:20 1:80
:tno 1:370
:10
:10
:10
:10
:IO
:10
:10
:10 1:10
:10 1:10
:10 1:10
:10
:10 1:10
:10 1:10
:10 1:10
:10 1 10
:10 1:10
:IO 1:10
:10 1:10
:10 1:10
:10 . 1:10
:10 1:10
:IO 1:10
:10 1:10
:IO 1:10
:IO 1:10
Source: Stewart, R. D., Gay, H. H., Erley, D. S., Hake, C.'L., and
Schaffer, A. W., 1961 (2).
no
-------
Tetrachloroethylene does not possess great potential for causing
serious liver or kidney injury, but repeated vapor exposures to high
concentrations have produced hepatitis in experimental animals.
Acute renal failure, occasionally observed in man, is probably a
consequence of the shock produced by the peripheral vascular collapse
secondary to central nervous system depression.
The SGO-T and SGP-T (serum glutamic oxaloacetic transaminase
and serum glutamic pyruvate transaminase) concentrations are useful
indices of induced hepatocellular injury. In most cases, the degree
and duration of elevation are related to the extent of liver damage.
Following are the results of laboratory studies on a man who had
been overcome with tetrachloroethylene while cleaning a tank with
this solvent. This patient experienced marked central nervous system
depression, followed by transient, minimal liver damage.
Tim*
Alter
Etpotur*
l'/4hr
2 days
3 days
Sdayt
9 days
10 days
SCOT,
Unlit
12
41
31
14
14
SORT.
Unit*
10
10
10
10
10
...
24-hr
Urinary
Uroblll-
nogen,
Ehrllch
Unlit
...
2.4
2.6
2.1
7.2
Total
Scrum
Protein,
gm/
100ml
...
7.1
6.9
6.4
6.5
Scrum
Albu-
min. %
...
64
62
69
69
Serum
Dlllrubln
Total/
Direct,
m*;/
100ml
0.4/0.2
0.4/0.2
0.4/0.1
0.4/0.1
Alkaline
Phoipha-
tate. King-
Armstrong
Unit*
11.4
11.4
10
13
11.4
DUN,
me/
100 ml Urlnalytlt
Specific gravity 1.015;
no albumin;
microscopically
normal
... No albumin;
microscopically
normal
No albumin;
microscopically
normal
12 No albumin;
microscopically
normal
... No albumin;
microscopically
normal
...
WBC/
cu mm
10.200
8.700
11.400
10,200
11.900
9.800
Hema-
toc,,,.
45
46
45
44
44
46
Retlcu-
locyt*
Count.
%
...
' ' *
0.7
0.3
0.5
0.4
Source: Stewart, 1969
Patel, Janakiram, Johnson, and Elman (1973) described a case of ex-
posure to tetrachloroethylene in which acute pulmonary edema was the
predominant symptom. The patient was admitted to the hospital in a
111
-------
deep coma; the pulse rate was 88 beats per minute; the blood pressure
was 88/20 mm Hg; the temperature was 34.4°C (94°F); and respirations
were 48 per minute. Bubbling rales were heard over the entire lung
fields.
After four days of treatment, the patient was well enough to
leave the hospital. Tests of liver and kidney function, done during the
four-day hospital stay and biweekly for several weeks afterwards, gave
normal results.
> .
Fatal poisoning by chronic Inhalation of tetrachloroethylene
vapor was reported by Transe and Zimmerman (1969) . The symptoms of
pulmonary disease which the patient initially manifested were diagnosed
as miliary tuberculosis. Later, jaundice and oliguria appeared and
the patient died nine days after the onset.
On autopsy, the lungs showed fibrin-rich exudate and intraparen-
chymal hemorrhage. The liver, large and greenish, showed extensive
acute to subacute centrilobular necrosis. The heart showed fatty de-
generation.
10. Ingestion of Tetrachloroethylene
No reports on human ingestion of tetrachloroethylene were found
in the literature.
11. Skin Contact with Tetrachloroethylene
This solvent is poorly absorbed through the intact skin (Stewart,
1969) .
12. Behavioral Effects of Tetrachloroethylene
Stewart, Baretta, Dodd, and Torkelson (1970) report an abnormal
modified Romberg test in three subjects within the first three hours of
112
-------
exposure to 100 ppm. After five hours of exposure, the Crawford manual
dexterity tests and the Flanagan coordination and arithmetic tests re-
mained normal.
A series of timed, human-skin exposures to methyl chloroform,
trichloroethylene, and tetrachlbroethylene were run by Stewart and Dodd
(1964).
The results of these experiments are as follows:
Human Skin Exposure to Chlorinated Aliphatic Hydrocarbon Solvents
Experi-
ment
1
o
4
5
6
1
No. of
Subjects
3
3
t
i;
l
1
Solvent
Trii'hlnri
M.'tiivln
1. 1. I-T
1. 1. I-T
1, 1. I-T
llu-l
. H,l
irhlo
irlil..
irliln
n<-
irii
or
or
or
!,:,.,,
liiinr
h:iiii>
LenRlh of
KxpOHure
(niin.)
:lil n i
:<(i n
.'ID n
.'ID n
:il) in
Skin Exposed
.
I hut
thui
llmi
hi.iict
hand t
.
i n
n
n
i t ii
1 TM
t rn
» rn
SIO
> JJCUl (Up
n)
n)
n)
)
lifiition)
Mean Peuk Drouth
("onrontrution
After Exposure
_
o.r, P|l
o.:u i>i>
:i.i pp
1.0 pp
2i.r> i>i>
O.iir> ppm
Mean Brtath
li >K>urd Afrer
Kxposure.
O.OH ppm
O.i;9 ppm
0.31 ppm
l.r>.ri ppm
0.31 ppm
I.I.I TRICHLOflOETHAME
TCTRACHLOROCTHVLENE
METHTLfNE CMLO»IDE
CARBON TETRACHLOHlOE
20 2.9 50 35
TIME IN HOURS
The mean alveolar air concentrations during skin exposure and in the
early postexposure period are plotted for the five solvents. The thumb of one hand was
iimni.TScd in the solvent for the above charted period of time.
113
-------
Individual Variation in Alveolar Air Concentration Following 30-Minute Skin Exposures
Experi-
ment
1
2
3
4
5
Solvent
Carbon telrarhloride
Trichloroethvlcne
To;r:ich!orotnyk>ne
Mc'.Jivlrne Chloride
1,1, i-TrichloroL-'.hnne
Solvent Volume
Displaced bv
Thumbs (ml)
15. 15, 17
15. 20. 20
25. 28, 27. 30, 3S
20.21.24
19, 20, 22, 25. 25. 28
RnnRfi of Alveolar Air Concentration, ppm
During Exposure
10 Min.
0.00-1-0.13
0 -0.27
0.02 -0.00
1.4 -2.4
.10 - .10
20 Min.
0.04 -0.05
0.008-0.51
0.11 -0.14
0.14 -0.17
30 Min.
0.11 -O.R3
O.OS'i-O.TU
0.17 -0.17
2.a -n.o
C.'.l -1. 02
Postoxposure
10 Min.
0.27 -0.79
0.01 -0.8
0.2G -0.36
2.1 -4.1
0.24 -0.97
30 Min.
0.45 -0.79
0.10 -0.40
0.2G -0.35
1.1 -fi.G
0.54 -0.77
1 Hour
0.24 -0.49
0.13 -0.32
0.23 -0.39
O.C -4.1
0.46 -0.78
2 Hours
0.19 -0.4S
.05 -0.14
0.1H -0.28
0.26 -1.7
0.18 -0.3^
5 Hours
0.12 -0.14
0 -0.010
0.1G -0.2'5
<0.1
0.03 -'J.tr.
H»NO- CONTINUOUS IMMCHSION
THUMB-CONTINUOUS IMMERSION
H»NO-TOn»L IMPLICATION
TIME IN HOURS
The alveolar air concentrations for 1,1,1-trichloroetharie during and
following 30 minutes of skin exposure are plotted versus time. Topical application of
the solvent to the skin of the hand resulted in far less absorption than when the hand
was continuously immersed for a similar period of time.
It was concluded, that although the solvents penetrated the skin,;methyl
chloroform, trichloroethylene and: tetrachloroethylene did not do so in toxic
amounts. .
liU
-------
B. TOXICITY TO NON-HUMAN MAMMALS
1. Acute, Subacute, and Chronic Toxicity
a. Inhalation
Mice were exposed to an atmosphere containing 2500-3000 ppm of
methyl chloroform for twenty-four hours. The animals were then sacri-
ficed and the methyl chloroform concentration in the liver was markedly
greater than that in the blood. The average methyl chloroform concentra-
tion found in the blood was 94 ± 17 mymol/g and the average concentra-
tion found in the liver was 954 ± 65 mpmol/g (Fuller, Olshan, Puri,
and Lai, 1970).
Heim (1966) found that the inhalation by mice of 1.8% by volume
of trichloroethylene in air anesthetised the animals. The animals were
sacrificed at 30 minute and 60 minute intervals after the beginning of
the inhalation. An analysis of the livers showed decreased levels of
glycogen, glucose, fructose diphosphate, dihydroxyaceteone phosphate,
and lactate. Glucose-6-phosphate and pyruyic acid levels were not
significantly altered. Creatinine phosphate, ADP, and AMP were re-
duced while ATP increased, showing that trichloroethylene can dis-
turb the metabolic processes in the mouse liver.
Tetrachloroethylene was found to disturb the metabolic processes
in the mouse liver by Ogata, Tomokuni, and Watanabe (1967). After three
hours of exposure to 800 ppm of tetrachloroethylene in air, liver ATP
had dropped to 46% of normal and remained so for twenty hours. Liver
total lipids increased to 134% immediately after exposure and gradually
increased to 158% after eight hours.
In comparison studies, trichloroethylene and tetrachloroethylene
115
-------
were inhaled by mice. Each group of ten mice were given a single
four-hour exposure to a series of different concentrations of each
compound. Two animals died during trichloroethylene exposure at 6,400
ppm (LDso = 8.450 ppm). At this concentration there was
no (or only slight) histologically detectable fatty infiltration of the
liver. Tetrachloroethylene caused fatty infiltration of the liver at
440 ppm, but necrosis of the liver cells could not be detected. Tri-
chloroethylene did not produce any significant increase in the amount of
extractable liver fat, thereby confirming the histological findings.
Tetrachloroethylene caused an increase of the extractable liver fat with
increasing concentrations in the air. The authors concluded from this
study that trichloroethylene seemed to be less dangerous to the liver
than tetrachloroethylene (Kylin, Reichard, Sumegi, and Yllner, 1962).
These same authors (1963) studied this subject further. On histo-
logical examination of the livers of mice which had been exposed to
trichloroethylene at concentration levels of 1600-3200 ppm, no increase
in liver fat was observed. Tetrachloroethylene, on the other hand,
induced an increase in liver fat at 400 ppm. Neither agent increased
the ornithine carbamoyltransferase activity in serum. The authors
concluded that the hepatotoxic effects of trichloroethylene and tetra-
chloroethylene were in the approximate ratio of 1:10.
s -.'".
Friberg, Kylin, and Nystrom (1953) also concluded from their LDso
studies on mice that tetrachloroethylene is more toxic than trichloro-
ethylene.
To determine the lethal dose, groups of eight female white mice
were exposed to different concentrations of trichloroethylene or
116
-------
tetrachloroethylene for four hours. The calculations of LDso showed
8,450 ppm (45.4 mg/L of air) of trichloroethylene and 5,200 ppm
(35.4 mg/L of air) of tetrachloroethylene.
To determine the effect upon the central nervous system, two
groups of 14 and 15 white mice were exposed to trichloroethylene
(12,200 and 6,800 ppm, respectively) and two groups of 14 and 15 white
mice were exposed to tetrachloroethylene (12,200 and 6,800 ppm, respec-
tively) . According to the stages of narcosis experienced by the animals,
the narcotic effect of tetrachloroethylene to mice is greater than
that of trichloroethylene. An analysis of variance showed a signifi-
cant difference (P = 0.001).
In long-term inhalation studies, mice were exposed to trichloro-
ethylene at 1600 ppm or to tetrachloroethylene at 200 ppm, for four
hours daily, six days per week, for one, two, four, and eight weeks.
No external effect on the animals was discernible. No animal died as
a result of the exposure. Histological examinations of the livers
showed only slight fatty degeneration, and this tended to abate after
two weeks. Fatty degeneration was particularly marked for tetrachloro-
ethylene and tended to be more severe with longer exposure. The histo-
logically evaluated degree of fatty degeneration and the amount of
liver fat determined by extraction were in agreement; the correlation
coefficient was +0.74. The kidneys from the exposed groups and from
the control groups showed no appreciable difference (Kylin, Sumegi,
and Yllner, 1965).
In a later long-term series of inhalation studies (Prendergast, Jones,
Jenkins, and Siegel, 1967), rats, guinea pigs, dogs, and rabbits were
117
-------
used as experimental animals.
In a thirty-day series of repeated exposures to methyl chloroform
(12,060 mg/m3), ho animals died and no toxic signs were visible in
the test animals. Gross and histopathologic examinations of brain,
heart, lung, liver, spleen, and kidney did not reveal any abnormalities
that could be attributed to the exposure.
Continuous exposure to methyl chloroform (2059 mg/m3) did not
result in death or visible toxic signs in the test animals after
ninety days. Microscopic examination of tissue showed nonspecific
inflammatory changes in the lungs of all species.
During continuous exposure to methyl chloroform (754 mg/m3),
2/15 of the rats died on days 27 and 77, and 1/3 of the rabbits died
on day 38. The survivors exhibited no toxic signs. Varying degrees of
lung congestion and pneumonitis were noted in all species and in a num-
ber of the controls. In view of the three deaths and the pneumonitis
present in the surviving animals, no positive conclusion could be drawn
as to whether the effects were associated with the exposure; at the
higher exposure of 2059 mg/M3 no deaths occurred and no pathologic ab-
normalities were noted.
In repeated exposures to trichloroethylene (3825 mg/M3), animals
were exposed repeatedly for eight hours a day, five days a week, for
thirty exposures over a six-week period. No mortalities occurred.
Nonspecific inflammatory changes were found on histopathologic examina-
tion in the lungs of all animals, but there was no evidence of specific
chemically-induced changes in any of the organs which could be attributed
to the exposure. Histochemical studies of enzymatic activity were per-
118
-------
formed on liver tissue from three selected experimental rats; no
changes were found. .
During continuous exposure to trichloroethylene (189 mg/M3) for
ninety days, no animals died and no visible signs of toxicity were
noted. Histopathologic examination of heart, liver, lung, spleen,
and kidney tissue showed no indication of chemically induced changes.
b. Inges tion
Trichloroethylene was mixed in olive oil and fed in various con-
centrations (5-60%; 0.36-4.3 mg/gm) to 200 mice. The mice were sac-
rificed 72 hours after exposure. The results were as'follows: minimal
narcotizing dose, 10% or 0.72 mg/gm; minimal lethal dose, 40% or 2.92
mg/gm; minimal hepatotoxic dose, 10% or 0.72 mg/gm; midzonal liver
fatty change, 10% or 0.72 mg/gm; central liver fatty change, 12.5% or
0.91 mg/gm; moderate liver changes, 20% or 1.46 mg/gm; and severe liver
changes, none observed (Jones, Margolis, and Stephen, 1958).
c. Intraperitoneal administration
Hepatic function and kidney function were determined in mice by
sulfobromophthalein retention and serum glutamic-pyruvic transaminase
activity following intraperitoneal injections of methyl chloroform,
trichloroethylene, and tetrachloroethylene. The solvents were adminis-
tered in corn oil to deliver a final volume of 0.01 mg/g (Klaassen and
Plaa, 1966).
The LDso values after intraperitoneal injection were as follows:
Methyl chloroform in ml/kg, 3.8; in mmole/kg, 37
Trichloroethylene in ml/kg, 2.2; in mmole/kg, 24
Tetrachloroethylene in ml/kg, 2.9; in mmole/kg, 28
119
-------
These three solvents produced liver dysfunction only near the
lethal range when administered intraperitoneally. Tetrachloroethylene
was shown to produce hydropic degeneration with a minimal amount of
necrosis of the convoluted tubules of the kidneys, while methyl chloro-
form and.trichloroethylene elicited little or no microscopic change.
In later studies conducted by Klaasen and Plaa (1967), intraperi-
toneal LDso values for dogs were found to be:
Methyl chloroform, 31 mmole/kg
Trichloroethylene, 21 mmole/kg
Tetrachloroethylene, 21 mmole/kg
By this same route, the EDsg values for the elevation of serum
glutamic-pyruvic transaminase were found to be 8.6 mmole/kg of methyl
chloroform, 6.3 mmole/kg of trichloroethylene, and 7.2 mmole/kg of
tetrachloroethylene.
The liver dysfunction EDso values as measured by the serum gluta-
mic-pyruvic transaminase activity show that the three solvents are
capable of producing some degree of liver dysfunction. Tetrachloro-
ethylene can produce kidney dysfunction in dogs at near lethal doses,
as shown by the results of phenolsulfonephthalein excretion tests.
2. Sensitization
No sensitization studies are reported in the literature at hand.
3. Teratogenicity
Nothing is reported on the teratogenic activity of these three
solvents.
4. Carcinogenicity
Nothing is reported on any carcinogenic effects of these three
solvents.
120
-------
5. Mutagenicity
No mutagenicity studies have been reported on these solvents.
6. Behavioral effects
Trichloroethylene vapor at concentrations of 400-800 ppm reduced
the frequency of the spontaneous alternating behavior of rats. Their
running speed was significantly increased at 400-600 ppm but was signi-
ficantly decreased at 1600 ppm (Zahner, 1961; Grandjean, 1964).
Trichloroethylene vapors when repeatedly inhaled daily by rats
produced a specific inhibition of avoidance behavior at concentrations
which did not produce motor imbalance. No dose-dependent response was
apparent, and results obtained from repeated inhalation of 1568 ppm
did not differ from those with 200 ppm. Rats exposed to 4380 ppm
were grossly ataxic.
Tetrachloroethylene produced inhibition of the avoidance response
only at concentrations which caused frank depression and ataxia (Gold-
berg, 1964).
Four rats were individually exposed to trichloroethylene vapor (400
Y/L) for a period of 72 to 121 days. In all animals, dynamics of
cortical activity were noted with signs of excitation. These effects
were demonstrated by a disturbance of differential inhibition and
occurrence of positive reflexes with short latent periods and motor
unrest in the intervals between stimulations (Khorvat, 1959).
C. TOXICITY TO LOWER ANIMALS AND INSECTS
Trichloroethylene was found to be comparatively non-toxic when
applied topically to adult houseflies. Tetrachloroethylene produced
tremors with subsequent recovery (Kocher, 1954).
121
-------
Tetrachloroethylene acts on the nervous system of hookworms by
inhibiting the metabolic enzymes pf muscle fibers and other somatic
cells and induces death by disturbing the respiratory mechanism
(Iwata, 1961).
D. TOXICITY TO PLANTS
Phytotoxicity studies were carried out by making water emulsions
or solutions of the compounds to be tested and applying them to the
foliage of seeding plants with the following results (Cast, 1956):
. Bean Corn Cotton Cucumber Tomato
5% .5% 5% .5% 5% .5% 5% .5% 5% .5%
Methyl chloroform 2 0 2.5 0 0.6 0 101 0
Trichloroethylene 3.5 0 2.5 0 1.5 1 1 0 21
Key: 0 = no inury, 1 = slight injury, 2 = moderate injury,
3 = heavy injury, 4 = severe injury or dead plant
E. TOXICITY TO MICROORGANISMS
Tetrachloroethylene was found by Horsfall (1955) to reduce
sporulation of Monilinia fructicola.
Trichloroethylene reduces the survival time of Escherichia coli
to an extent which is generally proportional to the concentration of
the compound used (Horton, Sussman, and Mushin, 1970).
