Vinyl Cellulose

Prog, Polym. Sci., Vol. I0, pp. 1-50, 1984 0079-6700/84 $0.00 + .
50
Printed in Great Britain. All Rights Reserved. Copyright © 1983 Pergamon Press Ltd.
GRAFTING OF VINYL MONOMERS TO

CELLULOSE BY C E R I C I O N I N I T I A T I O N
D. J. McDOWALL, B. S. GUPTA and V. T. STANNETT
School o f Textiles, North Carolina State University, Raleigh, NC 2 7650, USA
CONTENTS
1. Introduction I
2. Kinetics and mechanism 2
2.1. Ceric oxidation 3
2.2. Graft polymerization 6
2.3. Oxidation site 10
2.4. Alternative mechanisms 16
3. Conditions affecting grafting 18
3.1. Time 19
3.2. Initiator 20
3.3. Acid 21
3.4. Monomer 22
3.5. Temperature 24
3.6. Substrate 26
3.7. Other variables 28
4. Characterization of grafted products 29
4.1. Proof of grafting 29
4.2. Fine structure and morphology 30
4.3. Molecular structure 31
5. Properties of the grafted products 32
5.1. Mechanical properties 32
5.2. Water sorption and penetration 32
5.3. Ion exchange and membrane properties 38
5.4. Other properties 38
1. I N T R O D U C T I O N
Grafting has been utilized as an important technique for modifying physical and
chemical properties of polymers. A particular advantage of grafting is that the
modification can be performed on pre-existing polymers which may or may not be
in the form of a shaped object such as fiber or fdm. This is of particular importance
in dealing with natural polymers such as cellulose. Ideally certain properties can be
imparted to the substrate without significantly altering others. For example, by
grafting various monomers onto cellulose it is possible to attain many different
2 D.J. McDOWALL, B. S. GUPTA and V. T, STANNETT
properties including elasticity, sorbancy, ion exchange capabilities, thermal resis-

tance and resistance to microbiological attack.
A number of grafting methods have been developed which may be classified into
three groups: (1) free radical; (2) ionic; and (3) condensation and ring opening
polymerizations. The free radical methods have received the greatest amount of
attention due to their practicality. Free radicals are formed on the cellulose molecu-
les either by chemical means or by irradiation. The general field of grafting onto
cellulosics has been reviewed by a number of authors, 1-s and more recently in a
monograph. 9 A discussion has also appeared recently on "Challenges in Cellulose
Grafting") ° Among the most interesting of these grafting methods is the formation
of free radicals on the cellulose molecules by direct oxidation with ceric ions. The
use of ceric ions to initiate graft polymerization was first discussed by Mino and
Kaizerman in 1958.11 Schwab and coworkers 12 were among the first to extend this
method to the grafting of cellulose. Following their work, numerous papers have
appeared in the literature on the grafting of vinyl monomers onto cellulose by this
technique. Since a detailed review of this grafting method has not been published
in the literature, it is felt that a thorough review of the work in this field would be
of interest and make a timely contribution to the literature in this area.
The three major areas covered in this review are:
(1) the kinetics and mechanism of ceric ion grafting;
(2) the effect of various reaction variables;
(3) the characterization of the resulting products.
Also included is a small section at the end which summarizes the changes which
take place in the physical properties of the substrate as a result of grafting as well as
a table summarizing the various monomers and cellulosic substrates which have
been grafted via this technique. Possible applications for ceric grafted cellulosics
will not be discussed here, since these are similar to those of other initiation
methods which have been reviewed elsewhere. 9
2, K I N E T I C S AND MECHANISM
The oxidation of various alcohols, aldehydes and glycols by ceric salts has been
well documented) 1'13-19 In 1943, Smith and Duke 13 examined the oxidation of
several organic compounds, including cellulose, by ceric ions. Mino and Kaizer-
man 11 were among the first to study the initiation of vinyl polymerization by the
transient free radicals produced from an oxidation-reduction reaction of ceric salts
with alcohols, thiols, glycols, aldehydes and amines. They also suggested the use
of cellulose as the reducing agent, leading to the initiation of graft polymerization.
The precise kinetics and mechanism governing the grafting of vinyl monomers
onto cellulose are difficult to determine since the reaction is heterogeneous. There-
fore, a great deal of work has been performed on alcohols and other model com-
pounds. These will be discussed along with the work available on cellulose.
GRAFTING OF VINYL MONOMERS TO CELLULOSE 3
2.1. Ceric oxidation

