WATER POLLUTION CONTROL RESEARCH SERIES • 12040 EFC 01/71
Pollution Abatement
by Fiber Modification
ENVIRONMENTAL PROTECTION AGENCY • RESEARCH AND MONITORING
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WATER POLLUTION CONTROL RESEARCH SERIES
The Water Pollution Control Research Series describes
the results and progress in the control and abatement
of pollution in our Nation's waters. They provide a
central source of information on the research, develop-
ment, and demonstration activities in the Environmental
Protection Agency, through inhouse research and grants
and contracts with Federal, State, and local agencies,
research institutions, and industrial organizations.
Inquiries pertaining to Water Pollution Control Research
Reports should be directed to the Head, Project Reports
System, Office of Research and Monitoring, Environmental
Protection Agency, Room 801, Washington, DC 20242.
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POLLUTION ABATEMENT BY FIBER MODIFICATION
by
Institute of Forest Products
College of Forest Resources
University of Washington
Seattle, Washington 98105
a report for the
Environmental Protection Agency
Program #12040 EFC
January 1971
For sate by tin Superintendent of Documents, U.S. Government Printing Office
Washington, D.C. 20*02 - Price 68 cents
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EPA REVIEW NOTICE
This report has been reviewed by the Water Quality
Office, Environmental Protection Agency, and approved
for publication. Approval does not signify that the
content? necessarily reflect the views and policies
of the Environmental Protection Agency, nor does
mention of trade names or commercial products constitute
endorsement or recommendation for use.
ii
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ABSTRACT
Laboratory studies were conducted to determine if the collection of
pollutants from water using fibers was a feasible concept.
Any cellulosic or lignocellulosic fibers can be reacted with di- or_
tri-halogeno-s-triazines in simple aqueous conditions so that about
10% by weight of reactive sites can be built into the fiber. The mod-
ified fibers can be regarded as polychloro-s^-triazinylated fibers in
which each sj-triazine ring contains approximately one or two reactive
chlorine atoms. The extent of reaction is generally determined by
the stereotopochemistry of the fiber and in particular by its lignin
content and its mfcroporous structure. Ch1oro-s_-triazines are capa-
ble of reacting in aqueous solutions with amines, mereaptans and
phenols, typical of those present in pulping wastes and bleach plant
effluent. The efficiency of this system is obviously increased as
the size of the pollutant removed per reactive fiber size is increased,
Methods to increase the size of 1ignosulfonates by condensation have
therefore been developed.
Two new methods for the collection of pollutants by fibers based on
oxidative grafting and physical entrapment by hydrodynamic volume
changes have also been discovered and a procedure for the character-
ization of copolymer compositions by surface tension has been estab-
lished.
This report was submitted in fulfillment of project 120^0-EFC under
the sponsorship of the Federal Water Quality Administration.
iii
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CONTENTS
Abstract iii
Contents v
List of Figures vii
List of Tables ix
Conclusion 1
Recommendation 1
Introduction 3
Discussion of Results 5
Fiber reactive dyes 6
Phenolic model compounds Jl
Lignosulphonate polymerizations 12
Amine reactions 14
Cyanuric chloride 17
Polyethylenimine reactions 25
Phenolic oxidative coupling 28
Experimental 33
Materials and Chemicals 33
Analytical methods 34
Fiber reactive dye reactions
a) pulp fibers 34
b) wood and bark fibers 35
Dyed fiber - phenol reaction 35
Cyanuric chloride - phenol reaction 35
Lignosulfonate molecular weight augmentation 36
Cyanuric chloride - kraft fiber reaction 3?
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Cyanuric chloride hydrolysis 37
Dyed fiber - amine reaction 37
Batch and continuous oxidatlve coupling reactions 38
Thiol reaction 39
Acknowledgments 39
Key to References 40
References 41
List of Patents and Publications 54
vi
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LIST OF FIGURES
FJj3jjre_Np. LlXL^-PJLfJAHT®. Page No
1 Effect of fiber reactive dye concentration on paper- 7
making fiber receptivity.
2 Effect of reaction time on receptivity of a-cellulose. 7
3 Effect of beating time on fiber receptivity. &
k Effect of bleaching on fiber receptivity. S
5 Effect of reaction pH on dye receptivity of 9
ct-cel lulose.
6 Effect of fiber reactive dye concentration on fiber 9
receptivity of Mason Ite bark and wood pulps.
7 Effect of fiber reactive dye concentration on fiber 10
receptivity of Asplund pulp and whole wood fibers.
3 Effect of pH on the fiber receptivity of white fir 10
Asplund whole wood fibers.
9 Effect of reaction pH on the reaction efficiency of 15
animation of dyed fibers by m-phenylenediamine.
10 Effect of reaction pH on the reaction efficiency of 16
am in at ion of dyed fibers by the various amines used.
11 Effect of amine concentration on the reaction efficiency 17
of animation by mj-aminophenol and m-phenylenediamine.
12 Temperature dependence of hydrolysis of cyanuric IS
chloride at pH 10.
13 Effects of temperature on the rates of hydrolysis and 18
fiber receptivity of cyanuric chloride.
l*t Effect of cyanuric chloride concentration on fiber 21
receptivity.
15 Efficiency of reaction of cyanuric chloride with kraft 21
fibers as a function of cyanuric chloride concentration.
16 Effect of base concentration on fiber receptivity at 23
various cyanuric chloride to fiber ratios.
17 Preparation and structure of polyethylenimines. 2&
18 Retention of protein by a-cellulose after elution with 2?
water at pH 7*
vii
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19 Retention of protein by a-cellulose after elution at 2?
various pH's in the range pH 3 - pH 10.
20 Formation and rearrangement of free radicals from 28
phenolic hydroxyl groups.
21 Co-polymerization of free radicals from phenolic 28
pollutants and Iignocellulosic fibers.
22 Effect of pH on fiber receptivity of o-chlorophenol 30
lignocellulosic fiber co-polymerization.
23 Repetitive entrapment of a model pollutant. 30
2k o_-Bromophenol receptivity of a-cellulose and Masonlte- 31
type fibers.
25 Effect of amount of pollutant grafted on the ultimate 33
tensile strength.
viii
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Jj.bJ-S.i!£' Title of Table Page No.
I Monomeric phenols used as models to simulate the reac- 12
tivity of phenolic hydroxyl groups in lignins and bleach
plant effluent.
II Products obtained from the reaction of phenolic hydroxyl 13
groups in various environments with cyanuric chloride.
Ill Treatments used in the modification of 1ignosulfonates 14
and the intrinsic viscosities of the modified products,
both after dialysis and after further reaction with
formaldehyde.
IV Amine compounds reacted with dyed fibers. 14
V Effect of temperature on fiber receptivity. 19
VI Effect of reaction time on fiber receptivity. 19
VII Effect of cyanuric chloride concentration on fiber 20
receptivity.
VIII Effect of the pre-reaction adsorption time on fiber 22
receptivity.
IX Effect of the reaction medium composition on fiber 22
receptivity.
X Chemical and physical properties of the polyamines used. 25
XI Effect of pH on intrinsic viscosity and molecular volume 26
of PEL
XII Amounts of various phenols grafted to cellulosic fibers 29
under different reaction conditions.
XIII Continuous entrapment of model pollutant (p_-Chlorophenol) 31
by a column of kraft pulp.
XIV Effect of dichloromethane extraction on the bromophenol 32
content of fibers.
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ons
CONCLUSIONS
1. Water pollutants consisting of amines, mercaptans and phenols
can be removed from solution by three methods of entrapment on
or within fibers.
2. Of these, fiber modification by halogeno-s_-triaz?nes is the most
general and technically flexible procedure for pollutant entrap-
ment.
3. From a technical and economic standpoint the most attractive
procedure for the removal of 1ignosulfonates from spent sulfite
waste liquor will probably be based on their oxidative grafting
to 1ignocellulosic fiber sheets for the improvement of strength
properties.
A. The oxidative grafting procedures using 1ignocellulosic fibers
offer promise as a general means of removing low concentration
of phenolic pollutants from water. Thus, this research is of
potential importance for three main reasons:
(a) New methods for modifying 1ignocellulose fiber surfaces have
been developed which, with further work, may be industrially
acceptable within the framework of existing papermaking
practices.
(b) The modified fibers may extend the range of utility of
1ignocellulosic fiber and lead to paper products with im-
proved rigidity when wet.
(c) If these improvements can be achieved using the materials
present in discharged pulp liquors it should reduce river
and stream pollution both by providing a large volume out-
let for this waste and the incentive to attempt to utilize
it.
RECOMMENDATIONS
1. Research in the area of pollution abatement by fiber modifica-
tion should be continued.
2. Emphasis in future research should be placed on the development
of a viable process suitable for a pilot demonstration project.