122
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ION-EXCHANGE RESINS: SUMMARY AND CONCLUSIONS
Although there are available figures which give the amounts of
resin materials produded annually in the United States, there are no
available figures which give the amounts of ion-exchange resins
specifically. Neither were there available figures on the amounts of
ion-exchange resins which were used in various applications.
If ion-exchange resins were released into the environment to
any extent, their physical and chemical properties would indicate per-
sistence under normal environmental conditions. However, these same
properties would argue against toxic hazards. It is unlikely that these
resins would find accidental entry into living systems by any route other
than oral. The many medical studies that were done in the years shortly
following 1950 used human subjects who ingested ion-exchange resins. No
consequences were noted other than the expected electrolyte imbalance
and the disturbance of acid-base equilibria, and these readjusted to their
starting values after the ion-exchange resin was excreted.
However, when a certain ion-exchange resin was fed to female mice
during the reproductive cycle, the offspring of these females were below
normal in weight and showed some retardation in tooth eruption.
Although commercial ion-exchange resins are insoluble and infusible
polymers, they may contain minute quantities of soluble impurities. In
most cases rinsing with water is adequate to remove the impurities before
certain critical applications. Nothing was found in the literature collected
to indicate exactly what these impurities are, nor was any mention made of
precautions to be taken in disposing of the rinse water. There are standard
procedures for obtaining greater purity, and manufacturer's data sheets
contain such information.
131
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According to Food and Drug Regulation 121.1148, extractable sub-
stances must be reduced to certain levels. There are established proce-
dures for attaining this degree of purity before applying ion-exchange
resins to food treatment.
The potential toxicity of the ion-exchange resins cannot be
minimized. Nothing was found in the literature concerning the inhalation
of ion-exchange particles or dusts by humans or by animals. Therefore,
there is no information on hand relating such inhalation to excretion
of the particles or their fate in the respiratory system. Experiments
with mice showed that after a suspension of ion-exchange resin was
administered intraperitoneally, granuloma formation was induced at sites
of phagocytosis by one of the resins used. Particles of other types
of resins were phagocytized without further consequence.
In summary, until further information is made available concerning
the environmental and biological behavior of the ion-exchange resins, no
statements can be made concerning the potential hazard which these agents
might present.
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ION-EXCHANGE RESINS
I. PROPERTIES
An ion-exchange resin is a cross-linked polymer which contains either
acidic or basic structural units and which can exchange either cations
or anions on contact with a solution. Resins are insoluble in all sol-
vents, due to their infinite molecular size which arises from the cross-
links. Despite the enormous size of the resin molecules and their com-
plete insolubility, such a polymeric acid or base will exhibit the chemical
activity of a monomeric acid or base, subject to the restrictive conditions
imposed by the insolubility and the immobility of the massive organic
ion (Craig, 1953) . These resins are essentially infusible polymers and
are resistant to common acids and alkalies. They may also be considered
as insoluble acids or bases, the salts of which are also insoluble.
These resins are characterized as anion exchangers (with basic
functional groups) and cation exchangers (with acidic functional groups).
The various matrices to which these functional groups are attached may be
of polystyrene, epoxy-polyamine, phenolic, polyacrylic, and styrene-di-
vinylbenzene frameworks. The resins are beads or granules in physical
form with standard mesh range of 16/50 and particle size from 0.3 mm to
1.2 mm.
Strong-acid cation exchangers are normally supplied in the sodium
form, weak-acid resins in the hydrogen form, strong-base resins in the
chloride form, and weak-base resins in the mixed salt form.
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Types of Ion-Exchange Resins and Typical'Commercial Products
Type
Chemical characterization
Chemical structure
Selected commercial
products
strong acid . sulfonated styrene-divinyl-
benzene copolymers
CH CH, CH CH,
nj) |^b
C-50
Amberlite IRC-84
Duolite CS-101
lonac C-270
Dowex CCR-1
Duolite CS-100
Type I:
Amberlite IllA-400
Arnberlifco IHA-401
Amberlite IRA-402
Amberlite iltA-900
Duolite A-101-D
Duolite ES-1V1
Dowex 1
Dowex 11
Dov.ex2lK
lonnc A-o'-tO
Type II:
Amberlite IKA-410
Amberlite IRA-911
Dowex 2
Duolite A-102-D
lonac A-542
lonac A-550
Amberlite IUA-GS
Dowex 44
Duolite A-7
lonac A-2CO
Amberlite IR-fo
AmberlitoIRA-'j::
Dowex 3
Duolite A-l-t
Dowex A-l
CHCH,
CHX
,CH,.COO"
^CH.COQ-
Source: Snell, 1972
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Characteristics of Typical Ion-Exchange Resins
Cation-exchanger3 Anion-exchangers
Strongly acidic Weakly acidic Strongly basic Weakly basic
Functional group Sulfonic Carboxylic Quarternary Amino
ammon i *fm
Effect of increasing
pH value on
capacity
Independent
Increases
Independent
Decreases
Salts
Stable
Hydrolyse on
washing
Stable
Hydrolyse on
washing
Regeneration of
salts to free acid
on free base
Exesss of
strong acid
required
Readily
regenerated
Excess of
sodium hydrox-
ide required
Readily
regenerated
with sodium
carbonate or
ammonia
Rates of exchange
Rapid
Slow unless
ionized
Rapid
Slow unless
ionized
Source: Pepper, 1952
135
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The chemical stability of the ion-exchange resin as a whole depends
both on the stability of the main framework and on the stability of the
substituent groups. The sulfonated polystyrene resins are stable at
100°C for long periods in the presence of dilute acids and alkalis. The
salts of the strongly basic resins are stable up to 50°C and the free
bases possess good stability at room temperature.
II. PRODUCTION
The leading producers of ion-exchange resins in the United States
are The Diamond Shamrock Chemical Company, Resinous Products Division
(the Duolite exchangers); The Dow Chemical Company (the Dowex exchangers);
lonac Chemical, division of Sybron Corporation (the Sonac exchangers);
and Rohm and Haas Company (the Amber lite exchangers).
A styrene-divinylbenzene copolymer is the most frequently used
matrix for ion-exchange resins. Polystyrene beads cross-linked with
divinylbenzene are modified by chemical reactions to make ion-exchange
resins. Cation-exchange resins are produced by sulfonation of the styrene-
divinylbenzene copolymer. Anion-exchange resins contain quaternary
ammonium or amine groups. There are no available specific descriptions
for the manufacture of ion-exchange resins (trade' secrets) .
Manufacturing sites and production figures for the ion-exchange
resins are not readily available.
III. USES
Ion-exchange resins have many very practical uses. Their applica-
bility is attributable to their ability to substitute desirable ions for
136
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undesirable ions. Thus, they are highly favored in water softening.
They can eliminate ionic impurities in various media. They are capable
of isolating ionic constituents and fractionation (as in ion-exchange
chromatography).
i
Water treatment (both softening and deionlzation) accounts for the
largest single use of these resins. Their utilization in sugar purifi-
cation is quite extensive. Nearly all Impurities associated with sugar
in nature are ionic, so the ion-exchange resins are most suitable to
purify sugars obtained from beets, cane, corn starch, etc.
Chemical processing is another major area where the ion-exchange
resins are used. They are used in the Isolation and purification of
antibiotics, uranium extraction, and formaldehyde purification.
The ion-exchange resins are also used in the treatment of waste
liquors from the pulp and paper industry.
The Federal Food, Drug,,and Cosmetic Act allows many ion-exchange
resins to be used in the treatment of food, including potable water,
_ I , ^ _
to replace less desirable ions with Cl , H , OH and S04 , if the
resins are subjected to a preuse treatment by the manufacturer and the
resin results in no more than 1 ppm of organic extractive with H20,
15% EtOH, and 5% HOAc (Anon, 1964). Sailer (1957) demonstrated the
biological stability of fruit juices which have been treated with ion-
exchange resins. However, the chemical constitution of the juices was
so modified, resulting from a reduction in mineral content, that the
nutritional value of the juices was substantially minimized.
137
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IV. CURRENT PRACTICES
No specific regulations were found in the literature collected con-
cerning handling, storage, or transport of ion-exchange resins. The in-
ertness of these resins should make their handling problem-free.
V. ENVIRONMENTAL CONTAMINATION
No publications are available which discuss any environmental con-
tamination from the ion-exchange resins. There seem to be no specific
recommendations in the literature for the disposal of these resins.
VI. MONITORING AND ANALYSIS
The organic constituents of ion-exchange resins can be decomposed
by a wet combustion method using nitric and perchloric acids as an
alternative to elution when analyzing small amounts of ion exchange
resins for metals (Hoegfeldt, 1954). This method is suitable for both
cationic and anionic exchangers, since metals can be retained on an ion
exchangers as anionic complexes. The samples used were Wofatit KS and
Duo lite C-3 as examples of phenol formaldehyde resins and dowex 50 and
Lewatit S 100 as examples of polystyrene resins. All are cationic and
contain sulfonic acid groups. The anion exchanger used was Amberlite-
IRA-400, a polystyrene divinylbenzene copolymer containing quaternary
ammonium groups. After the wet combustion, the metals were determined
radiochemically and polarographically.
The total amount of amino groups, the amount of tertiary amino
groups, and the amounts of secondary and tertiary amino groups were
138
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determined by Kopylova (1969) by treating three samples of ion-exchange
feslns with acetic acid, acetic anhydride, and salicylaldehyde. After being
mixed with 0.1 N HCIO^ the samples were potentiometrically titrated against
0.05 N potassium hydrogen phthalate solution.
Calmanovici (1965) describes the application of ultraviolet spectro-
scopy to the analysis of cationic exchange resins.
Ion-exchange resins can be characterized by pyrolysis-gas chromato-
graphy. Parrish (1973) gives a method for rapid comparisons of pyrograms
of an unknown resin and standard resin using a single resin bead. Poly-
styrene resins, cation-exchange resins, effects of counterions, effects
of crosslinking, effect of capacity, anion-exchange resins, isoporous
resins, acrylic resins, and miscellaneous resins are discussed.
Ion-exchangers based on copolymers of styrene and divinylbenzene
may contain fragments which are introduced after manufacture. The frag-
ments show structural similarity to the resin and have properties associ-
ated with electrolytes. Mass spectrometry can be used to obtain informa-
tion on the nature of the reactions leading to eventual fragmentations
(Armitage, 1973) .
The possibility that a given resin preparation may be contaminated
by particles having a different charge was investigated by Burger (1967).
He developed staining methods to detect such a condition and also to
detect variation in cross-linkage.
A review of the standard methods for analyzing ion-exchange resins
is given by Snell (1972) .
139
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VII. CHEMICAL REACTIVITY
Extremely strong oxidizing agents such as boiling nitric acid or
chromic-nitric acid mixtures will rapidly degrade the polymer matrix.
Slower degradation with oxygen may be catalytically induced, so ions such
as iron, manganese, and copper should be minimized in an oxidizine solu-
tion. With cation-exchangers attack is primarily on the polymer backbone;
with anion-exchangers attack is on the functional groups. Amine struc-
tures may be attacked by low-valent sulfur compounds.
The thermal stability of anion resins is determined by the strength
of the C-N bond. A low pH favors higher stability. The quaternary ammon-
ium salts are the least thermostable, limited to 50° C. The tertiary
amines are stable up to 100° C. Cation resin stability also depends
on pH. Sulfonic acid resins in the acid form are not suitable for use
above 150° C in the presence of water. Depolymerizatlon of anhydrous
cation resins begins at 250-300° C.
Gamma radiation can cause a variety of simultaneous reactions to
occur - polymerization, depolymerization, oxidation, and rupture of C-S or
C-N bonds. The results are gas evolution, bead swelling, and weight loss
(Wheaton, 1966).
-------
VIII. BIOLOGY
A. ABSORPTION
Because of their mqlecular magnitude, the ion-exchange resins
do not pass through the membranes of living systems. When they are con-
tained within the digestive tract, however, they induce an electrolyte
imbalance by exchanging with those ions which normally are absorbed and
transported through the body.
This is an advantageous property when the ion-exchange resins
are ingested for the purpose of fixing excess sodium which has caused
edema, or for regulating potassium levels.
No intestinal damage has been reported from resin ingestion.
No evidence of bone decalcification has been observed, other than that
which would be expected during the course of the disease being treated
(Harthon, 1952).
B. EXCRETION/ELIMINATION
After ingestion, the ion-exchange resins are excreted normally
from the intestinal tract. The resin remains essentially unchanged with
the only difference at the active sites where ions were exchanged.
After intraperitoneal injections of ion-exchange resin particles
into mice, Strecker (1956) found that the resin particles were phagocytized
by the mesenchymal cells without substantial cell damage. This was true
of sulfonic acid resins and weakly acid resins containing phenolic hydroxyl
groups, as well as strongly basic resins. The exception was the weakly
lUl
-------
acid Amberlite IRC 50 (carboxylic groups) which induced massive formation
of fibrous tissue.
C. TRANSPORT AND DISTRIBUTION
Following intraperitoneal injections into mice, the ion-
exchange resins showed no tendency to migrate in the capillary fluids
or lymph system (Strecker, 1956).
D. METABOLISM AND METABOLIC EFFECTS
When ion-exchange resin particles were introduced into thie
mouse peritoneum they did not enter into metabolic reactions but were
phagocytized, with the exception of the carboxylic Amberlite IRC 50 which
produced tissue reaction in the form of granulomas and fibrous tissue
(Strecker, 1956).
«
In human studies during ingestion of ion-exchange resins, the
only effects reported are attributable to electrolyte alterations (Levitt,
1953) and disturbance of acid-base equilibrium (Wolff, 1955; Danowski, 1953),
IX. ENVIRONMENTAL TRANSPORT AND FATE
A. PERSISTENCE AND/OR DEGRADATION
The constitution of the ion-exchange resins indicates that they
would persist under normal environmental conditions. There is nothing
reported in the literature, however, concerning the persistence or degrada-
tion of these compounds.
1U2
-------
B. ENVIRONMENTAL TRANSPORT
Nothing was found in the literature to indicate that these
resins are transported through the environment to any extent.
C. BIOACCUMULATION
There are no articles in the literature collected on hand which
report on inhalation of resin particles or dusts. After ingestion it has
been shown that the resins are excreted essentially unchanged through the
intestinal system.
Strecker (1956) found that the strongly acidic Dowex 50 (sul-
fonic acid groups), weakly acidic resins (phenolic OH groups), and the
strongly basic Amberlite IRA 410 and Levatit MIH (quaternary ammonium
groups) were phagocytized by the mesenchytnal cells without essential dis-
turbance to the cells after the intraperitoneal administration of resin
particles to mice.
However, the behavior of the weakly acidic Amberlite IRC 50
(carboxylic groups) demonstrated a possibility of a most hazardous mode
of bioaccumulation. During the process of its phagocytization, localized
nodular granuloma formation was noted.
X. TOXICITY
A. HUMAN TOXICITY
1. Inhalation
Nothing is reported in the literature concerning the inhala-
tion of ion-exchange resin particles or air-borne dust during the manufac-
turing and handling of the resins.
1U3
-------
However, Astanina (1969) reports on toxicity occurring
during manufacture of anion-exchange resins from inhalation of some.start-
ing products. Workers were afflicted with headaches, nose and larynx
dryness, dermatitis, disturbed liver function, and other symptoms. Air
analysis showed that chloromethyl methyl ether, trimethylamine, dimethyl-
amine, formaldehyde, benzene, hydrochloric acid, methanol, and dimethoxy-
methane were present in the air.
2. Ingestion
In the many medical experiments reported, during which
;
patients ingested various amounts of different types of ion-exchance resins,
it was not the presence of the resin framework or its contact with the
gastrointestinal tract that produced toxic symptoms in the body. The ion-
exchange properties of these resins lead to electrolyte imblance and
disturbance of the acid-base equilibrium (Danowski, 1953; Wolff, 1955;
Levitt, 1953).
There are no reports of any instances in which ion-exchange
resins were accidently ingested.
B. TOXICITY TO'NON-HUMAN MAMMALS
1. Acute, Subacute, and Chronic Toxicity
In investigations of anion-exchange resins on experimental
dental caries and tooth eruption in the rat, the experimental animals
received diet supplements of the strongly basic anion-exchange resin
Dowex 2X8 in its chloride form ("resin 1"), the weakly basic anion-exchange
resin Amberlite XE58 in its hydroxyl form ("resin 2"), and Amberlite XE58
-------
saturated with chloride to nullify its anion-exchange ability ("saturated
resin 2").
These resins were toxic when fed to postweaned rats, as evidenced
by varying reductions in the rates of growth when compared to control
animals. This symptom was accompanied by retardation in the time of
eruption of the third molars (Shaw, 1963).
2. Sensitization
Rabbits treated subcutaneously with suspensions of
Dowex 50-X4 produced antiserum to this resin. Serum from untreated
rabbits and from human subjects gave no agglutination reaction with this
resin (Konishi, 1956).
3. Teratogenicity - Reproductive Effects
No teratogenic effects of ion-exchange resins are reported
in the literature. However, Shaw (1963) noted some reproductive effects.
The offspring of female rats which had been fed weakly basic anion-
exchanger Amberlite XE58 (hydroxyl form) had lower weaning weights and
slower growth rates than the controls. The offspring of females fed
Amberlite XE58 saturated with chloride had weaning weights approximately
two-thirds those of the controls.
4. Carcinogenicity
No specific carcinogenic studies were reported in the
available literature.
Strecker (1956) reports on granuloma formation following
-------
Intraperitoneal administration of weakly add Amberlite IRC 50 (carboxylic
groups) and subsequent phagocytosis by the mesenchymal cells.
5. Mutagenicity
No studies relating ion-exchange resins to mutagenicity
are reported in the available literature.
6. Behavioral Effects
No studies were found on the behavioral effects of the
ion-exchange resins.
C. TOXICITY TO LOWER ANIMALS
No studies were encountered on the toxicity of the ion-
exchange resins toward lower animals.
D. TOXICITY TO PLANTS
Ion-exchange resins have been recommended as agents in the
control of aquatic plants, specifically Florida elodea (Martin, 1970).
The resins would achieve the desired effect by sequestering or rendering
unavailable to the plant certain ions such as manganese and iron. Elodea
died in the presence of cation-exchange resin. The exact role of the
cation-exchange resin and the identity of the critical metal were not
determined.
E. TOXICITY TO MICROORGANISMS
Nothing was available concerning the toxicity of ion-exchange
resins toward microorganisms.
1U6
-------
LITERATURE CITED
Anon (1964), "Food Additives - Ion-Exchange Resins", Federal
Register 29_, 9708 12322
Armitage, G.M. and Lyle, S.J. (1973), "Mass Spectrophotometric
Study of the Deterioration of Polystyrene - Based Ion-Exchangers;
Talanta 20, 315-20 15936
Astanina, F.S. (1969), "Industrial Eygiene in the Production of
Anion-Exchange Resins", Gig. Tr. Prof. Zabol. 13 (1), 15-21
(Russ.). 12191
Burger, C.L. (1967), "Interaction of Dyes with Ion-Exchange Resins",
J. Chromatogr. 26. (1), 334-6 12373
Calmanovici, B. (1965), "Spectrophotometric Method for the Characteri-
zation of Ion-Exchange Resins. I. Cation Exchangers",
Materials Plas. 2^ (6), 369-71 (Rom.) 10670
Craig, P.N. (1953), "Synthesis of Ion Exchange Resins", Ann, N. Y.
Acad. Sci. 57., 67-68
Danowski, T.S. and Greenman, L. (1953), "Changes in Fecal and Serum
Constituents During Ingestion of Cation and Anion Exchangers",
Ann. N. Y. Acad. Sci. 57., 273-9 12428
Harthon, J.G;L. and Sigroth, K.I.E. (1952), "A Case of Uremia and
Hyperpotassemia with Sulfonic Cation - Exchange Resin", Acta.