Duke and coworkers ~4'is examined the kinetics of ceric ion oxidation of glycols.
Since tetravalent cerium has a coordination number of six, the formation of mono-,
di-, and tri-glycolated intermediates are possible:
CeX 6 + A ~ CeAX4 + 2X (1)
CeAX4 + A ~ CeA2X2 + 2X (2)

CeAX2 + A ~- CeA3 + 2X (3)
where A is a glycol, Ce is tetravalent cerium and X the groups coordinated with
tetravalent cerium, e.g. OH-, NO~ and H20.
It is generally assumed, as originally shown by Duke from his kinetic data, 14
that only monoglycolated intermediates are formed to any appreciable extent.
This intermediate then dissociates forming a free radical which is rapidly oxidized
by another ceric ion as follows:
K kd H +
Ce(IV) + A ~ B~ Ce(III) + A" + (4)
Ce(IV) + A" -~ Products + Ce(III) + H+ (5)
where B is the complex formed. Since the disproportionation of the complex is
the rate determining step, the expression
d[Ce(IV)]
- kd[B] (6)
dt
holds. Substituting for [B]
dICe(IV)]
[1 + K[A] ] [Ce(W)l (7)
dt
where [Ce(IV)] is the total concentration of cerium (IV). (See ref. 20 for more
details.)
At constant alcohol concentrations expression 7 may be written as:
d[Ce(IV)]
= k' [Ce(IV)] (S)
dt
where
k'= kd K[A] (9)

1 + K[A]
or
I 1 1
k-;- = k-~ + ka K[A-----~ (9a)
4 D.J. McDOWALL, B. S. GUPTA and V. T. STANNETT
A series of pseudo first order rate constants k' can be obtained at various alcohol
concentrations. Plots of 1/k' vs 1/[A] result in a straight line if the kinetic scheme
in eq. 4 is followed; i.e. an intermediate complex is formed. This type of linear
behavior has been observed by both kinetic and spectroscopic means for the oxida-
tion of various alcohols, and substrates containing alcohol groups, by ceric ions in
perchloric and nitric a c i d s , 14-t6'21-32 and, in some cases, in sulfuric acid. a3-4° In
other instances, the oxidation of alcohols by ceric salts in a sulfuric acid medium
followed second order kinetics. 18'19'22'39"47 Muhammed and Rao 41 have proposed
the direct oxidation of alcohols (A') by ceric ions in sulfuric acid:
A' + Ce(IV) -+ [ C e ( I V ) . . . A'] " u , A'" + Ce(IIl) + H + (10)
thus,
d[Ce(IV)]
= kli [k'] [Ce(IV)] (11)
dt
At constant alcohol concentrations, the kinetics will again be pseudo first order;
however, the pseudo first order rate constant will be a linear function of the alcohol
concentration. It has been pointed out that second order kinetics may also result
when a complex is formed if the equilibrium constant, K, is small. 19'22'46
Evidence of complex formation between cerium(IV) and cellulose has been
studied by several investigators. 48-sa Kurlyankina and coworkers 4a'49 observed spec-
troscopically that the ceric-ceilulose complex had a characteristic absorption
maximum at 320 m# as seen in Fig. 1. Others have proposed complex formation on
the basis that the initial absorption of cerium(IV) was rapid and the amount
absorbed was much greater than the carbonyl content of the cellulose.S°-s2
o \- ,
, , ,
240 280 320 360 40O O

mft
FIG. 1. The percentage of the complex in hydrated cellulose film as a function of the concen-
tration of cerium perchlorate. I - Without Ce4+; II - Conc. o f Ce** ions in a solution of 0.0005
mole/l; I I I - 0.001 mole/l; IV - 0.002 mole/l; V - 0.0025 mole/l; VI - 0.0030 mole/l. (From
reference 48).
GRAFTING OF VINYL MONOMERS TO CELLULOSE
TABLE 1. Equilibrium constants for ceric-alcohol complex formation in