3. Such a process should focus on the change in the strength pro-
perties of groundwood fiber sheets caused by the grafting of
1ignosulfonates from spent sulfite waste liquor.
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INTRODUCTION
Wood is a natural fiber composite consisting of approximately 60%
polysaccharide and 30% polyphenolic macromolecules. For many uses,
the pulp and paper industry separates the polysaccharide material as
fibers and simultaneously generates water soluble derivatives of the
natural insoluble phenolic polymer of the tree. It is important to
appreciate the tremendous quantities of these lignin derivatives
available because thus far only relatively minor uses for this poly-
mer have been discovered. In effect, there is roughly one pound of
these pulp wastes for every two pounds of paper, and the U. S. pro-
duction of paper in 1969 was approximately 50 million tons. The
phenolic material can broadly be divided into two categories; kraft
lignin and 1ignosulfonates. The former is the larger nationally and
originates from the kraft pulping process. The 1ignosulfonates on
the other hand are predominant in the Pacific Northwest where some of
the world's largest sulfite mills are located. Washington has approx-
imately 32 pulp mills and these are large in size. Immense quanti-
ties of Hgnosulfonates are therefore generated and discharged Jnto
the waterways of the Pacific Northwest. Kraft lignin can be disposed
of by burning and does not constitute an intrinsic water quality
hazard although this is a poor use of a polymer carefully grown and
protected for more than half a century. Nonetheless, kraft lignin
may end up in part as a water pollutant since it is not completely
removed from the fiber during pulping and if the pulp is subsequently
bleached a bleach plant effluent is created. Washington and Oregon
also contain about 16 kraft mills which generate quantities of bleach
plant effluent. This may contain chlorinated phenolic material toxic
to aquatic life and derived from the residual lignin of the fiber.
The 1ignosulfonates however are much larger volume water pollutants
as their historical disposal has been simple dumping in streams,
rivers and waterways. This ?s manifestly undesirable, for in addition
to their water polluting qualities ge£ ^e, lignosulfonates function
as dispersants maintaining solid material in suspension which would
otherwise settle out.
It is therefore a worthwhile research goal to develop systems capable
of abating the pollution resulting from the discharge of lignosul-
fonates or bleach plant effluent into the waters of the Pacific North-
west by finding a suitable use for these pollutants. However, because
of the quantity of material in question there are relatively few uses
which can be seriously envisaged. The underlying concept of this work
has been that wood fiber composites themselves provide one such use
opportunity by virtue of their volume and intimate commercial connec-
tion with the production of the pollutants. More specifically, the
ultimate goal has been to devise procedures for the attachment of
lignosulfonates or other 1ignin-derived pollutants to wood or pulp
fibers to create useful fiber-polymer composites.
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DISCUSSION OF RESULTS
The original broad aims of this program were:
(l) to determine what species, size and shape of molecule can be
attached to lignocellulosic fibers using simple reactions com-
patible with the established processes for the manufacture of
fibrous products;
(2) to investigate the effect of the attachment of such molecules
on the physical properties of fibers and fiber composites, and
(3) to use this information to assess the feasibility of reducing
water pollution due to pulp liquor discharge by reattaching the
waste polymeric chemicals contained therein to paper and wood
fibers.
In the pursuit of these goals a number of technical and economic con-
straints have to be recognized from the outset. These include:
(a) The procedure for the attachment of the pollutants to the fiber
must be capable of being carried out in an aqueous medium prefer-
ably at ambient temperatures and in a pH range close to neutral,
(b) A relatively substantial amount of pollutant needs to be attached
per unit of fiber.
(c) The anticipated properties of the final fiber-pollutant compo-
site will indicate applications such as shipping containers where
strength and rigidity (but not whiteness) are important.
Attention was therefore initially directed towards gaining an under-
standing of the chemistry involved in the attachment of phenolic mat-
erials to fiber surfaces.
The original plan was predicated upon the then unrecognized potential
of fiber reactive dye chemistry as a general foundation for fiber
modification. The act of dyeing is, after all, a chemical modifica- .
tion and it seemed entirely rational to build up on the thousands of
man-years of research which had culminated in the development of fiber
reactive dyes in 1956. These dyes are known to form covalent bonds
with cellulosic fibers at ambient temperatures and at pH values be-
tween 10 and 11 by the reaction depicted in equation (1).
ci
Preparation of dye.
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SO,Na
SO.Na
Fiber
<•>
'
Reaction with fiber.
The long unperceived key to the selective reaction of dye with the
hydroxyl groups of the fiber rather than the infinitely more numerous
hydroxyl groups of the water resides in a combination of simple physico-
chemical facts. Thus, firstly, it is the hydroxyl and cellulosate
anions which are in competition for the modifying species, not the
water and cellulose hydroxyls and the latter are substantially in
excess within the pH range 1~\2. Second, the rate of reaction of the
modifying species with the fiber is determined by its concentration
in the fiber phase and not by its much lower concentration In the
surrounding water.
Our first task therefore was to determine whether the chemistry devel-
oped for dyeing cotton was applicable to wood derived fibers of diff-
ering morphology and chemical composition. A typical dichloro-s-
triazine fiber reactive dye was selected because of its availabTlity
and because after reaction it would still be expected to contain one
reactive chlorine suitable for the attachment of pollutants. This
dye was found to smoothly react with a wide variety of wood-derived
fibers in amounts theoretically suitable for the subsequent attach-
ment of substantial amounts of 1ignosulfonates or bleach plant efflu-
ents. The effects of various reaction conditions including pH and
time, were Investigated and are summarized in Figs. 1-8.
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25-
O Unbeaten •e-cdlulose
O OC-cdkllOSe, Ui|Mly tillin
• Glassine pulp
• Milled oc - cellulose
• Cotton, cut
® Cotton, uncut
100
150 200
additiw (JJ.JB-)
250
Fig. i. Dye receptivity of paperntaking fibers.
Fig 1 shows the fiber reactive dye receptivity (in mg dye/g fiber)
of cellulosic fibers at various dye addition levels, and shows that
beyond a certain value the addition of further dye is without effect
on the receptivity.
SI 100
Reiclion lime («• I
Fig. 2. Dye receptivity of unbeaten a.-cellulose as function of
reaction time.
Fig 2 shows the effect of reaction time on dye receptivity, and
as in Fig 1, shows that beyond a certain level, here about 50 min,
extended reaction times have little effect.
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90-
E
S
70-
50-
9 Filter piper cellulose i dye addition 124
a Unbleached kralt pulp,, • 129
• Unbleached kralt pulp, • 187
so So to
Beating lime (min.)
Fig. 3. Effect of beating on fiber receptivity.
Fig 3 shows the effect of beating upon the fiber receptivity, and
as might be expected, the creation of new surfaces due to beating
produces an increase in dye receptivity.
»
I
I
O» Unbleached kralt pulp, Oiwir,«niii°i
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GO
is 50-
s
40-
Fig. 3. Effect of pH on dye receptivity of unbeaten a.-cellulo$e.
Fig 5 shows the effect of pH on the dye receptivity of a-cellulose,
and shows the expected increase with pH as the concentration of cell'
ulosate ion increases over this range.
too
O Redwood Mosonite
• Douglas fir and Ponderoso
pine Mosonite
D Douglas fir bark 303
• Douglas fir bark 608
100
Dye addition
300
Dye receptivity of Masonite fibers and bark pulps
Fig 6 shows the dye receptivity of both Masonite fibers and bark
pulps, which are seen to be similar to the results obtained in Fig 1.
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I
110-
100-
I 80-
*
60
40-
| 20-
Asplund libers and pulp
a Redolder-cotlonwood pulp
O While fir
» Hemlock °-
• Red gum
100 200 300
Dye addition ( mg..**ye }
\ g fibers/
Dye receptivity of Asplund whole wood fibers and
Asplund pulp
Fig 7 shows the dye receptivity of Asplund fibers, and is seen
to be similar to Figs. 1 and 6.
65
60
Dye addition
,24
10.4
"iae ias"
pH
Effect of pH on fiber receptivity of white fir Asplund
whole wood fibers
Fig 8 shows the dye receptivity of Asplund fibers, as a function
of pH, and although similar to that in Fig 5 at pH less than 10.8,
shows an unexpected drop at pH 11.
10
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The important conclusion emerging from this phase of the research is
that any wood fiber can be easily modified in water suspension at
ambient temperatures so that 103 by weight of reactive sites can be
introduced onto the fiber, which corresponds to some 1020 reactive
sites per gram of fiber. The presence of the reactive sites was
shown by neutron activation analysis using the Nuclear Reactor facil-
ities of the University of Washington. The speed and facility of this
method of the analysis of fibers have made a tremendous contribution
to the rate of progress of this investigation and the technical assis-
tance of Dr. G. L. Woodruff and Mr. W. P. Miller and the administra-
tive cooperation of Professor A. Babb are gratefully and explicitly
acknowledged.