Med. Scand. 144t 230-6 12258
Hoegfeldt, E. and Kierkegaard, P. (1954), "Wet Combustion, and Alter-
native to Elution when Analyzing Ion-Exchange Resins", Acta. Chem.
Scand. 8, 585-90 10620 .
Konishi, T. and Kitamura, M. (1956), "Serological Studies on Ion-Exchange
Resins. I.", Igaku to Seibutsugaku 40_, 195-8 12399
Kopylova, V.D., Asambadze, G.D., and Saldadze, K.M. (1969), "Determina-
tion of Functional Groups in Anion-Exchangers", Zavod. Lab.
35 (40), 1180-1 (Russ.) 12077
Levitt, M.F. (1953), "The Interpretation of the Laboratory Data in
the Clinical Use of the Cation Exchange Resins", Ann. N.Y. Acad.
Sci. 57, 298-307 12427
-------
Martin, D.E., Doig, M.T., and Millard, D.K. (1970), "Potential
Control of Florida Elodea by Ion-Control Agents", Nature
(London) 226 (5241), 181-2 14713
Parrish, J.R. (1973), "Analysis of Ion-Exchange Resin by Pyrolysis -
Gas Chromatography", Anal. Chem. 45 (9), 1659-62 15941
Pepper, K.W. (1952), "Ion-Exchange Resins", Plastics Inst. (London)
Trans. 20. (41), 68-84 12271
Sailer, W. (1957), "Ion-Exchange Treatment of Fruit Juices",
Fruchtsaft-Ind. 2., 131-5 (Ger.) 12407
Shaw, J.H. and Griffiths, D. (1963), "Influence of Anion-Exchange
Resins on Experimental Dental Caries and Tooth Eruption,
"J. Dental Res. 42_ (4), 1004-14 12509
Snell, F.D. and Ettre, L.S. (1972), "Encyclopedia of Industrial
Chemical Analysis", Interscience 15, 2-3
Strecker, F.J. (1956), "The Reaction of Tissue to Ion-Exchangers",
Beitr. Silkkose Forsch., Sonderband 2., 475-84 (Ger.) 12433
Wheaton, R.M. and Seamster, A.H. (1966), "Kirk-Othmer: Encyclopedia
of Chemical Technology, 2. C11)* 871-99
Wolff, H.P., Pfeffer, K.H. and Jahrmarker (1955), "The Disturbance of
Inorganic Metabolism and Its Avoidance during Treatment with
Ion-Exchangers", Arztl. Wochschr. 10, 781-8 (Ger.) 12410
1U8
-------
APPENDIX
C. I. Fluorescent Brightener 1
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
C.I. 40630
[15339-39-6]
Tinopal BV, BVA, BVS (Ciba-Geigy
Corp.)
4,4'-Bis[4,6-diamino-s-triazin-2-
yl)amino]-2,2'-stilbenedisulfonic
acid, disodium salt
C20H20N12°6S2 * 2Na ' (CH20)x
Bright blue
Yellowish powder
Good solubility in water. Stable
to acids and reducing agents.
Fastness: Chlorine, moderate;
Light, good; Washing, very good
Cellulose
Ciba-Geigy Corp. reported production and sales of Fluorescent
Brightener 1 to the U. S. Tariff Commission in 1972. No production fig-
ures are given; they are included in the total brightener production
figures.
A-l
-------
C. I. Fluorescent Brightener 1:1
Colour Index Number Not given in the literature
C. A. Registry Number Not given in the literature
Commercial Names Phorwite GG (Verona Corp.)
Chemical Class Stilbene derivative
Molecular Formula Not given in the literature
Fluorescence Blue
Properties Fastness: Acids, good; Chlorine,
poor; Reducing agents, excellent
Applications Cellulose
C. I. Fluorescent Brightener 2
This C. I. generic name is discontinued. The brighteners formerly
listed under it now appear under C. I. Fluorescent Brightener 1:1.
C. I. Fluorescent Brightener 3
This C. I. generic name is discontinued. The brighteners formerly
listed under it now appear under C. I. Fluorescent Brightener 28.
A-2
-------
C. I. Fluorescent Brightener 4
Colour Index Number Not given in the literature
C. A. Registry Number Not given in the literature
Commercial Names Calcofluor Yellow HEB (American
Cyanamid Co.)
Chemical Class Naphthalimide derivative
Molecular Formula Not given in the literature
Fluorescence Yellow
Properties Insoluble in hydrocarbons and
water, very soluble in formic
acid, soluble in alcohol and
esters
Applications Nylon, acetate
Lacquers
C. I. Fluorescent Brightener 4 is not being manufactured at the present
time.
A-3
-------
C. I. Fluorescent Brightener 5
Colour Index Number C.I. 36900
C. A. Registry Number Not given in the literature
Commercial Names Fluorescent Purple 2G (Allied
Chemical and Dye Corp.)
Chemical Class Stilbene derivative
Molecular Formula Not given in the literature
Fluorescence Reddish-blue
Properties Good substantivity for cellulose,
Fastness: chlorine, poor; peroxide,
good; light, satisfactory
Applications Paper
Cellulose
C. I. Fluorescent Brightener 5 is not being manufactured at the present
time.
A-U
-------
C. I. Fluorescent Brightener 5:1
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
C. I. Fluorescent Brightener 6
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Not given in the literature
Trisazo derivative
Not given in the literature
Reddish-blue
Good substantivity for cellulose
Poor fastness to chlorine
Paper
Not given in the literature
Not given in the literature
Not given in the literature
Calcofluor White B (American
Cyanamid Co.)
Not given in the literature
Blue
Good fastness to chlorine
Cellulose
American Cyanamid Co. reported production and sales of Fluor-
escent Brightener 6 to the U. S. Tariff Commission in 1972. No
production figures are given; they are included in the total bright-
ener production figures.
A-5
-------
C. I. Fluorescent Brightener 7
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Calcofluor White 4B (American
Cyanamid Co.)
Benzidine sulfone derivative
Not given in the literature
Greenish-blue
Outstanding fastness to chlorine
Cellulose
C. I. Fluorescent Brightener 7 is not being manufactured at
the present time.
C. I. Fluorescent Brightener 8
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Calcofluor White 5B, 5BT, P5B
(American Cyananid Co.)
Benzidine sulfone derivative
Not given in the literature
Greenish-blue
Excellent fastness to chlorine
Cellulose
American Cyanamid Co. reported production and sales of Fluoree-
cent Brightener 8 to the U.S. Tariff Commission in 1972. No produc-
tion figures are given; they are included in the total brightener
production figures.
A-6
-------
C. I. Fluorescent Brightener 9
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Application
C.I. 40621
[133-66-4]
Blancophor HZP, Tintophen CX
(GAF Corp.); Blankophor HZP
(Farbenfabriken Bayer A.G., Ger-
many) ; Calcofluor White MR (Ameri-
can Cyanamid Co.); Leukophor DNH
(Sandoz Colors and Chemicals);
Ryluz PP (Chemopdl, Czech.);
Tinopal TAS, TASD (Ciba-Geigy
Corp.); Whitex SB (Sumitomo
Chemical Co., Ltd., Japan)
4,4' -Bis[(4,6-dianilino-s-triazin-
2-yl)amino]-2,2'-stilbenedisul-
fonic acid, disodium salt
2 Na
Not given in the literature
Poor fastness to chlorine
Cellulose
Detergents
American Cyanamid Co., GAF Corp., and Hilton-Davis Div. of
Sterling Drug Corp. reported production and sales of Fluorescent
Brightener 9 to the U.S. Tariff Commission in 1972. No production
figures are given; they are included in the total brightener pro-
duction figures.
Production figures which have been reported in the past are:
1965 3,749,000 Ibs.
1967 318,000 Ibs.
1968 234,000 Ibs.
1969 254,000 Ibs.
A-T
-------
C. I. Fluorescent Brightener 9:1
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Hiltamine White BPK, EPS, EP
(Hilton-Davis Div. of Sterling
Drug Co.)
Bistriazinylaminostilbene deriva-
tive
Not given in the literature
Not given in the literature
Poor fastness to chlorine
Cellulose
C. I. Fluorescent Brightener 10
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literatura
Not given in the literature
Calcof luor Whit* ZRT (AtttriM*
Cyanamid Co.)
Stilbene derivative
Not given in the literature
Blue
High substantivity, good solu-
bility, good fastness to light,
not fast to chlorine
Cellulose
C. I. Fluorescent Brightener 10 is not being manufactured at
the present time.
A-8
-------
C. I. Fluorescent Brightener 11
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Calcofluor White 4R (American
Cyanamid Co.)
Stilbene derivative
Not given in the literature
Reddish-blue
Excellent fastness to chlorine
Cellulose
C. I.. Fluorescent Brightener 11 is not being manufactured at
the present time.
C. I. Fluorescent Brightener 12
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Fluorosol AC (Allied Chemical
and Dye Corp.)
Stilbene derivative
Not given in the literature
Bluish
.. Good substantivity and moderate
fastness to chlorine
Cellulose
C. I. Fluorescent Brightener 12 is not being manufactured at
the present time.
A-9
-------
C. I. Fluorescent Brightener 13
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Fluorosol ACL (Allied Chemical
and Dye Corp.)
Stilbene derivative
Not given in the literature
Bluish
Moderate fastness to chlorine
Cellulose
C. I. Fluorescent Brightener 13 is not being manufactured at
the present time.
C. I. Fluorescent Brightener 14
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the lit«ratur»
Not given in the literature
Leucophor RG (Sandos, Inc.);
Whitex RG (Sumitomo Chemical
Co., Ltd., Japan)
Stilbene derivative
Not given in the literature
Bluish
Greenish-gray powder
Compatible with ionic and nonionic
softening agents
Cellulose
A-10
-------
C. I. Fluorescent Brightener 15
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence .
Properties
Applications
Not given in the literature
Not given in the literature
Celumyl C (Societe de Produits
Chimiques et de Synthese, France);
Photine BH, 3BS, CM (Hickson and
Welch, Ltd., England); Photine C,
C33, UC (Hickson and Welch, Ltd.,
England; Hickson and Dadajee
Private, Ltd., India; S. A. Rovira,
Spain)
Stilbene derivative
Not given in the literature
Blue
Excellent substantivity, soluble
in aqueous media
Fastness: Acid, good; Alkali,
very good; Chlorine, very good;
Dithionite, very good; Peroxide,
very good; Light, moderate
Cellulose
Paper
A-ll
-------
C. I. Fluorescent Brightener 16
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluores'cence
Properties
Applications
Not given in the literature
Not given in the literature
Blancol DP (L.B. Holliday and
Co., Ltd., England); Celumyl D
(Societe de Produits chimiques
et de Synthese, France);
Heliofor DP (CZECH, Poland); Pho-
tine D, DK (Hickson and Welch,
Ltd., England; S. A. Rovira,
Spain)
Stilbene derivative
Not given in the literature
Blue
Excellent substantivity. Slightly
soluble in aqueous detergent solu-
tion
Fastness: Acid, poor; alkali,
very good; Chlorine, good; Dithi-
onite, very good:; Peroxide, very
good; Light, moderate
Cellulose
Wool
Nylon
A-12
-------
C. I. Fluorescent Brightener 17
Colour Index Number Not given in the literature
C. A. Registry Number Not given in the literature
Commercial Names Celumyl S (Societe de Froduits
Chimiques et de Synthese, France);
Photine S (Hickson and Welch,
Ltd., England; S. A. Rovira,
Spain)
Chemical Class Stilbene derivative
Molecular Formula Not given in the literature
Fluorescence Blue
Properties High solubility. Low substanti-
vity. Salt^sensitive. Good
stability to dithionite and per-
borate but poor fastness to chlorine
Applications Cellulose
Paper
C. I. Fluorescent Brightener 17:1
Colour Index Number Not given in the literature
C. A. Registry Number Not given in the literature
Commercial Names Photine DN (Hickson and Welch,
Ltd., England; S. A. Rovira,
Spain)
Chemical Class Stilbene derivative
Molecular Formula Not given in the literature
Fluorescence Blue
Properties Orange yellow powder
High substantivity. Dispensible
in water.
Fastness: Acid, poor; Alkali, very
good; Chlorine, good; Dithionite,
very good; Peroxide, very good;
Light, moderate
Applications Nylon
A-13
-------
C. I. Fluorescent Brightener 18
Colour Index Number Not given in the literature
C. A. Registry Number Not given in the literature
Commercial Names Tinopal SP (Ciba-Geigy Corp.)
Chemical Class Benzoyldiaminostilbenedisulfonic
acid derivative
Molecular Formula Not given in the literature
Fluorescence Bright bluish
Properties Yellow powder
Moderately soluble in water
Compatible with cationic softeners
Stable to resin finishing
Very good fastness to chlorine,
light, and washing
Applications Cellulose
C. I. Fluorescent Brightener 18 is not being manufactured at
the present time.
C. I. Fluorescent Brightener 19
Colour Index Number Not given in the literature
C. A. Registry Number Not given in the literature
Commercial Names Uvitex BT (Ciba-Geigy Corp.)
Chemical Class Stilbene derivative
Molecular Formula Not given in the literature
Fluorescence Yellowish white
Properties Yellowish white powder
Stable to peroxide and dithionite
Applications Cellulose
C. I. Fluorescent Brightener 19 is not being manufactured at
the present time.
-------
C. I. Fluorescent Brightener 20
Colour Index Number Not given in the literature
C. A. Registry Number Not given in the literature
Commercial Names Fluotex C2B (Compagnie Francaise
des Matieres Colorantes, France)
Chemical Class Stilbene derivative
Molecular Formula Not given in the literature
Fluorescence Not given in the literature
Properties Good fastness to perborate
and peroxide, moderate fastness
to chlorine and chlorites
Applications Cellulose
C. I. Fluorescent Brightener 20 is not being manufactured at
the present time. ,
C. I. Fluorescent Brightener 21
This C. I. generic name is discontinued. The brighteners
formerly listed under it now appear under C. I. Fluorescent
Brightener 5.
A-15
-------
C. I. Fluorescent Brightener 22
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Tinopal 4BMF Liquid (Ciba-Geigy
Corp.); Whitex 4BM, LSA (Sumitomo
Chemical Co., Ltd., Japan)
Stilbene derivative
Not given in the literature
Clear Bluish
Fastness: Chlorine, good; Light,
good; Washing, very good
Cellulose
Silk
Ciba-Geigy reported production and sales of Fluorescent Brigh-
tener 22 to the U. S. Tariff Commission in 1972. No production
figures are given; they are included in the total brightener pr«4uc-
tion figures.
C. I. Fluorescent Brightener 23
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Fluolite BW,: C (Imperial Chemical
Industries, Ltd., England)
Stilbene derivative
Not given in the literature
Bluish-violet
Good fastness to chlorine
Paper
A-16"
-------
C. I. Fluorescent Brightener 24
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
[12224-02-1]
Fluolite HSP Liquid (Imperial
Chemical Industries, Ltd., Eng-
land); Heliofor P (CIECH, Poland);
Kayaphor BSN, SN (Nippon Kayaku
Co., Ltd., Japan); Mikephor BN
(Mitsui Toatsu Chemicals, Inc.,
Japan); Tinopal 2B, 2BF Liquid,
2BP (Ciba-Geigy Corp.); Whitex
BB, BP (Sumitomo Chemical Co.,
Ltd., Japan)
Bistriazinylaminostilbenedisul-
fonic acid derivative
Not given in the literature
Bluish-violet
Yellow powder
Very soluble in water
Fastness: Chlorine, very good;
Light, good; Washing, very good
Paper
Cellulose
A-1T
-------
C. I. Fluorescent Brightener 25
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Blancophor SV (GAF Corp.)
Stilbene derivative
Not given in the literature
Bluish-violet
Very soluble in cool or warm
water
Cotton, wool, mohair
GAF Corp. reported production and sales of Fluorescent
Brightener 25 to the U. S. Tariff Commission in 1972. No figures
are given; they are included in the total brightener production
figures.
C. I. Fluorescent Brightener 26
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Pontamine White CL (E.I. du Pont
de Nemours and Co., Inc.)
Thiazole derivative
Not given in the literature
Reddish-blue
Excellent fastness to chlorine
Cellulose
Paper
Nylon
C. I. Fluorescent Brightener 26 is not being manufactured at
the present time.
A-18
-------
C. I. Fluorescent Brightener 27
This C. I. generic name is discontinued. Brighteners for-
merly listed under it now appear under C. I. Fluorescent Brightener
5:1.
C. I. Fluorescent Brightener 28
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Not given in the literature
[4404-43-7]
[4193-55-9], disodium salt
Blancol CFB new (L. B. Holliday
and Co . , Ltd . , England) ; Blanco-
phor FB, Tintophen FB (GAF Corp.);
Calcofluor White PMS, BMW, ST
(American Cyanamid Co.); Hiltamine
Arctic White CWD (Hilton-Davis
Division of Sterling Drug Co.);
Paper White BN, BP, Pontamine
White BT, BTS (I.E. du Pont de
Nemours and Co., Inc.); Tinopal
4BM, 4BMA, 4BMT (Ciba-Geigy
Corp.)
4,4'-Bis[[4-anilino-6-[bis(2-
hydroxyethyl) amino ] -s-triazin-
2-yl]amino]-2,2'-stilbenedisulfonic
acid
Pale blue
Canary yellow powder or clear
solution
Readily soluble. in water
Excellent stability under reasonable
storage conditions
Resistant to peroxide and perborate
bleaching action; susceptible to
hypochlorite bleach
Excellent dyeing properties over
temperatures of 80°F to 212°F and
over pH ranges 5-12.
A-19
-------
Applications ZEFRAN acrylic and cellulosic
fibers
Shirtings, bed linen, towels,
dress goods
White ground prints, tapes, braids,
white sewing threads, decorative
yarns
Nylongives greener (less red)
shade of blue
Cold-water laundry formulations
Liquid detergents
Fabric softeners
American Cyanamid Co., Cincinnati Malacron Chemicals, Inc.,
E. I. du Pont de Nemours and Co., Inc., Hilton-Davis Chem., Co.,
and the Verona Division of Baychem Corp. reported production and
sales of Fluorescent Brightener 28 to the U. S. Tariff Commission
in 1972.
Following are production figures for those years in which this
brightener was given separate listing in the U. S. Tariff Commission
Reports.
1965 1,515,000 Ibs.
1966 1,240,000 Ibs.
1967 1,410,000 Ibs.
1968 1,420,000 Ibs.
1969 1,676,000 Ibs.
1970 1,593,000 Ibs.
1971 1,574,000 Ibs.
1972 1,604,000 Ibs.
According to the U. S. Tariff Commission Reports, 4,180 pounds
of Fluorescent Brightener 28 were imported into the U. S. in 1972.
A-20
-------
C. I. Fluorescent Brightener 29
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Uvitex .P. (Ciba-Geigy Corp.)
Not given in the literature
Not given in the literature
Pure blue
High substantivity for cellulose
Paper
C. I. Fluorescent Brightener 29 is not being manufactured at
the present time.
C. I. Fluorescent Brightener 30
Colour Index Number
C. A. Registry Numbers
Commercial Names
C. I. 40600
[17118-51-3], cis
[17118-50-2], trans
[2606-93-1], disodium salt
Blancol C (L. B. Holliday and
Co., Ltd., England); Blancophor R
(GAF Corp.); Blankophor R (Far-
benfabriken Bayer A. G., Germany);
Blancofor R (Bayer do Brasil
Industriea Quinicas S. A., Brazil);
Enianil White R (Estabelecimento
Nacional Industria de Anilinas
S. A., Brazil); Glowhite RRN
(Dye-Chem., Ltd., India); Leuco-
phor R (Sandoz, Inc.); Delft White
2RW (Delfland Produkten N.V., Hol-
land); Lumisol RV (Fine Dyestuffs
and Chemicals, Ltd., England);
Phorwite RN (Verona Corp.);
Photine R (Hickson and Welch,
Ltd., England; S. A. Rovira,
Spain); Tintophen R (GAF Corp.);
Whitex R Extra (Sumitomo Chemi-
cal Co., Ltd., Japan)
A-21
-------
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
4,4'-Bis(3-phenylureido)-2,2'-
stilbenedisulfonic acid, diso-
dium salt
2Na
Reddish-violet fluorescence in
daylight; bluish-violet fluores-
cence in ultraviolet radiation
Yellowish powder
Poor fastness to chlorine
Stable to hydrosulfite
Cellulose, protein fibers, nylon,
wool, paper
GAF Corp. reported production and sales of Fluorescent Brigh-
tening Agent 30 to the U.S. Tariff Commission in 1972. No pro-
duction figures are given; they are included in the total brigh-
tener production figures.