perchloric acid
Substrate K (l/mol) Reference
methanol 1.5 24
6.2 25
ethanol 4.3 16
4.6 25
n-propanol 4.9 25
isopropanol 0.65 25
trans-2-methoxycyclohexanol 2.1 22
cyclohexanol 2.9 22
ethylene glycol 19 25
1,2-propanediol 23 25
1,3-propanediol 8.5 25
gly cerol 25.0 23
77 25
cis-1,2-cyclohexanediol 29.0 22
trans-1,2-cyclohexanediol 18.0 22
The complexes formed by cerium(IV) with 1,2-glycol units may either be acyclic
or chelated species. Examination of the equilibrium constants for several compounds
containing either one hydroxyl or adjacent hydroxyls (cf. Table 1) showed a higher
stability; i.e. larger equilibrium constant, for compounds containing 1,2 glycol
units. This enhanced stability indicates that a chelated species is formed 22'2s'3Ls4
since these are known to be more stable than acyclic compounds, see ref. 55 for
example. However, Young and Trahanovsky 32 have suggested that the added
stability of diols is not due to a true chelated structure (A) but rather due to an
association between the second hydroxyl hydrogen bonded to one of the other
groups coordinated to the cerium(IV) (B) as depicted below:
I I I I
C~C , C~C
I I I I (12)
0-~ / 0
Ce O"ce O"H
~'X.'"
(A) (B)
Ogiwara and Kubota have suggested that the ceric-cellulose complex may be a
chelated species since the association of the ceric absorbed onto the cellulose was
too strong to be easily removed with dilute acid or alkali, s2,s6
From the evidence available on the oxidation of cellulose, an intermediate
complex appears to be formed between the ceric ion and the cellulose. This is
followed by the disproportionation of the complex to form a radical on the cellu-
lose molecule (cf. eq. 4 where cellulose may be substituted for the alcohol).
2.2. Graft polymerization

The polymerization of vinyl monomers initiated by free radicals, formed with
ceric oxidized alcohols is expected to proceed according to the following reaction
scheme: s7
Initiation
K
Ce(IV) + A ~ B ~ A" + Ce(III) + H + (13)
A'+ M ~ - M' (14)
Ce(IV) + M - ~ M" + Ce(III) + H+ (15)

Propagation
Mn + M - ~ Mn+1 (16)
Termination
Mn + Ce(IV) ~-~ Mn + Ce(III) + H÷ (17)
A" + Ce(IV) - ~ Oxidation products + Ce(IIl) + H + (18)

k'
M" + M~ ~ Polymer (19)
where A is the alcohol, M is the monomer and B the ceric-alcohol complex. Katai
Kulshrestha and Marchessault s7 obtained the following expression for the rate of
polymerization, Rp:
d [M] k.--E [M]2 {k~ + kdK[A] ) (20)

Rp = dt - kt [M] + (ko/ki) ICe(IV)]
They assumed that a steady state exists for both [M'] and [A'] separately and that
the formation of a ceric-alcohol complex is much more rapid than its decom-
position. It was also assumed that termination of the growing polymer chain
is by ceric ion (eq. 17) and not due to radical coupling or disproportionation
(eq. 19). This assumption was valid for polymerization systems initiated by several
alcohols, 19,a0,4s,sv-s9 dextran 6° and cellulose.61'62 However, evidence for radical
coupling was found by others42-~'47 and it has also been noted that termination at
lower ceric ion concentrations was mutual (eq. 19), while at higher ceric ion con-
centrations it proceeded via eq. 17. 43,63 Others have suggested that termination at
lower ceric ion concentrations was due to hydrogen radicals and chain transfer to
water molecules) 9 Termination in the cellulose polymerization system could be
anticipated to be primarily due to ceric ions and not another cellulose radical since
the movement of the cellulose chains is limited. However, the possibility of chain
transfer to solvent molecules and radical coupling with monomer radicals may be
important at low ceric ion concentrations.
Changes in the acid concentration have been shown to affect the observed rates
G R A F T I N G O F V I N Y L MONOMERS TO C E L L U L O S E 7
of ceric oxidation and polymerization.14-16' 18,22-27,29, 31,33,37-39,41,42,44-46, 54, 5'7, 59,64