With the means of activating any wood fiber now in hand, attention
was turned to a study of the reactivity of these fibers towards the
phenolic pollutants. To establish the basic reaction conditions some
model experiments were first undertaken. These employed cyanurlc
chloride as a model for the chloro-s_-triazinylated fiber and mono-
meric phenols with various substituents, selected to simulate the
structural environments of the phenolic hydroxyl groups in lignosul-
fonates and bleach plant effluent. Since the lignin hydroxyl groups
are often flanked by substituents in the 2 and 6 positions, reaction with
cyanuric chloride is difficult or impossible if the substituent groups
are too large, and the results in Table I illustrate this. In the
case of lignin and pulp wastes there may possibly be even greater steric
hindrance than in the case of the model compounds.
General Reaction Scheme
OR. OR, OR,
1
OR,
I 1 I
OL OR, OR.
I 1 I
N
11
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TABLE I
Monomeric Phenols Used as Models to Simulate the Reactivity of
Phenolic Hydroxyl Groups in Llgnins and Bleach Plant Effluents
Unreactive Phenols
2-t^-butyl-
2-benzoyl-J|-dodecyloxy -
2-methoxy't-formyl -6-nitro
4-tj-butyl-2-phenyl —
Phenols Giving Pi-substituted Products
A-aceto-2-methoxy -
2-chloro-4-phenyl -
2,6-dimethoxy —
2,6-dimethyl -
Phenols Giving TrJ-substituted Products
4-sec-amyl-
3-benzoxy-
2-benzyl-A-chloro-
4-bromo-
4-jt-butyl -
5-chloro-2-formyl-
4-formyl-2-methoxy-
2-1sopropyl-5-methyI -
3-isopropyl-
2-methoxy-
4-methoxy-
Jt-methylth?o-3-methyl-
4-methylthio-
^t-phenoxy-
8-quinolinoxy-
The results of this phase of the program gave the products described
in Table II and defined steric problems and established the reaction
conditions necessary for the combination of pollutants with cyanuric
chloride.
Concurrently with these two phases of this investigation a separate
research program was underway which involved studies of methods of
controlling the molecular weight of 1ignosulfonates. Several tech-
niques of building up the molecular weight were developed in this
program. These are simple technically and should be applicable to
sulfite pulp waste liquors. Molecular weights in excess of one mil-
lion were achieved by dialysis and by the use of acidic formaldehyde,
cyanuric chloride or oxidative coupling. The potentially low cost
condensation with formaldehyde was the most fully investigated and
the control of molecular size achieved is shown in Table III.
12
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TABLE I I
The products obtained from the reaction of phenolic hydroxyl
groups in various environments with cyanuric chloride
Characteristics of aryloxy-«-triazines.
Compound
2,4,6-Tri(4-sec-amylphenoxy)-«-triazme
2,4,6-Tri(3-benzoxyphenoxy)-«-triazine
2,4,6-Tri(2-benzyl-4-chlorophenoxy)-s-triazine
2,4,6-Tri(4-bromophenoxy)-«-triazine*
2,4)6-Tri(4-<-butylphenoxy)-«-triazine
2,4)6-Tri(5-ohloro-2-formylphenoxy)-s-triazine
2,4,6-Tri(4-formyl-2-inethoxyphenoxy)-«-triazine
2,4,6-Tri(2-isopropyl-5-methylphenoxy)-«-triazine **
2,4,6-Tri(3-isopropyIphenoxy)-«-triazine
2,4,6-Tri(2-methoxyphenoxy)-s-triazine
2,4,0-Tri(4-methoxyphenoxy)-a-triazine
2,4,6-Tri(4-methylthio-3-methylphenoxy)-s-triazine
2,4,6-Tri(4-methylthiophenoxy)-*-triazine
2,4,6-Tri(4-phenoxyphenoxy)-«-triazine
2,4,6-Tri(8-quinolinoxy)-«-triazine
2-Chloro-4,8-di(4-aoeto-2-m«thoxypheuoxy)-«-triazine#"
2.Chloro-4,6-di(2-ohloro-4-phenylphenoxy)-8-triazuie#1
2-Chloro-4,6-di(2,6.dimethoxyphenoxy)-«-triazine#s
2.Chloro-4,6-di(2,6.dimethylphenoxy)-«-triazine#*
Crystalline
form
blades ac
felted needles "
fine nodules '
thin strands"
spiky needles "
soft needles d
hard nodules*
rhombohedrons"
fine needles "
rhombohedrons"
felted needles "
blades'
felted needles"
fine needles "
fine prisms "*
hard nodules'
hard nodules"
prisms"
fine needles *
M.p. °C
183-184
187-189
144-145
130—131
191-193
176-177
208-210
158-160
130—132
164-166
199-200
237-238
216-217
219-221
260-262
204-205
188-190
195-197
163-165
Yield
Wt. %
6.7 g
10.5
4,0
5.0
4.1
1.8
7.5
3.8
5.0
4.2
4.2
5.5
8.1
2.5
2.8
5.3
2.8
8.0
6.8
59
75
55
8*
40
30
70
36
52
94
94
51
81
40
55
61
41
93
94
Formula
C36H45N303
C«H8,N309
C12H30N303C13
CzlH12NsOsBr3
C33H39N303
CS1H12N306C13
C,,H21N30,
C33H39N303
C30H33N303
CMH2IN30,
CHHuN.0.
C27H2,N303S3
C21H21N303S3
C39H2,N3Oe
C30H18N603
C21H18N306C1
0,^.^0,0,
C1,H18N306C1
C^H^OsCl
M.W.
567.8
717.7
731.1
594.1
525.7
544.7
531.5
525.7
483.6
447.5
447.5
537.7
495.7
633.7
510.5
443.9
520.8
419.8
355.8
Carbon % Hydrogen % Nitrogen %
Calc. Found Calc. Found Calc. Found
76.15 75.96
70.28 70.33
42.44 42.71
75.39 75.36
52.90 52.75
64.43 63.83
64.43 64.21
73.93 73.66
70.58 70.71
62.26 62.31
7.99
3.79
2.04
7.48
2.22
4.73
4.73
4.30
3.55
3.10
7.8
4.0
2.0
7.7
2.4
4.9
4.8
4.2
3.8
3.1
7.40
5.85
5.75
7.07
7.99
7.71
7.91
7.99
8.69
9.39
9.39
7.81
8.48
6.63
16.46
9.47
8.07
10.02
11.81
7.9
5.9
6.0
7.3
8.1
7.9
7.9
8.0
8.9
9.3
9.4
7.5
8.4
6.6
16.7
9.3
8.2
9.9
11.8
Crystallization solvents: * ethyl acetate, * dimethylformamide, c methanol, d hexane, * ace-
tone, ' dioxan, f ethanol.
* Bromine content; calc. 40.26 %, found 39.8 %.
(#1,2,3,4,) Chlorine content: (1) calc. 20.4 %, found 19.7 %; (2) calc. 8.0 %, found 7.8 %;
(3) cale. 8.4 %, found 8.2 %; (4) calc. 10.0 %, found 10.5 %.
** Otto 2I gives m.p. 151° for this compound prepared by the fusion of cyanuric chloride
and thymol.
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TABLE 11 I
Modification of Ammonium and Sodium Lignosulfonates by Dialysis
and/or Condensation with Formaldehyde.
Lignosul fonate
starting material
Haras perse N-22
Orzan A
Orzan A
Marasperse N-22
Mar as perse N-22
Orzan A
Orzan A
Marasperse N-22
Orzan A
Marasperse N-22
Duration
of
dialysis
12 days
15
15
0
18
15
15
18
15
12
Intrinsic
viscosity
after dialysis
0.051 dl/g
0.057
0.057
.036
0.051
0.057
0.057
0.051
0.057
0.051
Duration of
condensation
with
formaldehyde
0 hr
11
20
60
16
28
43
29
48
48
Intrinsic
viscosity
after
condensation
dl/g
0.078
0.097
0.013
0.146
0.182
0.238
0.303
0.385
0.47
Table III shows the treatments used in the modification of Hgnosul-
fonated and the intrinsic viscosities of the modified products,
both after dialysis and after further reaction with formaldehyde.
However, attempts to attach phenolic material to the reactive dyed
fibers by means of the chlorine containing dye moiety were unsuccess-
ful. This failure was shown to be caused by the presence of the neg-
atively charged suTfonate groups on the dye which effectively repelled
any approaching negatively charged phenolic material. Positively
charged material, exemplified by amines on the other hand, was readily
trapped by covalent attachment to the fiber. The amines used are
listed In Table IV; and the effect of pH on the efficiency of their
entrapment is illustrated by the data in Figs. 9-U.