C. I. Fluorescent Brightener 31
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Uvitex RSW (Ciba-Geigy Corp.)
Not given in the literature
Not given in the literature
Not given in the literature
Good fastness to chlorine
Mixtures of cellulose, protein
fibers, and nylon
C. I. Fluorescent Brightener 31 is not being manufactured at
the present time.
A-22
-------
C. I. Fluorescent Brightener 32
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
_Applications
C. I. 40620.
[1264-32-0]
Blancofor B Extra (Fabricacion
Nacional de Colorantes y Explo-
sives S. A., Spain); Enianil
White B (Estabelecimento Nacional
Industria de Anilinas, S. A.,
Brazil); Heliofor BGC (CIECH, Po-
land); Leukophor B, BCF (Sandoz,
Inc.); Whitex B, 3B (Sumitomo
Chemical Co., Ltd., Japan);
Delft White BS (Delfland Produk-
ten N.V., Holland)
4,4'-Bis[(4-anilino-6-hydroxy-
s-triazin-2-yl) amino]-2,2'-stil-
benedisulfonic acid, disodium
salt
C32H26N10°8S2 * 2Na
Bluish
Yellowish powder
Poor fastness to chlorine
Good fastness to washing
Cellulose, protein fibers, ny-
lon - - - - ....
According to the U. S. Tariff Commission Reports, 5,181
pounds of Fluorescent Brightener 32 were imported into the U.S.
in 1972.
A-23
-------
C. I. Fluorescent Brightening Agent 33
Colour Index Number Not given in the literature
C. A. Registry Number Not given in the literature
Commercial Name Blancophor SC (GAP Corp.)
Chemical Class Not given in the literature
Molecular Formula Not given in the literature
Fluorescence Blue (peak at 437 nm)
Properties Fair fastness to chlorine
Applications Cellulose, protein fibers, nylon
GAF Corp. reported production and sales of Fluorescent Brighten-
ing Agent 33 to the U.S. Tariff Commission in 1972. No production
figures are given; they are included in the total brightener pro-
duction figures.
C. I. Fluorescent Brightening Agent 34
Colour Index Number C. I. 40605
C. A. Registry Number [6416-25-7]
Commercial Name Pontamine White 2GT (E. I. du
Pont de Nemours and Co . , Inc . )
Chemical Class 4,4'-Bis(2,4-dimethoxybenzamido) -
2,2'-stilbenedisulfonic acid,
disodium salt
Molecular Formula
Fluorescence Not given in the literature
Properties Moderate fastness to chlorine
Applications Cellulose, protein fibers, nylon
A-2U
-------
C. I. Fluorescent Brightener 35
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Celumyl B (Societe de Produits
Chimiques et de Synthese, France);
Photine B (Hickson and Welch, Ltd.,
England; S. A. Rovira, Spain).
Stilbene derivative
Not given in the literature
Blue
Good solubility; moderate sub-
stantivity. Stable to alum and
size
Fastness: Acid, very good;
Alkali, very good; Chlorine, good;
Dithionite, very good; Peroxide,
very good; Light, moderate
Paper
C. I. Fluorescent Brightener 36
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Blancol 61281 (L. B. Holliday
and Co., Ltd., England)
Balanced anionic-cationic complex
Not given in the literature
Bluish-violet
Stable to dithionite and peroxide
Protein fibers, acetate, nylon
A-25
-------
C. I. Fluorescent Brlghtener 37
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given In the literature
Not given in the literature
Uvitex RT (Ciba-Geigy Corp.);
Whitex Rt (Sumitomo Chemical
Co., Ltd., Japan)
Stilbene derivative
Not given in the literature
Not given in the literature
Greenish powder
May be used in wash liquors and
oxidizing and reducing discharge
pastes
Mixtures of cellulose, protein
fibers, and nylon
C. I. Fluorescent Brightener 38
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the literature
Not given in the literature
Uvitex TW (Ciba-Geigy Corp.)
Not given in the literature
Not given in the literature
Not given in the literature
Stable to peroxide, chloride,
and peracetic acid. Good fast-
ness to light on acetate, polyes-
ters , and acrylics.
Polyester, acrylic, and protein
fibers
Nylon, acetate
Cellulose
C. I. Fluorescent Brightener 38 is not being manufactured at
the present time.
A-26
-------
C. I. Fluorescent Brightener 39
C, I. Fluorescent Brightener 39 (Uvitex U, Ciba-Geigy Corp.)
is not being manufactured at the present time.
C. I. Fluorescent Brightener 40
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
C. I. 40647
[7426-67-7]
Blankophor G (Farbenfabriken
Bayer A . G . , Germany)
4,4' -Bis (6-sulf o-2H-naphtho [1,2-
d] triazol-2-yl) -2,2' -stilbenedi-
sulfonic acid, tetrasodium salt
Blue
Stable to peroxide and hydrosul-
fite
Poor fastness to chlorine
Good fastness to washing
Cellulose, protein fibers, poly-
amide fibers, acetate
C. I. Fluorescent Brightener 40 is not being manufactured at
the present time.
A-27
-------
C.I. Fluorescent Brightening Agent 41
Colour Index Number
C. A. Registry Number
Commercial Name
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
C. I; 49015
[1483-30-3]
Uvitex RS (Ciba-Geigy Corp.)
Z-Styrylbenzothiozole
C15HnNS
Reddish-blue
Orange-yellow powder
Good fastness to chlorine
Stable to hypochlorite
Cellulose, nylon
C. I. Fluorescent Brightener 42
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in the" literature
Not given in the literature
Uvitex GS (Ciba-Geigy Corp.)
Stilbene derivative
Not given in the literature
Green
Yellow powder
Good fastness to chlorine
Cellulose and Nylon
C. I. Fluorescent Brightener 43
Application and properties are very similar to those of C. I.
Fluorescent Brightener 48.
C. I. Fluorescent Brightener 43 is not being manufactured at
the present time.
A-28
-------
C. I. Fluorescent Brightener 44
Colour Index Number
C. A. Registry Number
'''I'' - , la-.fe
Commercial Names
Chemical.
Molecular Formula
Fluorescence - -
Properties
Applications -
C. I. Fluorescent Brightener 45
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
Not given in, the literature
-YutfcmjH xsbftT vjLsoIo;
Not given in,the literature
^^ LJ-'Y f\ * * .,.,-.*._<_ *.
Blancol W (L. B. Holliday and
Co., Ltd., England)
Aminocoumarin derivative
Not given in the literature
Bluish-violet
Fast to peroxide and to reducing
agents . -^vs ^svo;!'!
Protein fibers,
Not given in the literature
Not given in the literature
Uvitex SIA (Ciba-Geigy Corp.)
Heterocyclic
Not given in the literature
Blue
Very good fastness to chlorine
and peroxide
Cellulose, acetate, nylon
GAF Corp. reported production and sales of Fluorescent Brighten-
er 45 to the U.S. Tariff Commission in 1972. No production figures
are given; they are included in the total brightener production
figures.
A-29
-------
C. I. Fluorescent Brightener 46 *
Colour Index Number C, I. 46625
C. A. Registry Numbers [4434-38-2]
[6416-68-8], sodium salt
Commercial Names Tlnbpal BBS (Ciba-Geigy Corp.)
Chemical Class 4-(2H-Naphth6[l,2-d]triaz61-2-
yl)-2-stilbenedisuifonic acid,
sodium salt
Molecular Formula C^BI 7^038 Na
Fluorescence Slightly bluish
Properties --,. Very good fastness on polyamldes
Applications Soaps, detergents
Ciha-Geigy Corp. reported production and sales of Fluorescent
Brightener 46 to the U.S. Tariff Commission in 1972. No production
figures are given; they are included in the total brightener pro-
duction figures.
A-30
-------
C. I. Fluorescent Brightener 47
Colour Index Number Not given in the literature
C. A. Registry Number Not given in the literature
Commercial Names Tinopal GS (Ciba-Geigy Corp.)
Chemical Class , Stilbyl-naphthotriazole derivative
Molecular Formula Not given in the literature
Fluorescence Greenish
Properties Orange-yellow powder
Very good fastness on polyamides
Cellulosic fibers, protein fibers,
polyamide fibers
Applications Soaps, detergents
According to the U.S. Tariff Commission Reports, 33,951
pounds of Fluorescent Brightener 47 were imported into the U.S.
in 1972.
A-31
-------
C. I. Fluorescent Brightener 48
Colour Index Number C.I. 40640
C. A. Registry Number [30587-99-6]
[6826-44-4], disodium salt
Commercial Names Blancol TW (L. B. Holliday and
Co., Ltdi, England); Fluorosol
WS (Allied Chemical and Dye
Corp.); Ultraphor WT (Badische
Anilin & Soda Fabrik A.G.,
Germany)
Chemical Class 4 , 4 ' - ( 2-Oxo-4-lmidazolin-4 , 5-diyl) -
dibenzenesulfonic acid, disodium
salt .. .
Molecular Formula C.l 5^12^20782 * ^a
Fluorescence Blue
Properties Moderate fastness to. chlorine
Stable to peroxide and to reducing
agents
Applications Protein fibers
According to U.S. Tariff Commission reports, 5,570 Ibs. of
Fluorescent Brightener 48 were imported into the U.S. in 1972.
Since there is insufficient information to establish correla-
tions between the remainder of the Fluorescent Brightener numbers
and molecular formulas, the molecular formula entry will not appear
in the following tables (C. I. Fluorescent Brighteners 155, 243,
and 245 are exceptions) .
There are no Colour Index numbers given for the remaining
C. I. Fluorescent Brightener numbers. This item will not appear
in the following tables (C. I. Fluorescent Brighteners 74, 243,
and 245 are exceptions) .
A-32
-------
C. I. Fluorescent Brightener 49
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Leucophor BS (Sandoz, Inc.);
Rylux BS, BSP (Chemopol, Czech.)
Bistriazinylaminostilbene
Bluish
Maroon-colored liquid
Anion-active, very stable to
acids and alkalis, light-sensi-
tive in solution
Cellulose
Nylon
Sandoz colors and chemicals reported production and sales of
Fluorescent Brightener 49 to the U.S. Tariff Commission in 1972,
No figures are given; they are included in the total brightener
production figures.
According to the U.S. Tariff Commission, 5,570 Ibs. of Fluor-
escent Brightener 49 were imported into the U.S. in 1972. ;
C. I. Fluorescent Brightener 50
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
i
Properties
Applications
Not given in the literature
Leucophor BB (Sandoz, Inc.)
Derivative of 4,4'-diamino-2,2'-
stilbenedisulfonic acid
Bluish
Readily soluble in hot water
Fastness: Acid, good; chlorine,
moderate; Light, good; Washing,
moderate
Cellulose
A-33
-------
C. I. Fluorescent Brightener 51
C. A. Registry Number Not given in the literature
Commercial Names Ultraphor API (Badische Anilin
& Soda Fabrik A. G., Germany)
Chemical Class Naphthalic acid derivative
Fluorescence Bright blue
Properties Not substantive to animal fibers
or cellulose. Unaffected by
hot water.
Fastness: Alkali, moderate;
Chlorine, light and washing,
very good
Applications Acetate, nylon, acrylic and
polyester fibers
C. I. Fluorescent Brightener 51 is not being manufactured at
the present time.
-------
C. I. Fluorescent Brightener 52
C. A. Registry Number Not given in the literature
Commercial Names Blancol WNS (L. B. Holliday &
Co., Ltd., England); Kayaphor
WN (Nippon Kayaku Co., Ltd.,
Japan); Leucophor WS, Leucopur
Base (Satido?., Inc.); Mikephor
WS (Mitsui Chemical Industry,
Ltd., Japan); Whitex WS (Sumi-
tomo Chemical Co., Ltd., Japan)
Chemical Class Coumarin derivative
Fluorescence Bluish violet
Properties Readily soluble in cold water.
Solution susceptible to prolonged
exposure to light.
Fastness: Washing, moderate to
gocd; Light, moderate
Applications Prntein fibers, acetate, nylon
Sandoz Colors and chemicals reported production and sales
of Fluorescent Brightener 52 to the U.S. Tariff Commission in 1972.
No production figures are given; they are included in the total
brightener production figures.
According to the U.S. Tariff Commission reports, 3,527 Ibs.
of Fluorescent Brightener 52 were imported into the U.S. in 1972.
A-35
-------
C. I. Fluorescent Brightener 53
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Blancol N62532 (L. B. Holliday
and Co., Ltd., England)
Aminocoumarin derivative
Reddish-blue
Stable to acids, peroxide,
and dithionite
Protein fibers, nylon, acetate
Soaps and detergents
C. I. Fluorescent Brightener 53 is not being manufactured at
the present time.
C. I. Fluorescent Brightener 54
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Tinopal WG (Ciba-Geigy Corp.);
Whitex WG (Sumitomo Chemical
Co., Ltd., Japan)
Not given in the literature
Greenish blue
Good solubility in water. Stable
to dithionate
Fastness: Light and washing
(protein fibers), good; Light
(nylon) good; Washing (nylon),
fairly good
Protein fibers, nylon
Ciba-Geigy reported production and sales of Fluorescent
Brightener 54 to the U.S. Tariff Commission in 1972. No production
figures are given; they are included in the total brightener
production figures.
A-36
-------
C. I. Fluorescent Brightener 55
C. A. Registry Number [12768-90-0]
Commercial Names Tiriopal AN (Ciba-Geigy Corp.)
Whitex AN (Sumitomo Chemical
Co., Ltd., Japan)
Chemical Class Oxacyanin derivative
Fluorescence . Reddish blue
Properties White powder
Substantive to silk, wook, and
cellulose
Compatible with cationic sof-
teners
Fastness: Chlorine, poor; Light,
very good; Washing, moderate
Applications Acetate, nylon, and acrylic
fibers
According to the U.S. Tariff Commission reports, 220 Ibs.
of Fluorescent Brightener 55 were imported into the U.S. in 1972.
C. I. Fluorescent Brightener 56
This C.I. generic name is discontinued. Those brighteners
formerly listed under it now appear under C. I. Fluorescent Brighten-
er 61.
A-3T
-------
C. I. Fluorescent Brightener 57
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Uvitex W (Ciba-Geigy Corp.)
Not given in the literature
Not given in the literature
insoluble in water
Soluble in organic solvents and
fatty acids
Protein fibers, acetate, nylon
C. I. Fluorescent Brightener 57 is not being manufactured
at the present time. . .
C. I. Fluorescent Brightener 58
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Uvitex NA (Ciba-Geigy Corp.)
Not given in the literature
Not given in the literature
Stable to peroxide and dithionite
Protein, acetate, nylon, and
acrylic fibers
C. I. Fluorescent Brightener 58 is not being manufactured at
the present time.
A-38
-------
C. I. Fluorescent Brightener 59
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Tinopal RBN (Ciba-£eigy Corp.)
Stilbene-triazole-sulfonic acid
derivative
Slightly reddish blue
Greenish-yellow powder
Fastness: Chlorine, very good;
Light, good; Washing (cellulose),
moderate, (nylon) very good
Protein fibers, nylon
Ciba-Geigy Corp. reported production and sales of Fluorescent
Brightener 59 to the U.S. Tariff Commission in 1972. No production
figures are given; they are included in the total brightener pro-
duction figures.
C. I. Fluorescent Brightener 60
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Blancol 61690 (L. B. Holliday
and Co., Ltd., England)
Cationic-npnionic complex
Bluish violet
Stable to dithionite and peroxide
Protein fibers, acetate, nylon
A-39
-------
C. I. Fluorescent Brightener 61
C. A. Registry Number [12224-04-3]
Commercial Names Blancophor AW, FFG; Tintophen
AW, FFG (GAF Corp.); Calcofluor
White RW, RWP, SD (American
Cyanamid Co.); Uvitex WGS
(Ciba-Geigy Corp.)
Chemical Class Aminocoumarin derivative
Fluorescence Bluish-violet
Properties Soluble in aqueous solution
and in alcohol; insoluble in
water
Applications Wool, nylon, acetate, silk
Ciba-Geigy reported production and sales to the U.S. Tariff
Commission in 1972. No production figures are given; they are
included in the total brightener production figures.
C. I. Fluorescent Brightener 62
C. A. Registry Number Not given in the literature
Commercial Names Uvitex NL (Ciba-Geigy Corp.)
Chemical Class Not given in the literature
Fluorescence Not given in the literature
Properties Excellent fastness to light
Applications Nylon
C. I. Fluorescent Brightener 62 is not being manufactured at
the present time.
A-ltO
-------
C. I. Fluorescent Brightener 63
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in.the literature
Blancol BT (L. B. Holliday
and Co., Ltd., England)
Triazinylaminostilbene derivative
Blue
Effect not cumulative on re-
peated laundering
Cellulose
C. I. Fluorescent Brightener 64
This C. I. generic name is discontinued. The brighteners
formerly listed under it now appear under C. I. Fluorescent
Brightener 28.
C. I. Fluorescent Brightener 65
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Uvitex NSI (Ciba-Geigy Corp.)
Not given in the literature
Not given in the literature
Good fastness to washing
Cellulose
C. I. Fluorescent Brightener 65 is not being manufactured
at the present time.
A-Ul
-------
C. I. Fluorescent Brightener 66
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Blancophor A-3, Tintophen A3
(GAF Corp.)
Stilbene derivative
Bluish violet
Sparingly soluble in water
Good fastness to chlorine (on
the fiber)
Soaps
C. I. Fluorescent Brightener 67
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Tintophen CX (General Dyestuff
Co.)
Bistriazinylaminostilbene deri-
vative
Blue (peak at 440 nm)
Sparingly soluble in water
Disperses well in soap
Soaps for laundering cotton
C. I. Fluorescent Brightener 67 is not being manufactured
at the present time.
-------
C. I. Fluorescent Brightener 68
This C. I. generic name is discontinued. The brighteners
formerly listed under it now appear under C. I. Fluorescent
Brightener 61.
Cincinnati Malacron Chemicals, Inc. and GAF Corp. reported
production and sales of Fluorescent Brightener 68 to the U.S.
Tariff Commission in 1972. No figures are given; they are in-
cluded in the total brightener production figures.
The production figures which have been listed separately in
the past for Fluorescent Brightener 68 are as follows:
1960 63,000 Ibs.
1961 72,000 Ibs.
1962 100,000 Ibs.
1964 31,000 Ibs.
C. I. Fluorescent Brightener 69
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Leucophor DC (Sandoz Colors
and Chemicals)
Coumarin derivative
Bluish-violet
Soluble in hydrocarbons, chlori-
nated hydrocarbons, acetone,
ethyl acetate
All fibers
-------
C.I. Fluorescent Brightener 70
C. A. Registry Number Not given in the literature
Commercial Names, Tinopal PCR (Ciba-Geigy Corp.)