The relationship between the observed rate of polymerization and the acid con-
centration depended upon the type of acid employedJ 8'23 Several explanations for
this behavior have been proposed. For example, in perchloric acid the following
equilibrium is established:
Ce4+ + H20 ~ CeOH 3+ + H + (21)
and the concentration of Ce4+, the reactive species, depends upon the hydrogen ion
concentration) 6'ls'23-2s'2%29,s''s4 It has also been noted that CeOH s÷ will dimerize
and further polymerize depending upon its concentration) 3'27'29'6s-67 On the
other hand, in sulfuric acid the existence of several ceric sulfate complexes is well
known. 68-7° The following equilibria are established:
Ce4+ + HSO7~ ~ CeSO~+ + H ÷ (22)

CeSO,~÷ + HSOg ~ Ce(SO4)2 + H+ (23)
C e ( S O 4 ) 2 "4- H S O 4 --~ C e ( S O 4 ) 2- nt- H÷ (24)
HS07~ ~ SO42- + H ÷ (25)
The concentration of any of the above species will depend upon the hydrogen
ion and sulfate ion concentration. Some investigators have proposed that only
one species is reactive and have suggested that the fluctuation in the observed
reaction rates with pH was due to the change in concentration of the reactive
species. 23's6-42'44'46'63 Others have suggested that all of these ceric species are
reactive each having its own equilibrium constant for complex formation, its own
complex dissociation constant and termination constant. 22'33'sT'64 The overall
equilibrium, dissociation and termination constants calculated at any particular acid
concentration would thus be expected to be a function of the concentration of the
ceric sulfate species and their respective constants.
A reaction scheme similar to that discussed earlier for alcohols has been proposed
by Ogiwara et al. 71 for cellulose grafting, as shown below:
Initiation
K kd
Ce(IV) + Cell-H ~ Complex , Cell" + Ce(III) + H + (26)
Cell" + M ~ Cell-M' (27)
Ce(IV) + M ~ M" + Ce(III) + H + (28)

Propagation
CeI1-Mn + M ~ Cell-Mn+ I (29)
Mm + M ~ M~a+t (30)
Termination
Cell-Mh + Ce(IV) ~ CelI-M n + Ce(lll) + H÷ (31)
Mm + Ce(IV)k_~ Mm + Ce(Ill)+ H+ (32)
Cell-Mn + Cell" ~ Stabilization (33)
Cell" + Ce(IV) ~-~ Oxidation products + Ce(lll) + H+ (34)

Ogiwara and coworkers 71 obtained eq. 20 from the above reaction scheme assum-
ing, along with previous assumptions, kp = kp' and kt = k't. Since ko[ki is generally
large, s7 ko/k i [Ce(IV)] >> [M], thus, eq. 20 could be written as:
= { kikdK[Cell-H]}
RD ~ [MI2 k'i+ (35)
kt kolCe(IV)]
A similar reaction scheme has been proposed by other workers for the grafting of
cellulosics. ~-76
As seen in eq. 20 and 35, the rate of polymerization, Rp, is inversely propor-
tional to the concentration of ceric ion, implying that the rate of polymerization
may be greater at lower concentrations. The actual grafting yields were generally
found to increase and then decrease with ceric ion concentration (cf. Section 3.2).
This has been discussed by Varma and Narasimhan77 who proposed that reactions
26, 27 and 28 should be reversible since according to their results, increases in the
hydrogen ion concentration suppressed grafting. Under these assumptions they
obtained the following expression for the rate of polymerization:
kpki[M]2 { kl [Ce(IV)] [Ceil-H[ }
Rp = (k-i) + kt [Ce(IV)] (k_~) [Ce(III)] [H +] + ki [M] + ko [Ce(IV)]
(36)
where kl is the rate of complex formation, ki the rate of initiation and k_~ and k_ i
the rates of the reverse reactions. At low ceric ion concentrations, eq. 36 becomes:
kpki [M]2 / k, [Ce(IV)l [Cell-Hl 1
Rp -- k, (37)
which predicts that the rate of polymerization will increase with ceric ion concen-
tration. Whereas at higher ceric ion concentrations, k_i < kt ICe(IV)l, therefore eq.
36 becomes:
Rp
- kpki[M]2 I kl [Cell-H[ /
(38)
kt [ ( k - l ) [Ce(III)] [H+] + k i[M] + ko [Ce(IV)] J
This indicates a decrease in the rate of polymerization as ceric ion concentration