TABLE IV
Ami no Compounds Reacted with Dyed Fibers
Aromatic Amines Other Amino Compounds
m-phenylene diamine
m-aminophenol
p-aminophenol
s-1 r i ami nobenzene
urea
melamine
-------
8Ch
17°1
I 60-
50-
40-
No additional
base added
Constant pH
7
PH
Fig 9 shows the effect of the reaction pH upon the reaction effi-
ciency, and indicates that there is a maximum when the system is
allowed to become self-buffering.
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I
.§
1
I
90
80
70
60-
50-
40-
30-
20-
10-
MAP
MPD
• m-Phtnylenediomin» (MPD)
O m-Aminophanol (MAP)
A * -Triominobenztn* (TAB)
• p - Aminophtnol (PAP)
A Ut«o (U)
O Mtlomirw (M)
6789
Initial pH of reaction
10
Fig 10 shows the effect of reaction pH on the efficiency of reac-
tion, and shows that in most cases there is an optimum pH for greatest
reaction efficiency.
16
-------
MPD reacted at pH 8.2
MAP reacted at pH 8.5
o m-Aminophenol (MAP)
• m-Rhenylenediomine (MPD)
40 80 120 160 200 240
Addition of amine mg/g fibers
Efficiency of amination of chloro-s-triazinyl fibers by
m-phenylenediamine and m-aminofhenol.
Fig 11 shows the effect of amlne concentration on the reaction
efficiency, and indicates, as in Figs. 1 and 2, that there is
a maximum beyond which further addition is pointless.
Thus the dyed fibers could perhaps be developed into an effective
process for removing amine-containing impurities from water.
Thiols could also be trapped by chlorotriazinylated fibers so that
sulfur-containing pollutants might be removable from water by this
approach. Lignin can of course be readily thiolated. Thiolated
fibers offer perhaps some promise as a means of trapping traces
of mercury in water. The name mereaptan originates from the Latin
"corpus mercurio aptum".
Of course, it had been recognized from the outsat that the fiber reac-
tive dye was only a convenient chemical tool to introduce reactive
sites onto the fiber. Clearly, it would be much more desirable ultim-
ately to use the parent moiety of the dye, cyanuric chloride, since
it is a bulk chemical of commerce. Moreover, It contains three reac-
tive sites and no unnecessary and unwanted dye moiety. An examination
of the reaction of cyanuric chloride with wood fibers was therefore
undertaken. By the use of a buffer system and a low temperature an
unexpectedly extensive and extremely rapid reaction with fibers could
be achieved as exemplified by the data in Figs. 12-16 and Tables V-IX.
17
-------
100
2468
REACTION TIME.min
Temperature dependence of the
hydrolysis of cyammc chloride at pH 10.
Fig 12 shows the temperature dependence of the hydrolysis of
cyanuric chloride at pH 10, and indicates a drastic drop in hydrolysis
with a drop in temperature.
100
-5 -10
Temperature dependence of fiber receptivity vs. hydrolysis of cyanuric chloride.
25 20 15 10 5 0
TEMPERATURE, °C
Fig 13 shows the effect of temperature on fiber receptivity, which
is seen to increase with decreasing temperature, presumably as a
result of the decrease in hydrolysis.
18
-------
TABLE V
Effect of Temperature on Fiber Receptivity
(which is seen to increase with decreasing temperature, presumably
due to the decrease in hydrolysis)
Effect of Temperature on
Fiber Receptivity
Reaction Procedure "A"
Temper-
ature,
°C
25
5
0
-10
Reac-
tion
time,
min
10
7
7
7
Nitrogen
content
of
fibers,
r»g/g
6.3
8.6
14.7
16.4
Cyanuric
chloride
reacted
with
fibers,
mg/g
27.6
38.0
64.5
71.9
. No. of
chlorine
atoms
pers-
triazine
ring
0.51
1.44
TABLE VI
Effect of Reaction Time on Fiber Receptivity
Effect of
Reaction Time on Fiber
Receptivity
Reaction Procedure "B,"
with addition of IN NaOH (12.5 ml)
Cyanuric
Nitrogen chloride
Reac-
tion
time,
min
1
5
10
content
of
fibers,
mgjg
12.8
13.6
15.8
reacted
with
fibers,
mg/g
56.2
59.8
69.0
Chlorine
content
of
fibers,
mg/g
15.6
16.5
18.8
No. of
chlorine
atoms
pers-
triazine
ring
1.36
1.44
1.42
19
-------
TABLE VII
Effect of Cyanuric Chloride Concentration on Fiber Receptivity
(which may be seen graphically in Figure
Effect of Cyanuric Chloride
Concentration on Fiber Receptivity
Reaction Procedure "B"
Cyanuric No. of
Alkali Nitrogen chloride Chlorine chlorine
addition content reacted content atoms
IN of with of pers-
NaOH, fibers, fibers, fibers, triazine
ml mg/g mg/g mg/g ring
50 mg cyanuric chloride added per 1 g fiber
1.0 4.7 20.6 6.1 1.54
2.0 5.6 24.6 8.2 1.73
3.5 5.4 23.7
8.0 5.5 24.1
100 mg cyanuric chloride added per 1 g fiber
1.0
2.5
3.5
5.0
7.5
10.0
5.0
6.9
7.3
9.5
10.3
7.7
21.9
30.3
32.0
41.7
45.2
33.8
12.7
9.9
8.2
2.0
1,23
1.00
• i >
200 mg cyanuric chloride added per 1 g fiber
2.5 7.5 32.9 7.5 1.19"
5.0 9.2 40.4 9.4 1.20"
7.5 13.6 59.6 12.2 1.07»
10.0 14.2 62.3
400 mg cyanuric chloride added per 1 g fiber
5.0 7.4 32,5 1.11 1.86
12.5 13.9 61.0
15.0 15.7 68.9 20.4 1.55
25.0 16.2 71.0 18.0 1.30
600 mg cyanuric chloride added per 1 g fiber
15.0 17.2 75.5 19.3 1.33b
20.0 20.4 89.5
1.42"
25.0
30. 0«
40. 0«
22.2
24.7
20.9
97.4
108.5
91.8
26.
• Dried at 110°, 24 hr.
fc Dried at 110°. 5 hr.
c Addition time, 2.5 min.
20
-------
100
£
S 80
<=Z
60
as
40
0>
E
z
0 0.1 0.2 03 0.4 0.5 0.6
CYANURIC CHLORIDE ADDITION, g/g fiber
Effect of cyanuric chloride con-
centration on fiber receptivity.
Fig lA shows the effect of cyanuric chloride concentration on the
receptivity, and is similar to that in Fig 1.
100
80
>' 60
o
z
LJ
o 40
20
•V
0 0.1 02 03 04 0.5 0.6
CYANURIC CHLORIDE ADDITION, g/g fiber
Efficiency of the reaction of
cyanuric chloride with kraf t fibers.
Fig 15 shows the efficiency of reaction of cyanuric chloride with
kraft fibers as a function of the amount of cyanuric chloride added
per gram of fiber, and indicates an almost linear relationship between
efficiency and cyanuric chloride addition.
21
-------
TABLE VII I
Effect of the Pre-reactlon Adsorption Time on Fiber Receptivity1
Effect of Prereaction
Adsorption Time on Fiber Receptivity
Reaction Procedure "B,"
with 1 min reaction time
and addition of IN NaOH (10
Adsorp-
tion
time,
min
0
2
10
15
Nitro-
gen
content
of
fibers,
mg/g
9.1
10.0
9.9
10.8
Cyanuric
chloride
reacted
with
fibers,
mglg
39.7
43.7
43.5
47.5
Chlorine
content
of
fibers,
mg/g
11.0
11.4
10.7
ml)
No. of
chlorine
atoms
pers-
triazine
ring
1.44
1.36
1.17
Here the fiber suspension and cyanuric chloride are mixed for the stated
adsorption time prior to the addition of base to start the reaction.
TABLE IX
Effect of the Reaction Medium Composition on the Fiber Receptivity
Effect of Acetone/Water
Ratio on Fiber Receptivity
Reaction Procedure "B,"
with addition of 0.2 g of
cyanuric chloride per 1 g
fibers and \N NaOH (6 ml).
Ace-
tone
con-
tent
of
mix-
ture,
%
60
80
100
Cyanuric
Nitrogen chloride
content reacted
of with
fibers, fibers,
mg/g mgjg
11.5
12.2
13.5
50.7
53.5
61.9
Chlorine
content
of
fibers,
mglg
14.5
15.3
15.0
No. of
chlorine
atoms/s-
Iriazine
ring
1.49
1.49
1.27
22
-------
CYANURIC CHLORIDE ADDED,
g/g fiber
0.2
2468
NaOH ADDITION, meq
Fiber receptivity vs. NaOH
addition.