Chemical Class Stilbyl-naphthotriazole deriva-
tive
Fluorescence Bluish
Properties Very good fastness to light
Applications Plastics
A-UU
-------
C. I. Fluorescent Brightener 71
C. A. Registry Number Not given in the literature
; ,
Commercial Names Blancophor DS-86 (GAtf Corp.);
Calcofluor White RC (American
Cyanamid Co.); Leukophor DU, DUK,
Leukopur PAM (Sandoz, Inc.); Pho-
tine CBV, CBVS (Hickson and Welch,
Ltd., England; S. A. Rovira,
Spain)
Chemical Class . Stilbene derivative
Fluorescence . Bluish-violet
Properties Water dispersible
, Stable to perborate but not to
chlorine
Fastness: Acid, poor; Alkali,
very good; Chlorine, very good;
Dithionate, very good; Peroxide,
very good; Light, good
Applications Laundry compositions containing
anionic or nonionic detergents
for use on cellulose
American Cyanamid Co. and GAF Corp. reported production and
sales of Fluorescent Brightener 71 to the U. S. Tariff Commission
in 1972. No figures are given; they are included in the total
brightener production figures.
C. I. Fluorescent Brightener 72
C. A. Registry Number Not given in the literature
Commercial Names Tinopal E (Ciba-Geigy Corp.)
Chemical Class Stilbyl-naphthotriazole derivative
Fluorescence Not given in the literature
Properties Fastness: Light, good; Washing,
very good
Applications Polyester fibers
Plastics
-------
C. I. Fluorescent Brightener 73
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Blancol SS (L. B. Holliday and
Co., Ltd., England)
Trimethyldihydropyridine deriva-
tive
Blue
Soluble in organic solvents
Insoluble in water
Lacquers and waxes
C. I. Fluorescent Brightener 74
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
C. I. 45550
Not given in the literature
Fluorol 5G
Xanthene derivative
Greenish-yellow
Soluble in organic solvents
Insoluble in water
Lacquers and coatings
C. I. Fluorescent Brightener 74 is not being manufactured at
the present time.
-------
C. I. Fluorescent Brightener 75
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications .
Not given in the literature
Fluorescent Brilliant Yellow R
(L. B. Holliday and Co.,
England); Fluorol 7GA (GAP Corp.)
Xanthene derivative
Green
Soluble in organic solvents
Insolvent in water
Lacquers and coatings
According to the U. S. tariff Commission reports, 1,200
pounds of Fluorescent Brightener 74 were imported into the U. S.
in 1972.
C. I. Fluorescent Brightener 76
C. A. Registry Number
Commercial Names
Chemical, Class
Fluorescence
Properties
Not given in the literature
Fluorol OB (GAF Corp.)
Naphthalimide derivative
Greenish-blue
Insoluble in water and hydrocar-
bons
Soluble in other organic solvents
Applications
Lacquers and coatings
-------
C. I. Fluorescent Brightener 77
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications ;
Not given in the literature
Fluorol OBR (GAF Corp.)
Stilbene derivative
Reddish-blue
Soluble in organic solvents
Insoluble in water
Lacquers and coatings
C. I. Fluorescent Brightener 77 is not being manufactured at
the present time.
C. I. Fluorescent Brightener 78
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Blancol 62531 (L. B. Holliday
and Co., Ltd., England)
Aminocoumarin derivative
Bluish-violet
Soluble in organic solvents
Insoluble in water
Lacquers, coatings, shellac
Plastics
A-U8
-------
C. I. Fluorescent Brightener 79
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12676-63-0]
Leukophor A, AC (Sandoz, Inc.):
Delft White BSM (Delfland Pro-
dukten N.V., Holland)
Not given in the literature
Not given in the literature
Good fastness to acid, alkali,
and chlorine
Cellulose
C. I. Fluorescent Brightener 80
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Delft White GS (Delfland Pro-
dukten N.V., Holland)
Not given in the literature
Yellowish-green
Not given in the literature
Cellulose
C. I. Fluorescent Brightener 81
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Delft White BSW (Delfland
Produkten N.V. (Holland)
Not given in the literature
Not given in the literature.
Good fastness to acid, alkali,
and chlorine
Cellulose
A-U9
-------
C. I. Fluorescent Brightener 82
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Delft White RS (Delfland Pro-
dukten N.V., Holland)
Stilbene derivative
Not given in the literature
Fastness: Acid, good; alkali,
excellent; Heat, good; Light,
good
Cellulose
C. I. Fluorescent Brightener 83
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Citalba B (Aziende Color! Na-
zionali Affini A.C.N.A., Italy)
Stilbene derivative
Bluish
Poor fastness to chlorine;
stable to dithionite and peroxide
Protein fibers, nylon
Cellulose
C. I. Fluorescent Brightener 83 is not being manufactured at
the present time.
A-50
-------
C. I. Fluorescent Brightener 84
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-05-4]
Kayaphor A, AK (Nippon Kayaku
Co., Ltd., Japan); Mikephor BA
(Mitsui Toatsu Chemicals, Inc.,
Japan); Whitex BC, BCK, BO, BT
(Sumitomo Chemical Co., Ltd.,
Japan)
Bistriazinylaminostilbene
derivative
Bluish-violet
Good solubility in water
Good fastness to chlorine, light,
peroxide, and washing
Cellulose
Paper
C. I. Fluorescent Brightener 85
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-06-5]
Kayaphor AB, B, BB, BNK, LB
(Nippon Kayaku Co., Ltd., Ja-
pan) ; Leukophor DK (Sandoz Co-
lors and Chemicals); Mikephor
BP, BX, BX Extra 200 (Mitsui
Toatsu Chemicals, Inc., Japan);
Whitex BH, BK, LBH (Sumitomo
Chemical Co., Ltd., Japan)
Bistriazinylaminostilbene
derivative
Bluish-violet
Not given in the literature
Cellulose
Paper
A-51
-------
C. I. Fluorescent Brightener 86
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-07-6]
Kayaphor FB (Nippon Kayaku Co.,
Ltd., Japan); Mikephor BI
(Mitsui Toatsu Chemicals, Inc.,
Japan); Whitex BN, LSB (Sumitomo
Chemical Co., Ltd., Japan)
Bistriazinylaminostilbene
derivative
Bluish-violet
Good solubility in water
Good fastness to chlorine, light,
peroxide, and washing
Cellulose, paper
Soaps, detergents
C. I. Fluorescent Brightener 87
C. A. Registry Number
Commercial Names
Chemical Class
Flourescence
Properties
Applications
Not given in the literature
Kayaphor S (Nippon Kayaku Co.,
Ltd., Japan)
Bistriazinylaminostilbene
derivative
Bluish-violet
Very good solubility in water
Good fastness to chlorine,
light, peroxide, and washing
Cellulose
Paper
C. I. Fluorescent Brightener 88
This C. I. generic name is discontinued. The brighteners for-
merly listed under it now appear under C. I. Fluorescent Brightener 24.
A-52
-------
C. I. Fluorescent Brightener 89
This C. I. generic name is discontinued. The brighteners
formerly listed under it now appear under C. I. Fluorescent
Brightener 52.
C. I. Fluorescent Brightener 90
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-08-7]
Kayaphor AS, ASC (Nippon Kayaku
Co., Ltd., Japan); Mikephor BS
(Mitsui Toatsu Chemicals, Inc.,
Japan); Whitex BF, EOF, HP (Su-
mitomo Chemical Co., Ltd.,
Japan)
Bistriazinylaminostilbene deri-
vative
Bluish-violet
Fairly soluble in water
Good fastness to chlorine, light,
and peroxide
Nylon
Cellulose
Paper
C. I. Fluorescent Brightener 91
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Kayalight B (Nippon Kayaku Co.,
Ltd., Japan)
Coumarin derivative
Bluish-violet
Very good solubility in organic
solvents
Poor solubility in water
Moderately fast to light and
washing
Wool, silk
Synthetic resins
A-53
-------
C. I. Fluorescent Brightener 92
This C. I. generic name is discontinued. The brightener for-
merly listed under it now appears under C. I. Fluorescent Brightener
84.
C. I. Fluorescent Brightener 93
This C. I. generic name is discontinued. The brightener for-
merly listed under it now appears under C. I. Fluorescent Brigh-
tener 24.
C. I. Fluorescent Brightener 94
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Mikephor FP (Mitsui Toatsu
Chemicals, Inc., Japan)
Triazinylstilbene derivative
Bright blue
Not given in the literature
Cellulose
C. I. Fluorescent Brightener 94 is not being manufactured at
the present time.
C. I. Fluorescent Brightener 95
This C. I. generic name is discontinued. The brightener for-
merly listed under it now appears under C. I. Fluorescent Brigh-
tener 85.
-------
C. I. Fluorescent Brightener 96
This C. I. generic name is discontinued. The brightener for-
merly listed under it now appears under C. I. Fluorescent Brigh-
tener 85.
C. I. Fluorescent Brightener 97
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Mikephor BH-2 (Mitsui Toatsu
Chemicals Inc., Japan)
Bistriazinylamino-stilbenedi-
sulfonic acid derivative
Bright blue
Not given in the literature
Cellulose
C. I. Fluorescent Brightener 97 is not being manufactured at
the present time.
C. I. Fluorescent Brightener 98
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Fluolite L Tablets (Imperial
Chemical Industries, Ltd.,
England)
Stilbene derivative
Blue
Soluble in water but not in
organic solvents
Fastness: Alkali, very good;
Chlorine, good; Dithionite, very
good; Peroxide, very good;
Washing, very good
Cellulose
C. I. Fluorescent Brightener 98 is not being manufactured at
the present time.
A-55
-------
C. I. Fluorescent Brightener 99
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
FluoliCe MP Liquid (Imperial
Chemical Industries, Ltd.,
England)
Stilbene derivative
Blue
Soluble in water
Insoluble in organic solvents
Fastness: Acid, good; Alkali,
very good; Chlorine, good; Di-
thionite, very good; Peroxide,
very good; Washing, very good
Cellulose
Paper
C. I. Fluorescent Brightener 100
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12270-49-4]
Fluolite XNR (Imperial Chemi-
cal Industries, Ltd., England)
Stilbene derivative
Reddish-blue
Soluble in water
Insoluble in organic solvents
Fastness: Acid, very good;
Alkali, very good; Chlorine,
good; Dithionite, very good;
Peroxide, very good; Washing,
good
Protein fibers, nylon
Cellulose
Paper
A-56
-------
C. I. Fluorescent Brightener 101
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Tinopal ACA (Ciba-Geigy Corp.)
Not given in the literature
Reddish-blue
Fastness: Acid, very good;
Alkali, good; Chlorine, good;
Dithionite, good; Light, moder-
ate; Peroxide, Moderate; Washing,
good
Acrylic fibers
C. I. Fluorescent Brightener 102
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-09-8]
Paper White SP, SPSW, Pontamine
White SP Solution (E. I. du Pont
de Nemours and Co., Inc.)
Stilbene derivative
Greenish
Soluble in water
Stable to alum
Paper
E. I. du Pont de Nemours and Co. and Verona Corp. reported
production and sales of Fluorescent Brightener 102 to the U. S.
Tariff Commission in 1972. No production figures are given;
they are included in the total brightener production figures.
A-57
-------
C. I. Fluorescent Brightener 103
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Tinopal BST (Ciba-Geigy Corp.)
Triazinylstilbene derivative
Slightly bluish
Not given in the literature
Cellulose
According to the U. S. Tariff Commission reports, 220 pounds
of Fluorescent Brightener 103 were imported into the U. S. in
1972.
C. I. Fluorescent Brightener 104
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-10-1]
Kayaphor PN (Nippon Kayaku Co.,
Ltd., Japan); Tinopal RP (Ciba-
Geigy Corp.); Whitex RP (Sumi-
tomo Chemical Co., Ltd., Japan)
Bistriazinylaminostilbene
derivative
Bluish-violet
Very good solubility in water
Fastness: Acid, very good;
Alkali, very good; Chlorine,
good; Dithionite, very good;
Light, very good; Peroxide, good;
Washing, good
Wool, silk, nylon
Cellulose-wool unions;
Cellulose-nylon unions
A-58
-------
C. I. Fluorescent Brightener 105
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Calcofluor White CW (American
Cyanamid Co.)
Triazinylstilbene derivative
Bluish-white
Miscible in water in all
proportions
Insoluble in petroleum solvents
Fastness: Acid, good; Alkali,
good; Chlorine, poor; Dithionite,
very good; Light, good
Nylon
Cellulose
Paper
C. I. Fluorescent Brightener 105 is not being manufactured at
the present time.
C. I. Fluorescent Brightener 106
This C. I. generic name is discontinued.
C. I. Fluorescent Brightener 107
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Blancophor GS-33, Tintophen
GS-33 (GAF Corp.)
Stilbene derivative
Bright greenish-blue
Levels well
Cellulose
A-59
-------
C. I. Fluorescent Brightener 108
C. A. Registry Number Not given in the literature
Commercial Names Blancophor CB-32, Tintophen
CB-32 (GAP Corp.)
Chemical Class Stilbene derivative
Fluorescence Blue
Properties Levels well
Applications Cellulose
GAF Corp. reported production and sales of Fluorescent Brigh-
tener 108 to the U. S. Tariff Commission in 1972. No figures are
given; they are included in the total brightener production figures,
C. I. Fluorescent Brightener 109
C. A. Registry Number Not given in the literature
Commercial Names Blancophor SB, Tintophen SB
(GAF Corp.)
Chemical Class Stilbene derivative
Fluorescence Blue
Properties Very good solubility in water
Applications Paper
GAF Corp. reported production and sales of Fluorescent Brigh-
tener 109 to the U.S. Tariff Commission in 1972. No production
figures are given; they are included in the total brightener pro-
duction figures.
A-60
-------
C. I. Fluorescent Brightener 110
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Blancophor HL-32, HL-72, Tinto-
phen HL-32, HL-72 (GAF Corp.)
Stilbene derivative
Bright greenish-blue
Water soluble
Insensitive to pH change
Paper
C. I. Fluorescent Brightener 111
C. A. Registry Number
Commercial Names
Chemical Class
Flourescence
Properties
Applications
Not given in the literature
Whitening Agent Wolfen BV, BVP,
BVP 60/100 (Farbenfabriken
Wolfen, Germany)
Bluish-violet
Soluble in water; Anion-active
Fastness: Acid, sensitive;
Chlorine, moderate; Dithionite,
good; Light, very good; Wash-
ing, good
Nylon
Cellulose
A-6l
-------
C. I. Fluorescent Brightener 112
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12270-50-7]
Blankophor ACF (Farbenfabiriken
Bayer A. G., Germany); Ultra-
phor NA (Badische Anilin & Soda
Fabrik A. G., Germany)
Coumarin derivative
Blue
Soluble in hot water
Fastness: Acid, very good; Al-
kali, very good; Chlorine, very
good; Dithionite, very good;
Peroxide, Very good; Washing,
very good
Acetate
According to the U. S. Tariff Commission reports, 250
pounds of Fluorescent Brightener 112 were imported into the U. S.
in 1972.
C. I. Fluorescent Brightener 113
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Blankophor BA (Farbenfabriken
Bayer A. G., Germany)
Stilbene derivative
Bright bluish-violet
Yellowish,white powder
Water soluble
Fastness: Acid, moderate; Al-
kali, very good; Chlorine, good;
Dithionite, very good; Light,
good; Peroxide, very good;
Washing, very good
Cellulose
A-62
-------
C. I. Fluorescent Brightener 114
C. A. Registry Number [12270-51-8]
Commercial Names Blancofor BBV (Fabricacion
Nacional de Colorantes y Explo-
sives, S. A., Spain); Blankophor
BBV Extra (Farbenfabriken Bayer,
A. G., Germany); Heliofor CAS
(CEICH, Poland); Ultraphor GPB
(Badische Anilin & Soda Fabrik
A. G., Germany)
Chemical Class Stilbene derivative
Fluoresdence Bluish-violet
Properties Greenish-yellow powder
Water soluble
Fastness: Acid, very good; Al-
kali, very good; Chlorine, good;
Dithionite, very good; Light,
good; Peroxide, very good;
Washing, good
Applications Cellulose
Verona Corp. reported production and sales of Fluorescent
Brightener 114 to the U. S. Tariff Commission in 1970. No pro-
duction figures are given; they are included in the total brightener
figures.
C. I. Fluorescent Brightener 115
C. A. Registry Number Not given in the literature
Commercial Names Blankophor BE Extra (Farben-
fabriken Bayer A. G., Germany)
Chemical Class Stilbene derivative
Fluorescence Bluish-violet
Properties Water soluble
Fastness: Acid, moderate; Al-
kali, very good; Chlorine,
good; Dithionite, very good;
Light, good; Peroxide, very
good; Washing, good
Applications Cellulose
A-63
-------
C. I. Fluorescent Brightener 116
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Blancofor BP (Fabricacion Na-
cional de Colorantes y Explo-
sives S. A., Spain) Blankophor
BP Extra (Farbenfabriken Bayer
A. G., Germany)
Stilbene derivative
Blue
Fastness: Acid, moderate; Al-
kali, moderate; Dithionite, very
good; Light, good; Peroxide,
very good
Paper
C. I. Fluorescent Brightener 117
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Blancofor BPN (Fabricacion
Nacional de Colorantes y Explo-
sives S. A., Spain) Blankophor
BPN Extra (Farbenfabriken Bayer
A. G., Germany)
Stilbene derivative
Blue
Water soluble, insoluble in or-
ganic solvents
Fastness: Acid, good; Alkali,
moderate, Dithionite, very good;
Light, good; Peroxide, very good
Paper
A-6U
-------
C. I. Fluorescent Brightener 118
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Blankophor CE (Farbenfabriken
Bayer A. G., Germany)
Stilbene derivative
Bluish-green
Water soluble
Fastness: Acid, very good; Al-
kali, very good; Chlorine, very
good; Dithionite, very good;
Light, good; Peroxide, very good;
Washing, moderate
Cellulose
C. I. Fluorescent Brightener 119
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12270-52-9]
Blankophor REV (Farbenfabriken
Bayer A. G., Germany); Ultra-
phor RPB (Badische Anilin &
Soda Fabrik A. G., Germany)
Stilbene derivative
Reddish-violet
Water soluble
Fastness: Acid, very good; Al-
kali, very good; Chlorine,
good; Dithionite, very good;
Light, good; Peroxide, very
good; Washing, good
Cellulose
According to the U. S. Tariff Commission reports, 125,040
pounds of Fluorescent Brightener 119 was imported into the U. S,
in 1972.
A-65
-------
C. I. Fluorescent Brightener 120
This C. I. generic name is discontinued. The fluorescent
brightener formerly listed under it now appears under C. I.
Fluorescent Brightener 104.
C. I. Fluorescent Brightener 121
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-11-2]
Blancofor BBH (Fabricacion
Nacional de Colorantes y Ex-
plosives S. A., Spain); Blanko-
phor DCB (Farbenfabriken Bayer
A. G., Germany)
Stilbene derivative
Bright bluish-violet
Fastness: Acid, very good;
Alkali, very good; Light (acry-
lic) very good, (acetate and
nylon) good; Washing, very good
Acetate, triacetate, nylon,
acrylics
According to the U. S. Tariff Commission reports, 79,210
pounds, of Fluorescent Brightener 121 were imported into the U. S.
in 1972.
C. I. Fluorescent Brightener 122
This C. I. generic name is discontinued.
A-66
-------
C. I. Fluorescent Brightener 123
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Rylux D (Chemapol, Czech.)
Morpholine derivative
Bright blue
Not given in the literature
Not given in the literature
C. I. Fluorescent Brightener 124
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Blankophor SN (Farbenfabriken
Bayer A. G., Germany)
Pyrazolone derivative
Bluish
Not given in the literature
Soap
-------
C. I. Fluorescent Brightener 125
C. A. Registry Number Not given in the literature
Commercial Names Calcofluor White EDW,. PUM (Am-
erican Cyanamid Co.)
Chemical Class Triazinylstilbene derivative
Fluorescence Slightly reddish-blue
Properties Amber liquid
Specific gravity 1.23
Fluorescent emission at 440 mu
Compatible with anionic and
nbnionic materials
Miscible with water in all pro-
portions
Applications Padding with resins
Cellulose
' Nylon
American Cyanamid Co. reported production and sales of Fluores-
cent Brightener 125 to the U. S. Tariff Commission in 1972. No
production figures are given; they are included in the total
brightener production figures.