increases. However, the reversibility of eqs 26 and 28 is not generally accepted.
Indeed, Dziegieds4 concluded that the oxidation of alcohols with cerium was not
2.0
22
2.4
" (B)
T
i 2.8
x x
o 3.0
i
(¢)
|
3.4
I I I I i i
I0 20 3O 4O 50 80
ReaCtion time (minutes)
FIG. 2. First-order plots of eerie ion consumption during oxidation and polymerization reaction
with eeUulose: (A) oxidation with 0.012 M eerie; (a) grafting with 0.012 M eerie; (B) oxidation
with 0.006 M eerie; (b) grafting with 0.006 M eerie; (c) oxidation with 0.003 M eerie (From
reference 51).
reversible since changes in the concentration of Ce(III) had no effect on the reac-
tion rates. Hence, according to him the changes in reaction rate with hydrogen ion
concentration were a result of changes in the equilibrium constant, K.
It was interesting to note that the rate of polymerization, Rp, would be directly
proportional to some power of the ceric ion concentration if it was assumed that
chain transfer and radical coupling, rather than eerie ions, were responsible for
termination. It is possible with cellulose, as was seen by some investigators with
alcohols, that at lower ceric ion concentrations, termination proceeds mainly
through these mechanisms, while at higher concentrations termination is pre-
dominantly controlled by ceric ions. This, would also explain the general grafting
behavior observed with changes in eerie ion concentration.
In summary, it can be stated that the general reaction scheme proposed for the
graft polymerization of cellulose (eqs 26-34) appears to be valid. Since during
grafting the eerie ion consumption was generally greater than the consumption due
to oxidation (cf. Fig. 2), one could assume that the homopolymerization reaction
by eerie ions (eq. 29) was responsible for its initiation, s°'~''~-s° Termination of the
grafted side chain with another cellulose radical (eq. 33) appears to be less signifi-
cant than termination by ceric ions, however termination by a monomer radical or
chain transfer should not be neglected. The equation for the rate of polymerization
10 D.J. McDOWALL, B. S. GUPTAand V. T. STANNETT
TABLE 2. Redox polymerization of styrene

by ceric salt and alcohols (adapted from
ref. 62)
Alcohol Polymer yield

none small
tert-Butyi small
ethyl 6.0
n-Octyl 6.1
n-Butyl 6.8
benzyl 8.4
isopropyl 2.0
see-Butyl 1.4
a-phenyl ethyl 1.4
2,3-butanediol 12.3
given by Varma and Narasimhan 77 takes into account changes in the hydrogen ion
concentration and provides an explanation for the changes in grafting behavior with
ceric ion concentration. However, this equation is based on the assumption that the
initiation reactions are reversible which has not been substantiated. It is also possible
to explain the changes in Rp with acid concentration if it is assumed that various
ceric ion species are present. It is, however, difficult to judge the validity of any of
the mechanisms proposed due to the heterogeneous nature of the grafting reaction.
2.3. Oxidation site

The cellulose molecule contains several possible sites for oxidation by ceric salts;
the hydroxyl at the C6 position, the glycol group at the C2-C3 position and the
hydroxyl at the end of the cellulose chain. Many authors have examined model
compounds to elucidate the relative rates of oxidation of these sites. For example,
Iwakura and coworkers 62 examined the polymerization of styrene initiated by free
radicals formed on various alcohols by ceric ions. Since primary alcohols and
1,2 glycols were found most effective (cf. Table 2) it was concluded that polymeri-
zation onto cellulose would occur at the C6 or C2-C3 positions.
Bergam et al. 2° found evidence of oxidation at the C6 position since paper
treated with NO2, which preferentially attacks the C6 carbon, failed to graft. It was
noted that NO2 oxidation is not totally selective and grafting at the C2-C3 position
was also possible. Support for grafting at the C2-C3 glycol group with cleavage of
the C-C bond was obtained by others. 19'81-83 The relative rates of oxidation of the
C6 hydroxyl and the C2-C3 glycol were examined by Hintz and Johnson. 22 They
used model compounds such as cyclohexanemethyl alcohol and tetrahydropyran-
2-methyl alcohol for the C6 hydroxyl, and trans.1,2 cyclohexanediol for the C2-C3
glycol. As indicated in Table 3, by the greater rate of oxidation with trans-l,2
cyclohexanediol, oxidation of cellulose with eerie ions will occur mainly at the
TABLE 3. Relative rates of oxidation of cellulose model com-