Figure 16 shows the effect of the amount of base added on the fiber
receptivity for various cyanuric chloride to fiber ratios.
This theoretically should yield a dich1oro-s_-triaziny1ated fiber since
only one of the original three chlorines has been used to attach the
s-trlazine ring to the fiber. However, some additional chlorine atoms
aVe dissipated hydrolytically or in inter-chain crosslinking and each
s-triazine ring attached to the fiber therefore contains on the aver-
age about 1.5 reactive site per is-triazine ring. These reactive
chlorine atoms are capable of reacting with phenolic, amino and also
thiol groups.
The research therefore had now reached the point where aqueous reac-
tion conditions had been established for the proposed attachment of
phenolic impurities to wood fibers using a cyanuric chloride bridge.
However, very little could be said about the points of attachment of
pollutant to be preferred from a strength point of view. The preferred
size of the pollutant to be attached to the fiber was likewise obscure.
To clarify these points some knowledge of the topography of the fibers
was needed and it was fortunate that a major contribution to this area
was forthcoming during the period covered by this grant. Thus, Stone
and Seal Ian, using a series of polysaccharides as molecular probes,
were able to show that typical pulp fibers have a multilamellar micro-
porous cell wall. Although their views may not be correct in every
detail, the concept is certainly applicable to the problem of attach-
ing macromolecules to fibers. That is, very large macromolecules
cannot penetrate Into the smaller pores of the fiber and are thus
located on the geometrical exterior of the fiber. Smaller molecules
on the other hand can penetrate and later crosslink the Interior of
the cell wall. The general validity of these views was assessed by
using a series of polyethylenlmine polymers of known molecular weight.
Polymerization of the monomer ethylenimlne under acidic conditions
23
-------
H2f\ acid
,NH —, , > vw-K?H= N
u r/ catalyst * °
Y\zU J PEI
Ethyleneimine
le
x^~N Hg
LJ M M
H2N N
1
N-
NM
IM
H H
125%
JT ^ 50%
V 1 25%
NM
i y
H 1
N....
H
M
IM
N..,
H
1° N
2° N
3° N
H
N.
H
U M
M
IN
-NH
;
Fig 17- Preparation and structure of polyethylenimine.
-------
(Fig 17) leads to a three dimensional network of ami no nitrogen atoms
which can assume a positive charge, become cationtc in neutral or
mildly acidic solution and thus are substantive to the naturally
anionic cellulose macromolecules. The varied molecular weights
and physical characteristics of the molecules used are shown in
Table X.
Fig 17 shows the preparation and structure of polyethylenimine.
TABLE X
The Chemical and Physical Properties of the Polyamines Used
Polyamine
Diethylenetriamine
DP
2
Triethylenetetramine 3
Tetraethylenepenta-
mine
Pentaethylenehexami
Polyethylene! mine
1 1
1 1
it
n
4
ne 5
14
116
700
1163
17^5
Molecular
Weight
103
146
189
232
600
5,000
30,000
=50,000
-75,000
Molecular
Diameter*
7.0A
7.8
8.5
9.0
12.3
24.7
44.9
53.3
61.0
Density
at 25°
0.95 g/cc
0.97
0.99
1.01
1.03
1.04
1.05
1.05
1.06
Mi trogen
Content
40.7%
38.3
37.0
36.2
33.4
33.0
33.0
32.7
33.0
*The molecular diameters of the amines were calculated using the for-
mulas for the volume of a sphere (V = 4.18 r ) and literature values
for their densities.
25
-------
During this particular phase of the investigation a completely new
method of trapping polyelectrolytes within microporous substrates
was discovered. This is the so-called "Jack-in-the-Box" effect where
a sudden expansion in the hydrodynamic volume of a polymer, triggered
by pH (Table XI) causes it to be trapped against the sides of the
containing pore.
TABLE XI
Variation of Intrinsic Viscosity and Effective Molecular Volume of
Polyethylenimine Mn=«75,000, s.g. 1.2, with pH
Effective Molecular
pH
12.5
10.0
7.0
3.5
Intrinsic Viscosity
1.00
1.06
1.85
2.22
Volume (A 3)
1038
1100
1920
2303
This phenomenon is more conveniently and clearly demonstrated exper-
imentally using proteins because their minimum hydrodynamic volume
occurs at the isoelectric point, which is quite centrally located on
the pH scale where the ionization of cellulose (pK=13.7) is relatively
smalI.
Thus, a-cellulose pulp fibers, impregnated with an aqueous solution
of collagenous animal protein (Technical Protein Colloid No. 5V,
Swift Chemical Co., Oak Brook, Illinois), give maximum retention of
the protein at its isoelectric point (Fig 18) because the protein
macromolcule is in its smallest form at this pH.
26
-------
1-20 n
Jo-80-
£
•8
I
JO-40-
BeaetlonpH
o-OeUuloM fibre (6 a , .
•qoeoiu protein ttlatlon (oH 8 to 10,
water OrH 7, 700
with 0-08 par cent (w/v)
with
._
_ mL) tor 1 h and elated
forSmln.
Fig 18 shows the amount of protein retained by a-cellulose fiber
after impregnation at various reaction pH's and elution with water
at pH 7.
It is therefore capable of penetrating the largest number of the fiber
pores. Conversely, if a series of protein-impregnated fibers are
separately washed with water which has been adjusted to different pH
values, maximum protein elution will be secured at the isoelectric
point (Fig 19).
1-20
[0-80
10-40
EluUonpH
aqueous
a-Celluloie fibre (5 g) Impregnated with 0-08 per cent (w/v)
protein lolutltm (p& 6, 260ml.) for SO h aiii elutod with
•olutlon {^H 8 to 0, 700 nil.} for 8 mta.
Fig 19 shows the amount of protein retained by a-cellulose fiber
after impregnation at pH5 and elution at various pH's in the range
pH3 - pH 10.
27
-------
At this pH, the macromolecules within the fiber will have adopted
their smallest and most elutable size. Above and below the isoelec-
tric point, the protein macromolecule is distended by the mutual re-
pulsions of its carboxylate anions or immonium cations respectively
and it is therefore retained by the "Jack-in-the-box" effect. As
anticipated, progressive destruction of the fibrous character (and
the associated pores) by beating diminishes the magnitude of this
type of polymer retention. This is also exhibited by a variety of
other microporous solids, including boiling stones, rayon and cotton
fibers. In conformity with the proposed "Jack-in-the-box" retention
mechanism, PEI irreversibly adsorbed onto cellulose fibers can be
readily eluted by washing at pH 12 where it assumes minimum hydro-
dynamic volume. Since lignosulfonates and other water pollutants
such as proteins are polyelectrolytes this technique may be valuable
for their nonchemical entrapment by porous substrates.
Another potentially attractive pollution abatement procedure emerged
and was briefly scouted during this research grant. Thus, 1ignocellu-
losic fibers contain phenolic hydroxyl groups as an integral part
of the fibers as depicted in Fig 20.
Fibre
Fibre
Fibre
M«0
Fig 20 shows the process of formation and rearrangement of a free
radical derived from a 1ignocellulosic fiber containing phenolic
hydroxyl groups.
Moreover, it has recently been established that phenols can be oxida-
tively polymerized. Clearly, then, if soluble phenols are polymerized
in the presence of 1ignocellulosic fibers the phenolic groups of the
lignin should ultimately copolymerize with the other phenolic species
in the polymerization. This, in fact, occurs as represented in Fig.
21 and Table XII and the soluble phenols are thus entrapped by the
fibers.
• fibw
Fig 21 shows the mode of polymerization of a typical phenolic
pollutant onto a Iignocellulosic fiber containing phenolic hydroxyl
groups (see Fig. 18).
-------
TABLE XI I
The Amounts of Various Phenols Grafted to Lignocellulosic Fibers
Under Different Reaction Conditions
icnol Grafted
o-bromo-
m-bromo-
p-bromo-
o-chloro-
2,6-dimethyl-
Fiber
Substrate
a
b
a
b
a
b
a
a
Reaction
pH
12
12
12
12
12
12
10
10
Amount of Grafting
to fibers
(u moles/g)
55
15
27
12
80
22
J|00
J{00
(a) unbleached kraft pulp of western red cedar and hemlock (85:15)
(b) Mason ite- type Redwood fiber
This polymerization is noteworthy kinetically because no general termin-
ation step can be written and pollutants can theoretically be continued
to be collected ad infinitum. The polymerization is induced by several
oxidants including low cost ferric chloride and in a non-aqueous sys-
tem, oxygen. It proceeds best at the pK value of the phenol (Fig. 22),
and can be used to remove very small amounts of phenol from water
solution.