A-68
-------
C. I. Fluorescent Brightener 126
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Hiltamine Arctic Paper White
(Hilton-Davis Div. of Sterling
Drug Co.)
Triazinylstilbene derivative
Bluish-violet
Liquid in form; anionic in na-
ture
Fastness: Acid, very good; Al-
kali, good; Chlorine, moderate;
Dithionite, good; Light, poor;
Peroxide, good; Washing, good
Suitable for use with practical-
ly all paper-making additives
Cellulose
Hilton-Davis Div. of Sterling Drug Corp. reported production
and sales of Fluorescent Brightener 126 to the U. S. Tariff Com-
mission in 1972. No production figures are given; they are in-
cluded in the total brightener production figures.
C. I. Fluorescent Brightener 127
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Hiltamine Arctic White Acid Sta-
ble (Hilton-Davis Div. of Sterling
Drug Co.)
Triazinylstilbene derivative
Bluish-violet
Liquid in form; anionic in nature
pH 8.5-9.5
Substantive to all cellulesic fibers
Compatible with most anionic and
nonionic textile additives
Cellulose
Textiles, silk, acetate
Exhaust padding
Thermosetting resin finishes
A-69
-------
C. I. Fluorescent Brightener 128
C. A. Registry Number Not given in the literature
Commercial Names Hiltamirie Arctic White DHL
(Hilton-Davis Div. of Sterling
Drug Co.)
Chemical Class Triazinylstilbene derivative
Fluorescence Bluish-violet
Properties Liquid in form; anionic in nature
pH 8.5-10.5
Substantive to all cellulosic
fibers
Compatible with cationic, ani-
onic, and nonionic softeners
Applications Cellulose
Paper
Silk, acetate
Fabric softeners
Hilton-Davis Div. of Sterling Drug Corp. reported production
and sales of Fluorescent Brightener 128 to the U. S. Tariff Com-
mission in 1972. No production figures are given; they are included
in the total brightener production figures.
C. I. Fluorescent Brightener 129
C. A. Registry Number Not given in the literature
Commercial Names Hiltamine Arctic White DP
(Hilton-Davis Div. of Sterling
Drug Co.)
Chemical Class Stilbene derivative
Fluorescence Bluish-violet
Properties Fastness: Acid, good; Alkali,
good; Chlorine, moderate; Di-
thionite, good; Peroxide, good
Applications Cellulose, silk, nylon, acetate
C. I. Fluorescent Brightener 129 is not being manufactured at
the present time.
A-70
-------
C. I. Fluorescent Brightener 130
C. A. Registry Number Not given in the literature
Commercial Names Calcofluor White LD (American
Cyanamid Co.); Hiltamine Arctic
White N (Hilton-Davis Div. of
Sterling Drug Co.)
Chemical Class Coumarin derivative
Fluorescence Violet
Properties Nonionic in nature
Insoluble in water; soluble in
alcohol, glycols, and Cellusolve
Applications Wool, nylon, silk, acetate,
triacetate, and acrylic fibers
Protein fibers
American Cyanamid Co. reported production and sales of Fluores-
cent Brightener 130 to the U. S. Tariff Commission in 1972. No
production figures are given; they are included in the total
brightener production figures.
C. I. Fluorescent Brightener 130:1
C. A. Registry Number Not given in the literature
Commercial Names Hiltamine Arctic White WNOA
(Hilton-Davis Div. of Sterling
Drug Co.)
Chemical Class Coumarin derivative
Fluorescence Not given in the literature
Properties Nonionic in nature
Readily dissolves in warm water
Applications Detergent formulation
Polyamides, acetate, triacetate
A-71
-------
C. I. Fluorescent Brightener 131
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Hlltamine Arctic White SP New
(Hilton-Davis Div. of Sterling
Drug Co.)
Stilbene derivative
Bluish-violet
Fastness: Acid, good; Alkali,
good; Chlorine, moderate; Di-
thionite, good; Light, poor;
Peroxide, good; Washing, good
Cellulose, silk, acetate
C. I. Fluorescent Brightener 131 is not being manufactured
at the present time.
C. I. Fluorescent Brightener 132
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Hiltamine White FMC, Mirawhite
White FAC (Hilton-Davis Div. of
Sterling Drug Co.)
Stilbene derivative
Blue
Soluble in glycols and Cellosolve
Fastness: Acid, poor; Alkali,
very good; Chlorine, very good;
Hydrosulphite, very good;
Light, good; Peroxide, very
good; Washing, very good
Cellulose, silk, acetate, acrylics
A-72
-------
C. I. Fluorescent Brightener 133
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Uvitex A (Ciba-Geigy Corp.)
Heterocyclic
Blue
Very good fastness to light and
washing
Acrylic staple fiber
C. I. Fluorescent Brightener 134
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Ultraphor BP (Badische Anilin
& Soda Fabrik A. G., Germany);
Uvitex CF (Ciba-Geigy Corp.)
Stilbene derivative
Blue
Good solubility in water. Sta-
ble to acids, peroxide bleach
liquors and reducing agents
Fastness: Chlorine, good;
Light, good; Washing, very good
Cellulose, nylon, wool
According to the U. S. Tariff Commission reports, 25,792
pounds of Fluorescent Brightener 134 were imported into the U. S.
in 1972.
A-73
-------
C. I. Fluorescent Brightener 135
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-12-3]
Uvitex ERN Cone. P (Ciba-Geigy
Corp.); Whitex ERN (Sumitomo
Chemical Co., Ltd., Japan)
Heterocyclic
Reddish-blue
Excellent fastness to light and
very good fastness to washing
on polyester. Stable in chlorite
bleach liquors and peracetic
acid
Polyester, acetate, nylon,
polyvinyl fibers
C. I. Fluorescent Brightener 136
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Not given in the literature
Uvitex PRS (Ciba-Geigy Corp.)
Stilbene derivative
Reddish-blue
Very good solubility in water.
Good stability to acid and alkali
Applications
Paper, cellulose
-------
C. I. Fluorescent Brlghtener 137
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Uvitex SIG (Ciba-Geigy Corp.)
Not given in the literature
Not given in the literature
Limited build up on repeated
use. Good stability in hopy-
chlorite and peroxide liquors
Cellulose, acetate, nylon
C. I. Fluorescent Brightener 137 is not being manufactured at
the present time.
C. I. Fluorescent Brightener 138
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Nwt given in the literature
Uvitex S3B (Ciba-Geigy Corp.)
Not given in the literature
Not given in the literature
Good fastness to chlorine and
good stability to acid
Cellulose
C. I. Fluorescent Brightener 138 is not being manufactured at
the present time.
A-T5
-------
C. I. Fluorescent Brightener 139
C. A. Registry Number
Commercial Names
Chemical Class
Flourescence
Properties
Applications
Not given in the literature
Uvitex S2R (Ciba-Ceigy Corp.)
Not given in the literature
Not given in the literature
Considerable build up on repeated
use. Good fastness to chlorine
and good stability to salts.
Withstands normal spray tempera-
tures when incorporated in
soap or detergents
Cellulose
C. I. Fluorescent Brightener 140
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Uvitex SWN (Ciba-Geigy Corp.)
Rylux VPA (Chemopol, Czech.)
Heterocyclic
Blue
Good stability to salts. With-
stand normal spray temperatures
Wool, silk, acetate, nylon
Soaps, detergents
According to the U. S. Tariff Commission reports, 441
pounds of Fluorescent Brightener 140 were imported into the U. S,
in 1972.
A-76
-------
C. I. Fluorescent Brightener 141
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Uvitex SWR (Ciba-Geigy Corp.)
Not given in the literature
Not given in the literature
Good stability to salts.
Withstand normal spray tempera-
tures
Wool, silk, acetate, nylon
Soaps, detergents
C. I. Fluorescent Brightener 141 is not being manufactured
at the present time.
C. I. Fluorescent Brightener 142
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Uvitex VR (Ciba-Geigy Corp.)
Stilbene derivative
Blue; reflects green
Orange-yellow powder
Good fastness to washing and
stability to dithionite and
peroxide
Cellulose
A-T7
-------
C. I. Fluorescent Brightener 143
C. A. Registry Number v
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Supra White BN (Dye-Chem, Ltd.,
India)
Stilbene derivative
i
Bright blue
Not given in the literature
Cellulose, paper
C. I. Fluorescent Brightener 143 is not being manufactured at
the present time.
C. I. Fluorescent Brightener 144
I
C. A. Registry Number ,-y
-------
C. I. Fluorescent Brightener 145
!*_
C. A. Registry Number
Commercial Names
Chemical Class
Fluores cence
Properties
Applications
Not given in the literature
Fluolite SE (Imperial Chemical
Industries, Ltd., England);
Photine BL, CP (Hickson and
Welch, Ltd., England; S. A.
Rovira, Spain); Photine CSP (Hick-
son and Welch, Ltd., England)
Stilbene derivative
Blue
Excellent solubility in cold
water. Stability to acids
(and resin-catalyst combina-
tions) excellent. Low substan-
tivity. Levelling excellent
Fastness: Acid, very good; Al-
kali, very good; Chlorine,
moderate, Dithionite, very good;
Light, good; Peroxide very good;
Washing, good
Cellulose
C. I. Fluorescent Brightener 146
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Photine STV (Hickson and
Welch, Ltd., England); White
STV (Hickson and Dadajee Pri-
vate, Ltd., India)
Stilbene derivative
Bluish-violet
Not given in the literature
Not given in the literature
A-79
-------
C. I. Fluorescent Brightener 147
C. A. Registry Number [12224-13-4]
Commercial Names Amar Supra White BRN (Dye-
Chem., Ltd., India)
Chemical Class Stilbene derivative
Fluorescence Bright reddish-blue
Properties Very soluble in slightly warm
water
Fastness: Chlorine, fair;
Light, good; Washing, excellent
Applications Cellulose, paper
C. I. Fluorescent Brightener 148
C. A. Registry Number [12224-14-5]
Commercial Names Blankophor RPA (Farbenfabriken
Bayer A. G., Germany)
Chemical Class Stilbene derivative
Fluorescence Reddish-blue
Properties Solutions are not stable to
chlorine or chlorite
Fastness: Chlorine, good; Light,
good; Washing, very good
Applications Nylon
According to the U. S. Tariff Commission reports, 5,250
pounds of Fluorescent Brightener 148 were imported into the U. S.
in 1972.
A-80
-------
C. I. Fluorescent Brightener 149
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12216-91-0]
Fluolite ttWP (Imperial Chemical
Industries, Ltd., England)
Bistriazinylaminostilbene
derivative
Not given in the literature
Readily soluble in water and
very resistant to acid conditions.
On paper its fastness to light
is only moderate but it is re-
sistant to chlorine, acid and
alkali
Cellulose, paper
C. I. Fluorescent Brightener 149 is not being manufactured at
the present time.
C. I. Fluorescent Brightener 150
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-15-6]
Tinopal IT (Ciba-Geigy Corp.)
Heterocyclic
Blue
Has both reducing and brighten-
ing properties. It is extremely
sensitive to acid. Fastness to
light and washing is good
Wool, cotton, nylon
A-81
-------
C. I. Fluorescent Brightener 151
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-16-7]
Tinopal ABR (Ciba-Geigy Corp.)
Triazinylaminostilbene derivative
Reddish-blue
Soluble in water, ethylene- and
diethyleneglycol and Cellosolve.
Insoluble in benzene, chloroben-
zene, ether, chloroform and
acetone
Fastness: Acid, very good; Al-
kali, very good; Chlorine, good;
Dithionite, very good; Light,
good; Peroxide, very good
Cellulose, wool, nylon
C. I. Fluorescent Brightener 152
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Tinopal PG (Ciba-Geigy Corp.)
Coumarin derivative
Greenish-blue
Insoluble in water, soluble
in benzene, chlorobenzene,
acetone and Cellosolve
Fastness: Acid, very gook; Al-
kali, good; Chlorine, good;
Dithionite, very good; Light,
very good; Peroxide, good
Nylon, acetate, polyester
A-82
-------
C. I. Fluorescent Brightener 153
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-18-9]
Tinopal CWS (Ciba-Geigy Corp.);
Whitex BWB, Whitex SF (Sumi-
tomo Chemical Co., Ltd., Japan)
Triazinylaminostilbene deriva-
tive
Blue
Soluble in water, ethylene and
diethylene glycols and Cello-
solve. Insoluble in benzene,
chlorobenzene, ether, chloro-
form and acetone
Fastness: Acid, poor; Alkali,
very good; Chlorine, good;
Dithionite, very good; Light,
good; Peroxide, very good
Cellulose, wool, nylon
Detergent compositions
I. Fluorescent Brightener 154
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-19-0]
Tinopal UP (Ciba-Geigy Corp.)
Triazinylaminostilbene derivative
Blue
Compatible with cationic soften-
ers. Soluble in water, ethylene
and diethyleneglycol and Cello-
solve. Insoluble in benzene,
chlorobenzene, ether, chloro-
form and acetone
Fastness: Acid, poor; Alkali,
very good; Chlorine, good; Di-
thionite, very good; Light,
good; Peroxide, very good
Cellulose, paper
Wool, nylon
A-83
-------
C. I. Fluorescent Brightener 155
Colour Index Number
C. A. Registry Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
C. I. 45555
[6250-49-3]
Not given in the literature
2 , 8-dimethylnaphtho [3,2, 1-kl ] -
xanthen-9-ol, acetate
Applications
Green
Soluble in hydrocarbons, the
solutions being stable to heat
and light. Also soluble in
alcohols, esters, ketones and
plasticisers
Lubricating oils
C. I. Fluorescent Brightener 156
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-20-3]
Tinopal ethyl (Ciba-Geigy Corp.)
Coumarin derivative
Blue
Insoluble in water, soluble in
benzene, chlorobenzene, chloro-
form, acetone and Cellosolve
Fastness: Acid, very good;
Alkali, moderate-good; Chlo-
rine, very good; Dithionite,
good; Light, very good; Peroxide,
moderate-good
Nylon, acetate, polyesters
A-8U
-------
C. I. Fluorescent Brightener 157
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-21-4]
Tinopal LAT (Ciba-Geigy Corp.)
Coumarin derivative
Greenish-blue
Insoluble in water, soluble in
benzene, chlorobenzene, chloro-
form, acetone, Cellosolve and
dioxan
Stable to chlorite
Fastness: Acid, very good; Al-
kali, good; Chlorine, very good;
Dithionite, very good; Light,
good; Peroxide, good
Acetate, triacetate, acrylics
C. I. Fluorescent Brightener 158
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-22-5]
Calcofluor White Art (American
Cyanamid Co.)
Triazole derivative
Reddish
Excellent stability to chlorite
and excellent fastness to light
Acrylics
American Cyanamid Co. reported production and sales of Fluores-
cent Brightener 158 to the U. S. Tariff Commission in 1972. No
production figures are given; they are included in the total
brightener production figures.
A-85
-------
C. I. Fluorescent Brightener 159
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-23-6]
Calcofluor White ABT (American
Cyanamid Co.)
Azole derivative
Blue
Amber liquid in physical form
Specific gravity 1.10
Miscible in water and in acetic
acid
Acrylic fibers
American Cyanamid Co. reported production and sales of Fluor-
escent Brightener 159 to the U. S. Tariff Commission in 1972. No
production figures are given; they are included in the total
brightener production figures.
C. I. Fluorescent Brightener 160
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Application
[12224-24-7]
Calcofluor White NCV (Ameri-
can Cyanamid Co.)
Benzidine sulfone derivative
Greenish blue
Insoluble in water; very soluble
in methanol, Methyl Cellosolve,
butanol and tetrahydrofurfuryl
alcohol; soluble in methyl
ethyl ketone and acetone; slight-
ly soluble in toluene and ethyl
acetate
Fastness to daylight good and
to artificial light excellent
Nitrocellulose
Cellulose acetate butyrate
Chlorinated rubber varnishes
C. I. Fluorescent Brightener 160 is not being manufactured at
the present time.
A-86
-------
C. I. Fluorescent Brightener 161
C. I. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-25-8]
Calcofluor White 2RP (American
Cyanamid Co.)
Stilbene derivative
Reddish
Exhausts slowly, has good fastness
to alum and is non-feathering.
Fluorescence little affected
between pH 4«5-6. Used in paper
coating compositions it is
satisfactory at pH up to 9
Paper
C. I. Fluorescent Brightener 161 is not being manufactured
at the present time.
C. I. Fluorescent Brightener 162
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-26-9]
Mikawhite AT (Nippon Kayaku
Co., Ltd., Japan; Mitsubishi
Chemical Industries, Ltd.,
Japan)
Naphthalic acid derivative
Blue
Usable at pH 3-11 and stable to
chlorite. Excellent fastness to
light, washing, perspiration
and heat
Polyester, acrylics, acetate
A-8?
-------
C. I. Fluorescent Brightener 162:1
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Leukophor EFR (Sandoz, Inc.);
Mikawhite ATN, (Nippon Kayaku
Co., Ltd., Japan; Mitsubishi
Chemical Industries, Ltd.,
Japan)
Naphthalic acid derivative
Not given in the literature
Not given in the literature
Polyester-cotton blends
C. I. Fluorescent Brightener 163
C. A. Registry Number [12224-27-0]
This C. I. generic name is discontinued. The brighteners
formerly listed under it now appear under C. I. Fluorescent
Brightener 162:1.
C. I. Fluorescent Brightener 164
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-28-1]
Mikawhite BTN (Nippon Kayaku
Co., Ltd., Japan; Mitsubishi
Chemical Industries, Ltd.,
Japan)
Naphthalic acid derivative
Blue
Usable at pH 3-11 and stable to
chlorite. Excellent fastness
to light, washing, perspiration
and heat
Polyester, acrylics, acetate
A-£
-------
C. I. Fluorescent Brightener 165
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Not given in the literature
Fluolite HM (Imperial Chemical
Industries, Ltd., England)
Stilbene derivative
Reddish-blue
Readily soluble in cold water.
Stable to acid, alum and rosin.
Good build-up
Paper
C. I. Fluorescent Rrightener 166
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-29-2]
Kayaphor 3BS (Nippon Kayaku
Co., Ltd., Japan)
Stilbene derivative
Bright greenish blue
Very good solubility in water.
Stripping with chlorite good
Cellulose, paper
Soaps, detergents
A-89
-------
C. I. Fluorescent Brightener 167
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-30-5]
v
Kayaphor RCS (Nippon
Kayaku Co., Ltd., Japan)
Stilbene derivative
Bright reddish
Good solubility in water. Good
fastness to chlorine, light,
peroxide and washing
Cellulose, paper
C.I. Fluorescent Brightener 168
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-31-6]
Kayaphor C (Nippon Kayaku Co.,
Ltd., Japan)
Stilbene derivative
Bright blue
Very good fastness to chlorine
and good fastness to light,
peroxide and washing
Cellulose, paper
C. I. Fluorescent Brightener 169
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-32-7]
Kayaphor PS (Nippon Kayaku Co.»
Ltd., Japan)
Stilbene derivative
Bright reddish-violet
Good fastness to chlorine, light,
peroxide and washing
Cellulose, paper
A-90
-------
C. I. Fluorescent Brightener 170
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12236-38-3]
Mikephor EN (Mitsui Toatsu
Chemicals, Inc., Japan)
Oxazole derivative
Bluish
Insoluble in water, soluble in
ethanol
Polyester
C. I. Fluorescent Brightener 171
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12236-39-4]
Mikephor EB (Mitsui Toatsu
Chemicals, Inc., Japan); Pho-
tine EB, EB Liquid (Hickson
and Welch Ltd., England)
Oxazole derivative
Bluish
Good fastness to acid and light,
very good fastness to alkali,
chlorine, dithionite and peroxide
Nylon, Triacetate, polyester
C. I. Fluorescent Brightener 172
C. A. Registry Number [12224-33-8]
This C. I. generic name is discontinued. The brighteners
formerly listed under it now appear under C. I. Fluorescent
Brightener 185:1 and 185:2.