pounds* (From ref. 22)
Substrate Relative rate

trans-1, 2-cy clohe xanedi ol 6.0
cyclohexane methyl alcohol 1.3
tetrahydropyran-2-methyl alcohol 1.0
*Obtained from kinetic data.
TABLE 4. Grafting of methyl methacrylate onto polymers containing sugar

residues (From ref. 87)
Backbone polymer Grafting Weight

time (min) increases,%
poly(6-metha~yloyl-D-galactose) 2 1300
poly(1 -methacr yloyl-D-galactose) 5 110
poly(6-methacryloyl-D-glucose) 2 1070
poly(1 -methacryloyl-D-glucose) 6 57
poly(N-methacr yloyl-D-glucosamine) 3 1070
C2-Ca glycol group and not the C6 position. This increased reactivity o f a-glycol
groups was also observed by others, ss'a4
Oxidation at the hemiacetal unit was also investigated. For example, model
compounds containing a hemiacetal unit, such as glucose, were more readily
oxidized than compounds in which this group was blocked, such as a-methyl
glucoside, s°'s2'ss It was found that vinyl polymerization also proceeded more
rapidly when initiated by compounds containing hemiacetal units (cf. Table 4). 86-89
To further examine the most likely site for grafting, several polymers containing
glucose residues were grafted with methyl methacrylate. 9° Reduced reaction rates
were noticed only for the polymers in which the site of glucose attachment to the
polymer chain was the Cz position. On the basis o f these results, Imai, Masuhara
and Iwakura 9° proposed that the oxidation of cellulose by eerie ions occurred
primarily at the hemiacetal unit, as illustrated below.
"~'0
CHIOH
HOH
Ce÷4
-"-
\
jo. CI"~OH
(:~=0 (A)
(39)
"~ CHtOH
~0 =0 (B)
OH
12 D . J . McDOWALL, B. S. GUPTA and V. T. S T A N N E T T
TABLE 5. Oxidation of cellulose model compounds by ceric ions in 1.0 M perchloric acid at
15.0"C (From ref. 21)
Substrate Model for Relative rates

glucose reducing endgroup 360
Schardinger #-dextrin* anhydro-D-glucose repeat unit 1
methyl #-D-glueopyranoside nonreducing endgroup 1
1,5-Anhydro-D-glucitol nonreducing endgroup 1.5
*Concentration based on anhydro-D-glucose units.
They found the carbonyl radical (B) to be the more likely radical formed.
Pottenger and Johnson, as indicated in Table 5, also found support for the
rapid oxidation of the hemiacetal unit, i.e. reducing end group, using model com-
pounds for cellulose.21 Although the rate of oxidation of the hemiacetal unit was
360 times that of the C2-C3 hydroxyls, the relatively large number of the latter
groups in cellulose compared with the end groups indicates that they are still
probable reaction sites. Examination of the products of the oxidation of glucose
by cerium(IV) in perchloric acid showed the presence of arabinose, formic acid
and cerium(Ill). From these results, the following reaction mechanism was
proposed: 21
o M ~ ~H CHzXX~_
/~O\ (CHELATE
H HOH * C e ( ~ K =HO~oH ./~-H COMPLEX)
OH ~-~/Cenvl
- H ~ OH * Cell]]) ÷ H÷ (401
H 1-~/Ce(]~r) H
(FREE- RADICAL)
CHzOH
~-:--o.
FREE-RADICAL , Ce ¢m FAST. L\;..O + C e ( ~ • H+
1
( 4 - 0 - FORMYL- D - ARABINOSE)
4-O -FORMYL - D- ARABINOSE ~ m ARABINOSE÷ FORMIC ACID
Although the free radical may form at either the C1 or the C2 carbon, the C1
position may be preferred due to the possibility of greater resonance stabilization.
This mechanism was supported by others for cellophane 91,92 and ramie. 93 It was
also suggested that the site of grafting was the C1 position since an analysis of the
grafted polymer showed the presence of an aldehyde. 91,92 This mechanism differs
from that discussed previously in that the CI-C2 bond is broken, not the C-O
bond.
Oxidation of Schardinger/~-dextrin and cellulose by cerium(IV)yielded erythrose