29
-------
400
Effect ofpHon the amount of o-chlorophenol grafted to kraft pulp
Fig 22 shows the effect of pH upon the fiber receptivity during
p-chlorophenol grafting, and indicates a maximum receptivity in the
"region of the pK of the phenol.
3
A more complex study has shown that both batchwise and columnar reactors
are feasible, and that in the batchwise process, repetition of the
whole reaction cycle increases the pollutant grafted almost linearly
with the number of reaction cycles (Fig. 23).
o>
u
4)
-O
i
Q.
as
125 1
100
75 "
50
- 25
o
0.
1 2 3 *» 5
Reaction cycle
Fig. 23 shows the entrapment of p_-Bromophenol by kraft pulp. The
column process as a model for a continuous system used p_-halophen-
ols as pollutants end potassium ferricyanide db oxldant. Table Xiil
shows that, as expected, the collection efficiency is a maximum at
the top of the column.
30
-------
TABLE XIII
Continuous Entrapment of Model Pollutant (o-Chlorophenol)
by Column of Kraft Pulp
Co 1 umn
Temperature
25°C
55 "
Pol lution
at Top of Column
122 p mol/g
158 "
Entrapment by Fiber
at Bottom of Column
75 P mol/g
5k "
A more extensive study of the chemistry of this copolymerization tech-
nique has also been made. In this, the relative reactivity of the
isomeric halophenols has been determined, and the efficiency of various
oxidizing agents has been evaluated. Proof that copolymerization is
indeed occurring onto the lignin in the fiber rather than homopolymer-
ization in solution, is obtained by the difference in receptivities
of Masonite and a-cellulose fibers (Fig. 24).
Extraction of both these grafted fibers with dichloromethane showed
that phenolic material in the a-cellulose, while present, was not
firmly attached and is probably only physically entangled within the
fiber matrix. Table XIV shows results obtained using various
halophenols and oxidants.
K Fe(CN)6
FeCl
None
Fiber Substrate
Masonite
a-cellulose
Masonite
a-cellulose
Masonite
a-cellulose
Masonite
a-cellulose
ymol phenol/g fiber grafted
5 10 15
I
Fig 2k o-Bromophenol receptivity of a-cellulose
Masonite-type fibers.
31
-------
TABLE XIV
Effect of Dichloromethane Extraction on the Bromophenol
Content of Fibers
Fiber Oxidant
Substrate System
a-Cel lulose None
a-Cel lulose K,Fe(CN),
Mason fte None
Masonite K.Fe(CN),
3 o
Kraft None
Kraft K,Fe(CN),
Kraft K2S2Og-FeSO^
Kraft FeCl3
Kraft K3Fe(CN)6
Kraft Fed
Kraft K Fe(CN),
Kraft FeCl_
Kraft K-Fe(CN),
Kraft Fed,
Phenol receptivity of fiber
Bromophenol u mol phenol/g fibers
Grafted
ortho
ortho
ortho
ortho
ortho
ortho
ortho
ortho
ortho
ortho
meta
meta
para
para
Unextracted
A.I
A. 9
1.2
16.8
0.3
11.3
20.7
9.5
107
121
A5
41
97
95
Extracted
1.1
A. 7
0.7
15.3
0.5
11.2
20.8
10.0
82
102
37
35
78
76
The relative receptivity of kraft and Masonite fibers is not found to
be proportional to their lignin content, and an explanation advanced
for this is that the kraft lignin is more accessible (due to pulping)
and also less condensed, thus containing more phenolic hydroxyl groups
capable of reaction.
Studies as yet incomplete indicate that low molecular weight lignin
fractions can be coupled to groundwood fibers using reaction conditions
similar to the above.
The benefits to be anticipated from this system are demonstrated by
32
-------
Fig. 25 which summarizes the improvements obtained in the tensile
strength of unbleached kraft sheets by the grafting of pulp wastes.
c
O"
O)
0)
•M
CO
0)
c
V
1000
10
20
Weight increase,
50
Fig 25 shows the increase in ultimate tensile strength in pounds
per square inch with the amount of pulp waste pollutant grafted to
the sheet.
EXPERIMENTAL SECTION
Materials.
Cellulosic fibers used comprised: a slightly beajen a-cellulose
(Whatman No. 1 filter paper, W 6 R Balston Ltd, England). Cotton,
uncut and cut to 3 mm lengths, from the Red Cross Cotton Co., John-
son and Johnson, New Brunswick, N. J. A commercial unbeaten
a-cellulose (Pulp-S-9^7, Rayonier Corp., Shelton, Washington.).
Lignocellulosic fibers comprised: glassine, containing 0.6% lignin,
was Powder paper #3, distributed by Eli Lilly & Co. and the product
of St. Regis Paper, Rhinelander, Wise, Asplund Wood Fibers
from: (a) white fir (Abies cqncojor), (b) western hemlock (Tsuga
heterophylla), (c) red gum "(Liqu i dambar styrac i f1ua). Asplund pulp
fibers (85? yield) from a neutral sulfite semi-chemical treatment
of an 80:20 mixture of western red alder (AInus rubra, Bong) and
cottonwood, (Populus deltoldes). Masonite fibers from redwood (Sequoia
sempervi rens) and a 70:30 mixture of Douglas fir (Pseudotsuga taxjjojjra)
and Ponderosa pine (Pinus ponderosa). Douglas fir bark fibers contain-
ing. 38 and 25.6% lignin (WEF 303 and 608). An unbleached kraft pulp
33
-------
containing 8.2% llgnin derived from an 85:15 mixture of western red
cedar (Jhu[a pi feata) and western hemlock (Tsuga heterophylla), don-
ated by the Weyerhauser Co., Everett, Wash. A dry, unbleached,
unbeaten sulfite pulp containing 12% hemicelluloses and 1.3% lignin,
also donated by the Weyerhauser Co., Everett, Wash.
Chemicals.
All chemicals used in this project were stock commercial items. The
1ignosulfonates used were Marasperse N-22 , (a sodium salt) from
the Marathon Division of the American Can Co., Menasha, Wise, and
Orzan A, (an ammonium salt) from the Crown Zellerbach Corp, Camas,
Wash.
Analytical Methods.
In this work the estimation of nitrogen and the halogens has been the
main method of estimation of reaction efficiencies. Nitrogen was
estimated by a modified Kjeldahl method. Halogen analysis was per-
formed using the neutron activation analysis technique at the Nuclear
Reactor facilities of the University of Washington. In this technique
a small (100-500 mg) sample of reacted fiber is irradiated in a
neutron flux of circa 2 x 10 neutrons/(cm sec) for time intervals
between 5 and 30 min. After appropriate cooling, the photopeak
of the halogen was counted with a 3" x 3" Nal(TI) crystal and multichannel
analyser. Spectrum stripping was occasionally necessary to eliminate
the interference encountered from both sodium and other metal Ions
present in trace amounts. Sulfur analysis was performed similarly
using the same conditions, but encounters more interference from sod-
ium in the sample, and for this reason exchange of lithium for sodium
by elutriation of the sample with a solution of a soluble lithium
salt prior to analysis has been found to be desirable when only small
amounts of sulfur are present.
Reaction of Pulp Fibers with Fiber Reactive Dye.
A stirred suspension of fiber (A.55 g) in distilled water (177.5 g)
at 25° having a consistency of 2.5% was treated with the fiber reac-
tive dye. After the dye had dissolved, sodium chloride C».55 g) was
added and the mixture was stirred for 15 min and adjusted to pH 10.50
using a 10% sodium carbonate solution. Stirring was then continued
for 90 min when the pH had dropped to 10.35. The fibers were collected
by filtration on a foraminous plate, washed with hot distilled water
(80°, 400 ml) for 70-90 min, refiltered and rewashed with hot distilled
water (80°, AOO ml) and again soaked in hot distilled water (80°,
400 ml) for 70-90 min. Finally the fiber mass was again filtered
off and washed with cold distilled water until the volume of the
combined washings was 2000 ml.
In addition to analysis for nitrogen and chlorine by Kjeldahl and
neutron activation methods, a check on the amount of dye unreacted was
made by UV spectrophotometry using the dye absorption maximum at 3600 A.
34
-------
Reaction of Wood and Bark Fibers with Fiber Reactive Dye.