A-91
-------
C. I. Fluorescent Brightener 173
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-34-9]
Whitex 10B (Sumitomo Chemical
Co., Ltd., Japan)
Stilbene derivative
Bright bluish
Good solubility in water. Good
fastness to chlorine, light,
peroxide and washing
Cellulose, paper
Soaps, detergents
C. I. Fluorescent Brightener 174
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12236-40-7]
Mikephor BE (Mitsui Toatsu
Chemicals, Inc., Japan)
Stilbene derivative
Greenish-blue
Readily soluble in cold water.
Fastness: Chlorine, poor;
washing, excellent
Cellulose, paper
C. I. Fluorescent Brightener 175
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12236-41-8]
Mikephor MX (Mitsui Toatsu
Chemicals,' Inc., Japan)
Stilbene derivative
Bluish
Water soluble
Cellulose, paper
A-92
-------
C. I. Fluorescent Brightener 176
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12236-42-9]
Mikephor RFA (Mitsubi Toatsu
Chemicals, Inc., Japan)
Stilbene derivative
Reddish blue
Water soluble
Cellulose
Detergents
C. I. Fluorescent Brightener 177
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12236-43-0]
Mikephor RP (Mitsui Toatsu
Chemicals, Inc., Japan)
Stilbene derivative
Bluish
Water soluble
Cellulose
C. I. Fluorescent Brightener 178
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12236-44-1]
Mikephor RP (Mitsui Toatsu
Chemicals, Inc., Japan)
Stilbene derivative
Bluish
Water soluble
Wool, nylon
A-93
-------
C. I. Fluorescent Brightener 179
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-35-0]
Fluolite XMF (Imperial Chemi-
cal Industries, Ltd., England)
Triazine derivative
Bluish
Stable to peroxide, salt,
sodium carbonate, sulphonic
acid, anionic and non-ionic
surfactants and some cationic
surfactants.
Acetate, triacetate, acrylic,
nylon
C. I. Fluorescent Brightener 180
C. A. Registry Number
Commercial Names
[12224-36-1]
Blancol HR (L. B. Holliday and
Co., Ltd., England)
This C. I. generic name is discontinued; this brightener is
not being manufactured at the present time.
C. I. Fluorescent Brightener 181
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-37-2]
Uvitex ALN ' (Ciba-Geigy Corp.)
Heterocyclic
Bluish to reddish-blue
Outstanding fastness to light
and washing
Acrylics
A-9U
-------
C.I. Fluorescent Brightener 182
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-38-3]
Uvitex MP (Ciba-Geigy Corp.)
Triazinylaminostilbene derivative
Bluish .
Not given in the literature
Nylon
C. I. Fluorescent Brightener 183
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-39-4]
Uvitex NB (Ciba-Geigy Corp.)
Triazinylaminostilbene
Blue
Good fastness to light and washing
Cellulose
Nylon
C. I. Fluorescent Brightener 184
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-40-7]
Uvitex OB (Ciba-Geigy Corp.)
Heterocyclic
Bluish
Not given in the literature
Acetate, polyvinyl chloride,
triacetate
According to the U. S. Tariff Commission reports, 551 pounds of
Fluorescent Brightener 184 were imported into the U. S. in 1972.
A-95
-------
C. I. Fluorescent Brightener 184:1
C. A. Registry Number Not given in the literature
Commercial Names Uvitex OB-C (Ciba-Geigy Corp.)
C. I. Fluorescent Brightener 184:1 is identical to C. I.
Fluorescent Brightener 184, but it is extended with chalk to
facilitate its dispersion in plastics.
C. I. Fluorescent Brightener 184:2
C. A. Registry Number Not given in the literature
Commercial Names Uvitex OB-P (Ciba-Geigy Corp.)
C. I. Fluorescent Brightener 184:2 is chemically identical to
C. I. Fluorescent Brightener 184, but contains a softening agent.
Its applications are: Plasticised poly(vinyl chloride).
C. I. Fluorescent Brightener 185
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-41-8]
Uvitex EBF (Ciba-Geigy Corp.)
Thiophene oxazole derivative
Bluish
Outstanding fastness to chlorine,
light, and washing on polyester
fibers
Acetate, triacetate, nylon,
polyester
Polypropylene, poly(vinyl chloride)
A-96
-------
C. I. Fluorescent Brightener 185:1
C. A. Registry Number Not given in the literature
Commercial Names Whitex SNK (Sumitomo Chemical
Co., Ltd., Japan)
Chemical Class Thiophene oxazole derivative
Fluorescence Bright bluish
Properties Stable in chlorite bleaching
baths and peracetic acid
Fastness: (polyester or poly-
propylene), light, excellent;
organic solvents, very good;
washing, excellent
Applications Polypropylene
Polyester, Polyvinyl, nylon
C. I. Fluorescent Brightener 185:1 is not being manufactured
at the present time.
C. I. Fluorescent Brightener 185:2
C. A. Registry Number Not given in the literature
Commercial Names Whitex NKR (Sumitomo Chemical
Co., Ltd., Japan)
Chemical Class Thiophene oxazole derivative
Fluorescence Bright reddish
Properties Stable in chlorite bleaching
baths and peracetic acid
Fastness: (polyester or poly-
propylene) , light, excellent;
organic solvents, very good;
washing, excellent
Applications Polypropylene
Polyester, Polyvinyl, nylon
A-9T
-------
C. I. Fluorescent Brightener 186
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-42-9]
Uvitex SFC (Ciba-Geigy Corp.)
Stilbene derivative
Blue
Excellent fastness to acid and
to perspiration
Soaps, detergents
C. I. Fluorescent Brightener 187
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-43-0]
Uvitex SFC (Ciba-Geigy Corp.)
Stilbene derivative
Bluish
Not given in the literature
Paper
C. I. Fluorescent Brightener 188
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-44-1]
Uvitex SBRN (Ciba-Geigy Corp.)
Stilbene derivative
Bluish
Not given in the literature
Cellulose, nylon
Detergents
A-98
-------
C. I. Fluorescent Brightener 189
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-45-2]
Uvitex SK (Ciba-Geigy Corp.)
Heterocyclic
Bluish
Stable in washing liquors con-
taining hypochlorite or chloro-
isocyanuric acid. Excellent
fastness (on fibre) to acids,
chlorine, light and washing
Detergents
C. I. Fluorescent Brightener 190
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12224-46-3]
Uvitex SOF (Ciba-Geigy Corp.)
Heterocyclic
Bluish
Stable in washing liquors con-
taining hypochlorite or chloro-
isocyanuric acid. Excellent
fastness (on fibre) to acids,
chlorine, light and washing
Detergents
A-99
-------
C. I. Fluorescent Brightener 191
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12270-53-0]
Blankophor CL (Farbenfabriken
Bayer A. G., Germany)
Stilbene derivative
Reddish-violet
Anionic. Stability (in soln),
acid, very good; alkali, good;
cationic softeners, pptd;
chlorite, very good; dithionite,
very good; heat, very good; hard
water, pptd; hypochlorite, good
at pH 10-12; peroxide, very good
Cellulose, nylon
According to the U. S. Tariff Commission Reports, 77,975
pounds of Fluorescent Brightener 191 were imported into the U. S.
in 1972.
C. I. Fluorescent Brightener 192
C . A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12270-54-1]
Blankophor PSL (Farbenfabriken
Bayer A. G., Germany)
Stilbene derivative
White
Cationic. Stable in solution to
acid and dithionite, not stable
to chlorine or chlorite
Acrylic, wool, silk
A-100
-------
C. I. Fluorescent Brightener 193
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12270-55-2]
Blankophor PSL (Farbenfabriken
Bayer A. G., Germany)
4,4'-Diaminostilbene-2,2'-
:.disulfonic acid derivative
Slightly reddish
Good solubility in water,
extremely good resistance to
acid, little substantive to
cellulose
Paper
C. I. Fluorescent Brightener 194
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12270-56-3]
Glowhite BBN (Amar Dye-Chem.,
Ltd., India)
Stilbene derivative
Bright blue
Very soluble in water. Fastness
to light good and to chlorine
and washing very good
Cellulose, paper
A-ior
-------
C. I. Fluorescent Brightener 195
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12270-57-4]
GlOwhite BRN (Amar Dye-Chem.,
Ltd., India)
Stllbene derivative
Bright reddish blue
Good solubility in water. Stable
to acids and reducing agents
Fastness: Chlorine, moderate;
Light, good; Washing, very good
Cellulose
C. I. Fluorescent Brightener 196
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12270-58-5]
Glowhlte NAN (Amar Dye-Chem.,
Ltd., India)
Coumarin derivative
Reddish-violet
Readily soluble in cold water
Fastness: Light, moderate;
Washing, moderate to good
Protein fibers, acetate, 7\ylon
Since C. A. Registry Numbers are not available for brighteners
beyond C. I. Fluorescent Brightener 196, this item will be deleted
from the following tables (C. I. Fluorescent Brightener 231 is an
exception).
A-102
-------
C. I. Fluorescent Brightener 197
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Ultraphor AL (Badische Anilin &
Soda Fabrik A. G., Germany)
Azacyanine derivative
Reddish-blue
Cationic. Good solubility.
Stable to cationic softeners and
peroxide, not stable to reducing
agent. Can be used in chlorite
bleaching baths
Acrylic, triacetate, acetate
C. I. Fluorescent Brightener 197 is not being manufactured
at the present time.
C. I. Fluorescent Brightener 198
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Pananil Brilliant White G
(Badische Anilin & Soda Fabrik
A. G., Germany)
Stilbene derivative
Greenish-blue
Non-ionic. Good solubility.
Stable to cationic softeners.
Can be used in chlorite, peroxide
and reduction bleaching baths
Polyester, acetate, nylon,
triacetate
A-103
-------
C. I. Fluorescent Brightener 199
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Palanil Brilliant White R
(Badische Anilin & Soda Fabrik,
A. G., Germany)
Stilbene derivative
Reddish-blue
Non-ionic. -Good solubility.
Stable to cationic softeners.
Can be used in chlorite, peroxide
and reduction bleaching baths
Polyester, acetate, nylon,
triacetate
C. I. Fluorescent Brightener 200
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Blankophor BK (Farbenfabriken
Bayer A. G., Germany)
Stilbene derivative
Bluish-violet
Anionic. Sensitive to hard
water and cationic softeners.
Stable to acids, alkalies, di-
thionite and heat
Cotton and Polyester-cotton
blends
According to the U. S. Tariff Commission.Reports, 46, 250
pounds of Fluorescent Brightener 200 were imported into the U. S,
in 1972.
A-10U
-------
C.I. Fluorescent Brightener 201
Commercial Names Blankophor ACB (Farbenfabriken
Bayer A. G., Germany)
Chemical Class Stilbene derivative
Fluorescence Bluish-violet
Properties Cationic. Good solubility in
water. Stable to cationic sof-
teners and dithionite
Applications Acrylics
C. I. Fluorescent Brightener 202
Commercial Names Blankophor ACR (Farbenfabriken
Bayer, A. G., Germany)
Chemical Class Nitrogen heterocycle
Properties Cationic. Good solubility in
water. Unstable in neutral
or alkaline baths
Applications Acrylics
C. I. Fluorescent Brightener 203
Commercial Names Blankophor KL (Farbenfabriken
Bayer A. G., Germany)
Chemical Class Coumarin derivative
Fluorescence Bluish
Properties Insoluble in water, soluble
in many solvents. Excellent
resistance to heat, acid and
alkali, n.p. 70°C
Applications Plastics, resins, plasticizers,
lacquers
A-105
-------
C. I. Fluorescent Brightener 204
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Blankophor RA (Farbenfabriken
Bayer A. G., Germany)
Stilbene derivative
Bluish-violet
Anionic. High substantivity,
riot dischargeable and difficult
to strip. Not stable in solution
to chlorine and chlorite
bleaching baths
Cellulose, Polyester-cotton
blends, Nylon-cotton blends
C. I. Fluorescent Brightener 205
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Blankophor RKH (Farbenfabriken
Bayer A. G., Germany)
Stilbene derivative
White
Anionic. Good solubility in
boiling water, good dispersi-
bility in cold water. Very
good resistance to spray drying,
alkalis and peroxides. Good
substantivity. In solution
unstable to chlorine but has
good fastness on the fibre
Cellulose
According to the U. S. Tariff Commission Reports, 490,665
pounds of Fluorescent Brightener 205 were imported into the U. S.
in 1972.
A-106
-------
C. I. Fluorescent Brightener 206
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Blankophor FBO (Farbenfabriken
Bayer A. G., Germany)
Nitrogen heterocycle
Reddish-blue
Non-ionic. Insoluble in water,
readily dispersible in water
in presence of detergents. Very
good stability to spray drying,
alkalis and peroxides. In
solution unstable to chlorine
Acetate, nylon, triacetate
C. I. Fluorescent Brightener 207
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Photine VN (Hickson and Welch,
Ltd., England)
Stilbene derivative
Bluish-violet
Water soluble. Good substantivity.
Fastness to acid, alkali, chlorine
and light good and to dithionite
and peroxide very good
Nylon
C. I. Fluorescent Brightener 208
Commercial Names
Chemical Class
Fluorescence
I
Properties
Applications
Photine LTD (Hickson and Welch,
Ltd., England)
Stilbene derivative
Reddish-blue
Water soluble. Good substanti-
vity. Fastness to acid and light
good, to alkali, chlorine, di-
thionite and peroxide very good
Cellulose
Soaps, detergents
A-107
-------
C. I. Fluorescent Brightener 209
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Photine PT New, Photine Paper-
white P (Hickson and Welch, Ltd.,
England; S. A. Rovira, Spain)
Stilbene derivative
Reddish-blue
Readily soluble in water. Stable
to high concentrations of alum.
Good sub s tant ivity. Fastnes s
to chlorine and light good, to
acid, alkali, dithionite and
peroxide very good
Paper
C. I. Fluorescent Brightener 210
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Photine BPM (Hickson and Welch,
Ltd., England)
Stilbene derivative
Blue
Readily soluble in water. Good
substantivity. Fastness to
chlorine and light good, to
acid, alkali, dithionite. and
peroxide very good
Paper
C. I. Fluorescent Brightener 211
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
A-108
Photine BTM (Hickson and Welch,
Ltd., England)
Stilbene derivative
Blue
Readily soluble in water. Moder-
ate substantivity. Sensitive
to electrolytes. Fastness to
chlorine and light good, to
acid, alkali, dithionite and
peroxide very good
Cellulose
Nylon
-------
C. I. Fluorescent Brightener 212
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Photine CXT (Hickson & Welch,
Ltd., England)
Stilbene derivative
Reddish-blue
Dispersible in cold water, solu-
ble in hot water. High substan-
tivity. Fastness to acid poor,
to light good and to alkali,
chlorine, dithionite and peroxide
very good
Cellulose
Nylon, protein fibers
C. I. Fluorescent Brightener 213
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Photine HV, HVS, VHP (Hickson
and Welch, Ltd., England; S. A.
Rovira, Spain; Hickson and Dada-
j ee Private Ltd., India)
Stilbene derivative
Reddish-blue
Readily soluble in water. Good
substantivity. Fastness to
chlorine and light good, to acid,
alkali, dithionite and peroxide
very good
Cellulose, paper
Nylon, protein fibers
A-109
-------
C. I. Fluorescent Brightener 214
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Photine HVD, RD245D (Hickson
and Welch, Ltd., England; S. A.
Rovira, Spain; Hickson and Dadajee
Private Ltd., India)
Stilbene derivative
Reddish-blue
Readily soluble in water. Good
Substantivity. Fastness to
chlorine and light good, to
acid, alkali, dithionite and
peroxide very good
Cellulose
Soaps, detergents
C. I. Fluorescent Brightener 215
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Photine LV (Hickson and Welch,
Ltd., England)
Stilbene derivative
Reddish-blue
Soluble in water. Medium sub-
stantivity. Fastness to alkali,
chlorine and light good, to
acid and dithionite very good
Cellulose
Nylon
A-110
-------
C. I. Fluorescent Brightener 216
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Kayaphor BR (Nippon Kayaku
Co., Ltd., Japan)
Bistriazinylamtnostilbene
derivative
Reddish-blue
Very good solubility in water.
Fastness to dithionite and light
good, to acid, alkali, chlorine
and peroxide very good
Cellulose
Nylon, protein fibers
Co I» Fluorescent Brightener 217
Commercial Names
Chemical Class
Fluorescence
Properties.
Applications
Kayaphor W .(Nippon Kayaku Co.,
Ltd., Japan); Whitex BRF (Su-
mitomo Chemical Co., Ltd.,
Japan)
Pyrazoline derivative
Reddish-blue
Good solubility in water. Fast-
ness to alkali and light good,
to acid, dithionite and perox-
ide very good
Wool, nylon
A-in
-------
C. I. Fluorescent Brightener 218
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Kayaphor N (Nippon Kayaku Co.,
Ltd., Japan)
Bistriazinylaminostilbene
Reddish-blue
Good solubility in water.
Fastness to light good, to
acid, alkali, chlorine, di-
thionite and peroxide very good
Cellulose
Wool, nylon
C. I. Fluorescent Brightener 219
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
White WP (Sumitomo Chemical
Co., Ltd., Japan)
Oxazole derivative
Reddish-blue
Insoluble in water but readily
dispersed in cold water. Fast-
ness to acid, alkali, chlorine,
dithionite, light and peroxide
very good
Polypropylene
Nylon, acetate, poly(vinyl
chloride)
A-112
-------
C. I. Fluorescent Brightener 219:1
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Kayaphor OLN (Nippon Kayaku
Co., Ltd., Japan)
Oxazole derivative
Neutral
Readily dispersible in water.
Fastness to chlorine, sublima-
tion and washing good and to
light excellent
Polypropylene
Polyester, nylon, poly(vinyl
chloride)
C. I. Fluorescent Brightener 219:2
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Kayaphor OLR (Nippon Kayaku
Co., Ltd., Japan)
Oxazole derivative
Slightly reddish
Readily dispersible in water.
Fastness to chlorine, sublima-
tion and washing good and to
light excellent
Polypropylene
Polyester, nylon, poly(vinyl
chloride)
A-113
-------
C. I. Fluorescent Brightener 220
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Fluolite PS Liquid (Imperial
Chemical Industries, Ltd.,
England)
Stilbene derivative
Bluish
Miscible with cold soft water
in all proportions. Stable
to alum and strong and weak
acids and alkalis
Paper
C. I. Fluorescent Brightener 221
This C. I. generic name is discontinued. The brighteners
formerly listed under it now appear under C. I. Fluorescent
Brightener 146.
C. I. Fluorescent Brightener 222
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Photine SPG (Hickson and Welch,
Ltd., England); White SPC (Hick-
son and Dadajee Private Ltd.,
India)
Stilbene derivative
Bluish-red
Soluble in water. Fastness
to chlorine poor, to acid, al-
kali, light and peroxide good
and to dithionite very good
Cellulose, paper
A-llU
-------
C. I. Fluorescent Brightener 223
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Kayaphor CR (Nippon Kayaku
Co., Ltd., Japan)
Bistriazinylaminostilbene deri-
vative
Bright reddish blue
Good solubility in water.
Fastness to acid, dithionite
and light good, to alkali,
chlorine and peroxide very good
Cellulose, paper
Nylon
C. I. Fluorescent Brightener 224
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Kayaphor HAS (Nippon Kayaku
Co., Ltd., Japan)
Bistriazinylaminostilbene
derivative
Neutral
Good solubility in water.
