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.

-------
                            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.

-------
                   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

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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

-------
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

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 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

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                          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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 253.   Tieman, F., Ber.,  24,  2855  (1891).

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 257.   Van Dart, H. M.,  De Jonge,  C. R. H.  I. and Mljs,  W.  J., J.
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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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