A stirred suspension of fiber (5g) in distilled water (200 ml) at 26°
was treated with the fiber reactive dye (1) and after 15 min sodium
chloride (5g) was added. Stirring was then continued for 15 min when
the mixture was adjusted to pH 10.50 using solid sodium carbonate for
the Asplund fibers and a 10% sodium carbonate solution for the Mason-
ite and bark fibers. During the following reaction period ($0 min)
the pH was kept constant by the addition of more of the same alkaline
reagent. The fibers were then collected by filtration on a forami-
nous plate, washed with distilled water (26°, 1800 ml for the Asplund
fibers, 900 ml for the Masonite and bark fibers), resuspended and
soaked in distilled water (26°, 500 ml) overnight, refiltered and
washed until the volume of the combined washings was either 3000
ml (Asplund fibers) or 2000 ml (Masonite and bark fibers).
Reaction of Dyed Fibers with Phenols or Thiophenols.
The reaction between dyed fibers and the phenols or tniophenols was
carried out by adding dyed redwood Masonite fibers (2.2g) to a stirred
solution of the phenol or thiophenol (I mmol) in distilled water
(80 ml) at 26°. The pH of the suspension was adjusted to and main-
tained at 11.0 for 2.5 hr using a 0.1N sodium hydroxide solution, when
the fibers were collected by filtration and washed with distilled
water (26°, 1000 ml). The amount of unreacted dye was again deter-
mined by UV spectrophotometry.
Reaction of Cyanuric Chloride with Model Phenols.
2,l»,6-Tri-(/»-sec-amylphenoxy)-s_-triazine. A solution of cyanuric
chloride (3.69g, 0.02 mo!) in acetone (100 ml) or dioxan (50 ml)
was added with vigorous stirring to ice-water (200 ml). The resul-
tant finely divided suspension, maintained at 0-5°, was then treated
dropwise with a sodium hydroxide (2.kg, 0.06 mol) solution (200 ml)
of l»-sec_-amy I phenol (9-85g, 0.06 mol) added over 15 min. The mix-
ture was stirred for 2-hr at the same temperature and then for a fur-
ther hour at room temperature. The crystalline solid which had sep-
arated was collected, washed well with water and then with methanol.
Subsequent crystallization from methanol-ethyl acetate yielded the
product characterized in Table II. The other eighteen compounds
listed in Table II were prepared similarly. Chlorine and nitrogen
analyses were carried out as previously described.
Augmentation of Lignosulfonate Molecular Weight.
Condensation of 1ignosulfonates with formaldehyde were typically
carried out by refluxing a solution of the dialysed or undialysed
lignosulfonate (8g) in water (150 ml) for 11-60 hr with an aqueous
formaldehyde solution (372, 2 ml) and concentrated (d, 1.8*1) sulfuric
acid (k ml). Sample withdrawal and the further addition of aqueous
formaldehyde (37%, 2-6 ml) were made intermittently.
35
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Dialyses were carried out over a period of days using seamless cello-
phane tubing (100 ml capacity, 3.8 cm diam) immersed in constantly
circulating water (l8,l). Molecular weight changes were followed by
intrinsic viscosity measurements made on 1ignosulfonate solutions in
0.1M sodium chloride at 25 ± 0.5°C using a Fenske viscometer.
Coup 1 ing of Lignosulfonates wj th Cyan^ric jChloride.
Cyanuric chloride (Ig) partially dissolved in dioxan (10 ml), was
slowly added dropwlse to a solution (55 ml) of dialysed sodium 1igno-
sulfonate (17g/d1, [nl=0.051 dl/g) at pH 9.1 and <5° with vigorous
stirring. As the cyanuric chloride was added, the viscosity of the
solution increased gradually initially and then dramatically until
the 1ignosulfonate almost became insoluble. When this point was
reached, the solution was diluted with water to prevent the larger
molecular weight lignosulfonates from becoming totally insoluble.
This dilution was carried out when the solution became so viscous
that the stirrer would no longer mix the solution of polymerizing
1iqnosulfonates. Caution in dilution was required because too great
a dilution caused the polymerization reaction to slow down perceptibly.
In addition, the more dilute the 1ignosulfonate solution, the larger
the amount of cyanuric chloride consumed to achieve an equal molecular
weight qain. The solution became viscous and was diluted several
times before the reaction was complete. The reaction was considered
complete when no further thickening of the solution occurred, irres-
pective of how much cyanuric chloride was subsequently added. The phi
was maintained above 9.0 with 5M NaOH throughout the reaction. After
centrifuging off the precipitated 1ignosulfonates, the soluble frac-
tion was dialysed for four days. By either adding less cyanuric
chloride or by extracting samples at intermediate points during the
reaction, a range in molecular weights similar to the formaldehyde
condensed 1ignosulfonates was obtained.
Oxidative Complexing of Lignosulfonates with Dichromate.
Acetic acid (11.4 ml) was added to a solution (189 ml, 6.5g/dl) at
room temperature of dialysed sodium 1 ignosulfonate ([r)]=0.051 dl/g)
with stirring. Na2Cr,07v2H20 (7.5g) was then added. Samples (25 ml)
were then removed every 10 min for 1 hr, and diluted with water
(300 ml) to stop the polymerization, neutralized with 5N NaOH, and
dialysed for 7 days in a similar manner to the cyanuric chloride sam-
ples. After 25 min, a noticeable thickening of the solution occurred.
In order to prevent precipitation of the lignosulfonates in solution,
water (50 ml) was added.
Ox idat_lye_ Coupling of Lignosul fonates.
A solution (200 ml, 6.5g/dl) at room temperature of dialysed sodium
1ignosulfonate ([n.]=0.051 dl/g) was adjusted to pH 10 with 5N NaOH.
K.Fe(CN)x (lAg) was then added and the pH was maintained above 10 with
5N NaOH throughout the reaction. Samples (25 ml) were taken
36
-------
intermittently, diluted with water (175 ml), the pH adjusted to 3-5
to stop the reaction, and dialysed for 7 days in a similar manner
as before.
Reactioni__ofCyanu/ic__ChJ_or_i__de w? th Kraft Fibers.
Two reaction procedures designated A and B were employed.
Procedure A: A vigorously stirred suspension of kraft fibers (5g) in
a" w'ater-acetone mixture (1:1, 200 ml) at -10° was treated with a sol-
ution of cyanuric chloride (2g) in acetone (50 ml) and then adjusted
to pH 12 with an aqueous 5N sodium hydroxide solution. After stirring
for 10 min, the fibers were collected by filtration on a foraminous
plate, sequentially washed with water (200 ml), acetone (300 ml) and
dioxan (150 ml) extracted with dioxan for 2 hr in a Soxhlet apparatus,
dried at 100°, and analyzed for nitrogen and chlorine.
Procedure B: A vigorously stirred and cooled suspension of kraft
fibers (5g) in water (100 ml) and acetone (100 ml) at -10° was treated
with a solution of cyanuric chloride (2g) in acetone (50 ml). When
the temperature of the fiber suspension was again -10° an aqueous IN
solution of sodium hydroxide (15 ml) was added dropwise during 2 min
and after 3 min more the pH was lowered to ^ by the addition of dilute
sulfuric acid, thereby terminating the reaction. The fibers were col-
lected as before, washed successively with water (2000 ml) and acetone
(^00 ml) soaked in acetone for 2k hr, filtered, rewashed with ace-
tone (200 ml), dried at room temperature under reduced pressure, and
analyzed for nitrogen and chlorine.
Rate of Hydrolysis of Cyanuric Chloride.
A solution of cyanuric chloride (ig) in acetone (50 ml) was added to
a vigorously stirred mixture of water (100 ml) and acetone (100 ml)
at -10° and a IN solution of aqueous sodium hydroxide was used to
adjust and maintain the mixture at pH 10. The consumption of the
sodium hydroxide was observed as a function of t4me and was used to
calculate the extent of hydrolysis of the cyanuric chloride.
Reac 11 on of_jDyed Kraft Fiber with Amino Compounds.
The ami no compound (500 mg) was added to a stirred suspension of the
dyed kraft fibers (5g) in water (200 ml) at 25°. The pH was adjusted
to selected values with 0.1N sulfuric acid or 0.1N sodium hydroxide,
and after a 2 hr reaction period, the fibers were collected by filtra-
tion and washed sequentially with dilute sulfuric acid (pH 2.5, 300 ml)
sodium hydroxide solution (pH 11, 300 ml), and distilled water (300
ml). This washing was repeated twice, followed by elutriation of
the'fibers with distilled water to a total filtrate volume of 3000
ml. Control dyed fibers were treated similarly without any addition
of amine.
37
-------
Batich Reactions.