Fastness to light good and
to acid, alkali, chlorine,
dithionite and peroxide very
good
Cellulose, paper
Wool, nylon
Poly(vinyl alcohol)
A-115
-------
C. I. Fluorescent Brightener 225
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Kayaphor LSK (Nippon Kayaku
Co., Ltd., Japan); Whitex
SKC (Sumitomo Chemical Co.,
Ltd., Japan)
Bistriazinylaminostilbene
derivative
Neutral
Slightly soluble in water.
Fastness to dithionite, light
and peroxide good, to alkali
and chlorine very good
Cellulose '
Nylon
Soaps, detergents
C. I. Fluorescent Brightener 226
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Mikawhite ACR (Nippon Kayaku
Co., Ltd., Japan)
Acenaphthene derivative
Neutral
Readily soluble in cold water.
Very good fastness to acid,
alkali, chlorine, dithionite,
light and peroxide
Acrylics
A-116
-------
C. I. Fluorescent Brightener 227
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Mikawhite SIN (Nippon Kayaku
Co., Ltd., Japan)
Acenaphthene derivative
Bluish
Insoluble but readily disper-
sible in water. Very good
fastness to acid, alkali,
chlorine, dithionite, light
and peroxide
Polyester, acrylic, acetate,
nylon
C. I. Fluorescent Brightener 228
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Photine TCA (Hickson and Welch,
Ltd., England)
Heterocyclic
Bluish-violet
Insoluble in water. High
substantivity. Fastness to
chlorine poor, to acid, dithi-
onite and peroxide good, to
light very good and alkali ex-
cellent
Acetate, triacetate, acrylic,
nylon
A-11T
-------
C. I. Fluorescent Brightener 229
Commercial Names Blankophor EBL (Farbenfabriken
Bayer A. G., Germany)
Chemical Class Coumarin derivative
Fluorescence Neutral
Properties Non-ionic. Stable in solution
and in the fibre to acid, al-
kali, chlorite, hard water,
b hypochlorite and reducing agents
Applications Polyester, 'polyester-cotton
blends
According to U. S. Tariff Commission Reports, 77,160 pounds
of Fluorescent Brightener 229 were imported into, the U. S. in
1972.
C. I. Fluorescent Brightener 230
Commercial Names Leukophor AP (Sandoz Colors
and Chemicals)
Chemical Class Bistriazinylaminostilbene
derivative
Fluorescence Blue
Properties Not stable to acids and electro-
lytes
Applications Cotton
Paper
A-118
-------
C. I. Fluorescent Brightener 231
C. A. Registry Number
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
[12676-64-1]
Leukophor C (Sandoz Colors
and Chemicals)
Bistriazinylaminostilbene
derivative
Blue
Excellent solubility in water.
Stable to acid and alkali.
Heavy metal salts lessen the
fluorescence
Cellulose, paper
C. I. Fluorescent Brightener 232
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Leukophor CK (Sandoz Colors
and Chemicals)
Bistriazinylaminostilbene deri-
vative
Blue
Stable to acid and alkali.
Heavy metal salts lessen the
fluorescence
Paper
A-119
-------
C. I. Fluorescent Brightener 233
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Leukophor DT (Sandoz Colors
and Chemicals)
Bistriazinylaminostilbene deriva-
tive
Brilliant blue
Solubility in water at 100°C
10 mg/1. Stable to perborate
and alkalis. Looses its fluor-
escence in warm liquors con-
taining hypochlorite but on
the fibre is negligibly affected
by chlorine
Washing powders for cellulose
and nylon textiles
C. I. Fluorescent Brightener 234
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Leukophor PAF (Sandoz Colors
and Chemicals)
Bistriazinylaminostilbene
derivative.
Reddish-blue
Soluble in hot water. Stable
to acids and alkalis, not
stable to chlorine
Nylon, nylon-wool blends,
nylon-cellulose blends, wool
A-120
-------
C. I. Fluorescent Brightener 235
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Leukophor SPA (Sandoz Colors
and Chemicals)
Bistriazinylaminostilbene
derivative
Very brilliant blue
Stable to acids and alkalis
but heavy, metal salts reduce
the fluorescence
Paper
C. I. Fluorescent Brightener 236
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Leukopur EGM (Sandoz Colors
and Chemicals)
Coumarin derivative
Blue
Soluble in hot organic solvents.
Stable to acids and alkalis
Polyester
C. I. Fluorescent Brightener 237
This C. I. generic name is discontinued. The brighteners
formerly listed under it now appear under C. I. Fluorescent
Brightener 222.
A-121
-------
C. I. Fluorescent Brightener 238
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Lyrcamine White NL (Compagnie
Francaise des Matieres Color-
antes, France)
Naphthalimide derivative
Violet
Cationic in nature. Soluble
in strong sulfuric acid
Acrylics
According to the U. S. Tariff Commission Reports, 1,587
pounds of Fluorescent Brightener 238 were imported into the U. S,
in 1972. :
C. I. Fluorescent Brightener 239
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Kayaphor NL (Nippon Kayaku Co.,
Ltd., Japan)
Bistriazinylaminostilbene
derivative
Bluish-violet
Readily soluble in cold water.
Fastness to chlorine moderate,
to alkalis and light good, to
acid, dithionite and peroxide
very good
Cellulose, paper
Protein fibers, nylon
A-122
-------
C. I. Fluorescent Brighteher 240
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Kayaphor SFN (Nippon Kayaku
Co., Ltd., Japan)
Bistriazinylaminostilbene
derivative
Bluish-violet
Very good solubility in hot
water. Good compatibility with
cationic compounds in detergent
compositions
Paper, cellulose
Wool, nylon
C. I. Fluorescent Brightener 241
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Kayaphor CPS Cone. (Nippon
Kayaku Co., Ltd., Japan)
Bistriazinylaminostilbene
derivative
Bluish-violet
Solubility in water 10 g/1
at 75°C. Esdiausts well on
cellulose from cold solution.
Fostness to chlorine moderate,
to light good and to acid, al-
kali, dithionite and peroxide
very good
Paper
Detergents for wool, nylon,
and cellulose
A-123
-------
C. I. Fluorescent Brightener 242
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Kayaphor PBN (Nippon Kayaku
Co., Ltd., Japan)
Bistriazinylaminostilbene
derivative
Bluish-violet
Fastness to chlorine moderate,
to alkali and light good and
to acid, dithionite and peroxide
very good
Cellulose, paper
Wool, nylon
C. I. Fluorescent Brightener 243
Colour Index Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
C. I. 40619
Heliofor 2BC (CIECH, Poland)
4,4' -Bis [ (4-amino-6-hydroxy-s-
triazin-2-yl) amino ] -2 , 2 ' -
stilbenedisulfonic acid, diso-
dium salt
* 2Na
Bluish
Soluble in water
Cellulose
A-12U
-------
C. I. Fluorescent Brlghtener 244
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Heliofor 3BC (CIECH, Poland)
Stilbene derivative
Bluish
Slightly soluble in water
Cellulose
C. I. Fluorescent Brightener 245
Colour Index Number
Commercial Names
Chemical Class
Molecular Formula
Fluorescence
Properties
Applications
C. I. 40615
Heliofor ZSP (CIECH, Poland)
4,4'-Bis[(4-chloro-6-amino-s-
triazin-2-yl)amino] -2,2'-stilben-
edisulfonic acid, disodium salt
C20H1i(Cl2N1006S2 2Na
Greenish-blue
Slightly soluble in water. Fast
to thermofixation
Nylon
C. I. Fluorescent Brightener 246
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Heliofor SPG (CIECH, Poland)
Stilbene derivative
Bluish
Soluble in water. Fast to ther-
mof ixation
Cellulose
Nylon
A-125
-------
C. I. Fluorescent Brightener 247
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Heliofor VM (CZECH, Poland)
Stilbene derivative
Bluish
Does not affect the viscosity,
stability or the filtration
and extrusion properties of
viscose solution
Viscose
C. I. Fluorescent Brightener 248
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Heliofor SPM (CIECH, Poland)
Stilbene derivative
Bluish
Soluble in water. Fast to
thereofixation
Acrylic, nylon
C. I. Fluorescent Brightener 249
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Heliofor V, VP (CIECH, Poland)
Stilbene derivative
Reddish
Soluble in water
Cellulose, paper
A-126"
-------
C. I. Fluorescent Brightener 249:1
Commercial Names Not given in the literature
Chemical Class Stilbene derivative
Fluorescence Reddish
Properties Not given in the literature
Applications Paper
C. I. Fluorescent Brightener 250
Commercial Names
Chemical Class
Fluorescence
Properties
Applications - .
Heliofor BDC (CIECH, Poland)
Stilbene derivative
Bluish
Excellent fastness to alkali
and perborates
Cellulose .
C. I. Fluorescent Brightener 251
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Tinopal 2BT (Ciba-Geigy Corp.)
Stilbyl-s-triazine derivative
Bluish
Not given in the literature
Cellulose
According to the U. S. Tariff Commission Reports, 220
pounds of Fluorescent Brightener 251 were imported into the U. S.
in 1972.
A-127
-------
C. I. Fluorescent Brightener 252
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Tinopal BHT (Ciba-Geigy Corp.)
Stibyl-s-triazine derivative
Bluish
Not given in the literature
Cellulose
C. I. Fluorescent Brightener 253
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Tinopal WHN (Ciba-Geigy Corp.)
Stibyl-s-triazine derivative
Bluish
Not given in the literature
Polyacrylonitrile
Wool
C. I. Fluorescent Brightener 254
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Tinopal ERT (Ciba-Geigy Corp.)
Coumarinyl-pyrazole derivative
Reddish
Not given in the literature
Polyester
According to the U. S. Tariff Commission Reports, 1,102
pounds of Fluorescent Brightener 254 were imported into the U. S.
in 1972.
A-128
-------
C. I. Fluorescent Brightener 255
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Tinopal NTH (Ciba-Geigy Corp.)
Stilbyl-s-triazine derivative
Slightly bluish
Not given in the literature
Not given in the literature
C. I. Fluorescent Brightener 256
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Tinopal 2RT (Ciba-Geigy Corp.)
Stilbyl-s-triazine derivative
Reddish
Not given in the literature
Not given in the literature
C. I. Fluorescent Brightener 257
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Blankophof ANR (Farbenfabriken
Bayer A. G., Germany)
Coumarin derivative
Reddish
In solution is not resistant
to hypochlorite, peroxide and
alkalis but on the fibre has
very good resistance to them.
Very good resistance both in
soln and on the fibre to
dithionite, acids and hard water
Acrylics
According to the U. S. Tariff Commission Reports, 1,050
pounds of Fluorescent Brightener were imported into the U. S.
in 1972.
A-129
-------
C. I. Fluorescent Brightener 258
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Whitex SNP (Sumitomo Chemical
Co., Ltd., Japan)
Oxazole derivative
Bluish violet
Insoluble in water
Polyolefin, polyester
C. I. Fluorescent Brightener 259
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Whitex AC (Sumitomo Chemical
Co., Ltd., Japan)
Oxazole derivative
Bluish
Soluble in water
Acrylics
C. I. Fluorescent Brightener 260
Commercial Names
Chemical Class
Fluorescence
Properties
Applications
Whitex SA (Sumitomo Chemical
Co., Ltd., Japan)
Stilbene derivative
Bluish
Fastness: Alkali, Chlorine,
Dithionite, Peroxide and Washing,
very good; Light, good
Cellulose
Soaps and detergents
A-130
-------
C. I. Fluorescent Brightener 261
Commercial Names Whitex SEC (Sumitomo Chemical
Co., Ltd., Japan)
Chemical Class Stilbene derivative
Fluorescence Bluish
Properties Fastness: Acid, Chlorine,
and Light, good; Alkali, Di-
thionlte, Peroxide and Washing,
very good
Applications Cellulose
Spaps and detergents
C. I. Fluorescent Brightener 265
According to the U. S. Tariff Commission Reports, 450
pounds of Fluorescent Brightener 265 were imported into the U. S.
in 1972.
No further correlations could be established between C. I.
Fluorescent Brightener numbers and miscellaneous data on the
brighteners, because of a lack of indicative information.
A-131
-------
Following are data on some optical brighteners for which
no C. I. Fluorescent Brightener numbers were obtained.
Hiltamine Arctic Paper White DSA (Hilton-Davis Division of Sterling
Drug Co.)
Chemical Class Triazinylstilbene derivative
Properties Liquid in form; pH 9.0-10.0
Anionic in nature
Miscible with water in all pro-
portions !
Applications Paper
Hiltamine Arctic Paper White HMS (Hilton-Davis Division of Sterling
Drug Co.)
Chemical Class Triazinylstilbene derivative
Properties Liquid in form; pH 8.6-9.8
Anionic in nature
Miscible with water in all pro-
portions
Applications Paper
Hiltamine Arctic Paper White LG (Hilton-Davis Division of Sterling
Drug Co.)
Chemical Class Triazinylstilbene derivative
Properties Liquid in form; pH 6.8-7.8
Anionic in nature
Miscible with water in all
proportions
Applications Paper
A-132
-------
Hiltamlne Arctic White GT (Hilton-Davis Division of Sterling
Drug Co.) .
Chemical Class Triazinylstilbene derivative
Properties Liquid in form; pH 8.8-9.8
Anionic in nature.
Miscible with water in all
proportions
Applications Textiles; resin finishes
Hiltamine Arctic White SC (Hilton-Davis Division of Sterling
Drug Co.)
Chemical Class Triazinylstilbene derivative
Properties Liquid in form; pH 8.2-9.2
Anionic in nature
Miscible with water in all
proportions
Applications Textiles
Liquid detergents, laundry
softeners
Hiltamine Arctic White CC (Hilton-Davis Division of Sterling
Drug Co.)
Chemical Class Triazinylstilbene derivative
Properties Liquid in form; pH 9.5-10.5
Anionic in nature
Compatible with cationic,
anionic, and nonionic softeners
Miscible with water in all
proportions
Applications Textiles
Fabric softeners
A-133
-------
Hiltamine Arctic White TX (Hilton-Davis Division of Sterling
Drug Co.)
Chemical Class Triazinylstilbene derivative
Properties Liquid in form; pH 8.5-10.5
Anionic in nature
Compatible with cationic,
anionic, and nonionic in
nature
Miscible with water in all
proportions
Applications Textiles
Fabric softeners
Hiltamine Arctic White MSO (Hilton-Davis Division of Sterling
Drug Co.)
Chemical Class Triazinylstilbene derivative
Properties Powder in form
Anionic in nature
Insoluble in aqueous acidic
solutions
Slightly soluble in aqueous
alkali
Applications Cold water, all-temperature, low-
phosphate, and no-phosphate
laundry formulations
Hiltamine Arctic White CWD (Hilton-Davis Division of Sterling
Drug Co.)
Chemical Class Triazinylstilbene derivative
Properties Powder in form
Anionic in nature
Low solubility at acidic pH
levels
Applications Cold water laundry formulations
Detergents
Fabric Softeners
A-13U
-------
Hiltamine Arctic White SOL (Hilton-Davis Division of Sterling
Drug Co.)
Chemical Class Coumarin derivative
Properties Powder in form
Nonionic in nature
Water insoluble
Soluble in alcohol, benzene,
ketones, detergents, and resins
Applications Fine fabric detergent formula-
tions
Textiles; polyamides
Safratone White WNOA (Hilton-Davis Division of Sterling Drug Co.)
Chemical Class Coumarin derivative
Properties Powder in form
Nonionic in nature
Readily dissolves in warm water
Applications Detergent formulations
Textiles; polyamides, acetate,
triacetate
Advabrite BMV (Cincinnati Milacron Chemicals Inc.)
Chemical Name 7-Hydroxy-4-Methylcoumarin
Molecular Formula
Properties Light tan powder :
M.P. 184-194°C
Outdoor durability
Exhibits strong blue fluorescence
under black light
Applications Pigmented coatings
Solvent and water-based coatings
A-135
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Advabrite MDAC (Cincinnati Milacron Chemicals Inc.)
Chemical Name 7-(Diethylamino)-4-MethyIc cm-
mar in
Molecular Formula
Properties White to light tan powder
M.P. 68-73°C
Excellent heat stability and
outdoor durability
Exhibits strong blue fluorescence
under black light
Applications Pigmented coatings
Solvent and water-based coatings
Advabrite M-10 (Cincinnati Milacron Chemicals, Inc.)
Properties Clear liquid
Safe for skin contact, but
not recommended for food
packaging
Application Plastic
Calcofluor White A2RT Solution (American Cyanamid Co.)
Properties Reddish-blue fluorescence
Excellent fastness to light
and stability to chlorine bleach
Amber liquid
Specific gravity 1.09-1.10
Miscible in water and acetic
acid
Application Acrylic fibers
Calcofluor White GBP Solution (American Cyanamid Co.)
Properties Characteristics of a low sub-
stantive direct dye
Pale amber liquid
pH 9.8
Slight odor of ammonia
Anionic in reaction
Soluble in water
Specific gravity 1.11
Application Paper
A-136
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Calcofluor White LPH Solution (American Cyanamid Co.)
Properties Amber solution
Negligible odor
pH 7.5-8.0 :
Specific gravity 1.2
Application Paper
Aclarat 8678 (Sandoz Colors and Chemicals)
Properties Powder in form
Insoluble in water
Soluble in equal weight of
sulfuric or hydrochloric acid
Soluble in nonionic, anionic,
and cationic surfactants
Soluble in nearly all common
organic solvents
Compatible with acids, reducing
agents, oxidizing agents,
anionics, cationics, and non-
ionics
Applications Nylon, acetate, wool, silk
Shampoo additive
Fabric softeners
Soaps
Suggested application Brightening agent in hydrogen
peroxide hair bleaches
Sandoz TH-40 (Sandoz Colors and Chemicals)
Properties Brown liquid
Anionic in nature
Substantive to cotton, rayon,
and nylon
Compatible with anionic and
nonionic compounds, thermo-
setting resins, alkalies,
slightly acidic media, oxygen
bleaches
Application Cellulosic materials
A-137
-------
Leucophor C7002, Leucophor CS, and Leucophor C6902 (Sandoz Colors
and Chemicals)
Properties Clear brown liquids
Anionic in character
Good stabilities to acids,
alkali salts, and hard water
Not compatible with cationic
compounds
Compatible with anionic com-
pounds, nonionic compounds,
fillers and shading pigments,
direct and acid dyes, acid
and alkaline starches, wet
strength resins
Application Paper
A-138
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TECHNICAL REPORT DATA
(Please read lattaictions on the reverse before completing}
! I. REPORT NO.
EPA-560/2-75-002
3. RECIPIENT'S ACCESSIOWNO.
4. TITLE AND SUBTITLE preiiminary Study of Selected Potential
Environmental Contaminants - Optical Brighteners, .
Methyl Chloroform, Trichloroethylene, Tetrachloro-
ethylene and Ion Fxrhangp Rp«;ins .
7. AUTHOR(S)
B. REPORT DATE
July 1975
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
'Science Information Services Department
Franklin Institute Research Laboratories
Philadelphia, Pennsylvania 19103
10. PROGRAM ELEMENT NO.
2LA328
11. CONTRACT/GRANT NOT
68-01-1897
12. SPONSORING AGENCY NAME AND ADDRESS
Office of Toxic Substances
Environmental Protection Agency
Washington, D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final .,
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
A comprehensive review of the literature published from 1953 through
1973 was conducted to prepare this preliminary investigation report on
the physical and chemical properties of optical brighteners, methyl chloro-
form, trichloroethylene, tetrachloroethylene and ion exchange resins, on
environmental exposure factors related to their consumption and use, on the
health and environmental effects resulting from exposure to these substances
and on any applicable regulations and standards governing their use.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
optical brighteners
cleaning solvents
trichloroethylene
methyl chloroform
tetrachloroethy1ene
ion exchange resins
-chemical properties
-physical properties
-environmental effects
-environmental exposure
06/F,J,P,T
07/A,C,D
18. DISTRIBUTION STATEMENT
Release unlimited
19. SECURITY CLASS (ThisReport)
unclassified
21. NO. OF PAGES
20. SECURITY CLASS (Thispage)
unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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