A suspension of fiber (2g) in distilled water (73g) at 25° was stirred
with the oxidizing agent for 30 min. The halophenol in acetone (5 ml)
was then added and stirring was continued for 120 min. Each of the
three isomeric bromophenols was used at two levels in combination with
the three oxidants, potassium persulfate-ferrous sulfate, alkaline
potassium ferricyanide and ferric chloride as follows: (a) bromophenol
(6.8 mmol), acetic acid (6 ml), potassium persulfate (2.kg) and fer-
rous sulfate (20 mg), (b) bromophenol (18.68 mmol), acetic acid (12
ml), potassium persulfate (4.8g) and ferrous sulfate (20 mg), (c)
bromophenol (6.84 mmol), potassium ferricyanide (1.820g) and sodium
hydroxide (440 mg), (d) bromophenol (13.68 mmol), potassium ferricy-
anide (3.64g) and sodium hydroxide (880 mg), (e) bromophenol(6.84
mmol) and ferric chloride (Ig). Control experiments (f) were also
carried out in which the oxidants were omitted and only the bromo-
phenol (6.84 mmol) was included with the fibers.
The fibers were collected by filtration on a foraminous plate,
washed consecutively with distilled water (200 ml), hydrochloric acid
(0.1M, 700 ml), aqueous sodium hydroxide (O.lM, 700 ml), distilled
water (700 ml) and acetone (200 ml). The washed fibers were dried
at 60°.
The effect of pH on the receptivity of the fiber was studied only in
the case of o_-chlorophenol oxidatively coupled using potassium ferri-
cyanide. The fibers were stirred with the oxidizing agent (4.6g) for
30 min at 25°. A solution of o-chlorophenol (6.56 mmol) in ethanol
(10 ml) was then added dropwise over 180 min. The pH was adjusted
using 5N sulfuric acid or 5N sodium hydroxide. The washing and dry-
ing procedures were unchanged.
jBatch_JEnt rapment_ of Phenol j c Po 11 ytan ts by j- ignoce 11ulos i c F 8 be rs.
A suspension of the 1ignoceIlulosic fiber (2g) in distilled water
(78g) at 25° was stirred with the oxidizing agent [K.Fe(CN)6, l.82g;
NaOH, 0.44g] for 30 min and then treated with a solution of the model
pollutant (£-bromophenol, 1.2g, 6.84 mmol) in acetone (5 ml). After
stirring for 2 hr the fibers were collected by filtration, washed
sequentially with distilled water (500 ml), dilute aqueous hydro-
chloric acid solution (0.1N, 200 ml), dilute aqueous sodium hydrox-
ide solution (0.1N, 200 ml), distilled water (500 ml) and acetone
(200 ml), dried at 60°, subjected to neutron activation analysis and
found to contain p-bromophenol (80 ymol/g). Repetition of the fore-
going procedure using the same fibers gave the increased entrapment
of pollutant with each reaction cycle summarized in Fig. 23.
Cont i nuous Ent rapmen t of P he no U c Po11u ta n t s by LJgnocelIulosic Fibers.
Solutions of the model pollutant (<3-chlorophenol, 0.85g, 6.56 mmol)
in distilled water (1400 ml) and potassium ferricyanide (4.6g), in
-------
distilled water (1400 ml) adjusted to pH 10 with sodium hydroxide,
were simultaneously added dropwise to the top of a column (2.5 x 14
cm) of a kraft fiber (2g) suspension (consistency, 5.61%) in water
and allowed to percolate downwards and through during a period of
kO hr. The fibers were then extruded from the column and divided
into two equal fractions corresponding to the top and bottom halves of
the column before application of the washing, drying and analytical
procedures detailed for the batch entrapment experiments. The results
obtained are collected in Table XII.
Reaction of Cyanuric ChiorIde Treated Fibers with Pentaerythritol
TetraTjfme reap top rop? pnajTe) .
Due to the ease of oxidation of thiols in basic media, this thiol
grafting reaction was conducted in a nitrogen atmosphere. To a
cooled and stirred suspension of cyanuric chloride treated a-cellu-
lose (Ig) in acetone (100 ml) at 0*was added pentaerythritol tetra
(3-mercaptopropionate) (0.29g, 0.6 mmol). After 30 min stirring,
sufficient IN sodium hydroxide (2.4 ml) to ionize all the thiol
groups in the thiol compound was added dropwise via a hypodermic sy-
ringe. After a further 30 min the flask was allowed to warm to am-
bient temperature, and after 1 hr the fibers were collected on a
foraminous plate and washed successively with acetone (200 ml).
ACKNOWLEDGEMENTS
The financial support of this project by the FWQA Is gratefully acknow-
ledged together with the able administrative support of Dr. H. K. Wil-
lard and Mr. G. R. Webster.
The technical assistance of Dr. G. L. Woodruff and Mr. W. P. Miller,
and the administrative co-operation of Professor A. Babb of the Nu-
clear Reactor Laboratories, University of Washington was also greatly
appreciated.
39
-------
KEY TO REFERENCES
The references classified below are relevant to the topics indicated.
1-83 The techniques and reactions of fiber reactive dyes
with cellulosic and 1ignocellulosic fibers.
Bk-]]f> The reaction of lignin model compounds with cyanuric
chloride.
117~163 The increase in molecular weight of 1ignosulfonates
by condensation with formaldehyde and the uses of the products.
163-186 The reaction of cyanuric chloride with 1ignocellulosic
fibers and the effects of various reaction conditions.
187-207 The reaction of fiber reactive dye treated 1ignocellu-
losic fibers with amines.
208-217 The oxidative coupling reaction of chlorophenols and
kraft pulp.
218-233 The mechanism of polyethylenimine retention by porous
materials.
233-263 The oxidative coupling of phenolic pollutant model
compounds to 1ignocellulosic fibers.
-------
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LIST OF PATENTS AND PUBLICATIONS
Although a number of findings believed to be patentable have been made
during this work, the necessary complete reduction to practice is not
yet concluded.
The following publications have been produced as a result of this
project.
Allan, G. G., Mauranen, P., Desert, M. D. and Reif, W. M.,
Paperi Puu, 50:523 (1968).
Allan, G. G., Lacitis, A., Lui , F-m., Lee, J-h. and Mauranen,
P., Bolzfovschung 23:198 (19^9).
Allan, G. G., Mauranen, P., Neogi, A. N. and Peet, C. E., Chem.
& Ind. 623 (1969).
Allan, F. J., Allan, G. G., Mattila, T. and Mauranen, P., Aota
Chem. Soand. 23:1903 (1969).
Allan, G. G. and Mattila, T. , Tappi 55:1^58 (1970).
Allan, G. G., Akagane, K., Mattila, T., Neogi, A. N. and Reif,
W. M., Nature 224:175 (1970).
Allan.G. G., Liu, F-m. and Mauranen, P., Paperi Puu £2:^03 (1970)
Allan, G. G., Maranen, P. and Neogi, A. M. , Paperi Puu, in press.
Allan, G. G. and Neogi, A. N., J. Adhesion, in press.
Allan, G. G., Mauranen, P., Neogi, A. M. and Peet, C. E.,
Tappi3 in press.
Allan, G. G. and Halabisky, D. D., Pulp & Paper Mag. Can., 71:
T50 (1970).
Allan, G. G. and Neogi, A. N., J. Appl. Poly. Soi., 14:333
(1970).
54
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1
Accession Number
w
5
2
Subject Field & Group
SELECTED WATER RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
Organization
Title
Pollution Abatement by Fiber Modification
]Q Authors)
Dr. G.G. Allan
16
21
Project Designation
Project No.
120AQ EFC
Note
22
Citation
23
Descriptors (Starred First)
Pulp and Paper Industry, Water Pollution, Fiber Modification, Ugnosulfonates,
Dye Chemistry
25
Identifiers (Starred First)
27
aooraTiory studies were conducted to determine if the collection of pollutants from
usins fibers was a feasible concept. Any cellulosic or lignocellulosic fibers can
-.ri^h .«_ or tri-halogeno-s.-triazines in simple aqueous conditions so that about
IDb
deteed
of reactive sites can be built into the fiber. The modified fibers can
as T»3jrchloro-£-triazinylated fibers in which each s_-triazine ring contains
one or two reactive chlorine atoms. The extent of reaction is generally
?ne Sereotopochemistry of the fiber and in particular by its lignin content
structure. Chloro-s-triazines are capable of reacting in aqueous
tionwas, mercaptans and phenols, typical of those present in pulping wastes
bleach riantef fluent. The efficiency of this system is obviously increased as the
of the^onutant removed per reactive fiber size is increased. Methods to increase
?ia of Senosulfonates by condensation have therefore been developed.
S nL mfthodTfSr the collection of pollutants by fibers based on coddative grafting
m* «hv^^ral entrament by hydrodynamic volume changes have also been discovered and a
procedure for the characterization of copolymer compositions by surface tension has been
established.
Abstracto
Instit
University of Washington
WR:!02 (REV. JULY t9S»)
WRSIC
SEND, '
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. O. C. 20240
* CPO! 1970-388-830
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