and glyoxal, suggesting cleavage at the C2-Ca bond. 21 The following reaction mech-
anism was proposed to explain this behavior.
CH20H CH20H
Ce(rv) K ~ 0 (CHELATE
COMPLEX)
H OH
Ce(I~
CH20H CH20H
kd 0 ~ Ce(.~I}* H+ (41)
SLOW" OH
O-N
C"
b
Ce(l~ ( FREE - RADICAL)
FREE-RADICAL " Ce0-91 FAS1

~ + Ce(]~ +H ÷
~~0 ~0
A similar mechanism was proposed by Arthur and coworkers 94 on the basis of ESR
examination of the ceric oxidation of cotton and microcrystalline cellulose. The
ESR signal was more symmetric for cotton than microcrystalline cellulose, pre-
sumably due to the larger number of endgroups in the latter which would form a
different radical.
Kulkarni and Mehta 5°'s= also examined the products of ceric oxidized cellulose
after hydrolysis. The anticipated reaction was"
(~HzOH CH20H
+ Ce~4 ~ Complex
OH OH
Cell-O.
Cellulose
CHzOH CH~,OH
0 0.,
14 D . J . McDOWALL, B. S. GUPTA and V. T. STANNETT
CH~OH CH20H
] r CH20H CH20H
OH
Hydrolysis
CHzOH ~H, OH 1 (42)
H~
~ H CHOH (~H,OH
HOH -I- J +
H CHOH Clio
I
OH CH~OH Glycol oldehyde
D- Glucole Erythritol
However, the actual reaction products were D-glucose and D-mannose, indicating
that the C2-C3 bond was not broken. The presence of D-mannose indicated that
the eerie ions did react with the C2-Ca hydroxyls and the following reaction was
proposed to explain this phenomenon.
CH20H CH~OH
+ Ce.4 • O\
i
OH 0
Anhydroglucose 2- oxoderivative
Reductionand
~hydrolyss (43)
CH20H CH~OH
H
OH
D-Glucose O-mannose
Analysis of the resulting products under more severe oxidation conditions showed
the formation of glycol aldehyde and D-glucose but no erythritol, indicating that
oxidation proceeded through the cleavage of the C2-Ca bond. This may have
resulted from the conversion of the carbonyl group at C2, formed under milder
oxidation conditions, to COOH. The absence of erythritol was presumably due to
an attack on the primary hydroxyl during oxidation, converting the --CH2OH group
to --COOH.
An interesting study by Kurlyankina and coworkers~'gs showed that the oxi-
dation of cellulose by eerie ions was accompanied by little change in the carbonyl
and carboxyl content of the cellulose (of. Fig. 3). However, formic acid and carbon
dioxide were generated upon eerie oxidation. This indicated that the carbonyl
1000 0.1(
900 O.OS
800 O.Oe
7OO 0.07
i
n-
600 O£)6
500 (:105
40O (104
300 0.03
200 :).02
I00 •01
0 "
7
rrr--
0 O~ 020 030 040
FIG. 3. Oxidation of cotton (I, II, III, IV) and of hydrated cellulose (I', II', III', IV', V') by a
solution of ceric ammonium nitrate at 20°C. I and I' - degree of polymerization of cellulose;
II and II' - percentage of carbonyl groups in cellulose; III and III' - percentage of carboxyl
groups in cellulose; IV and IV' - amount of abstracted HCOOH; V' - amount of abstracted
CO2 (From reference 48).
groups which were formed during ceric oxidation were readily oxidized to low mol.
wt compounds with extensive degradation o f the glucose units.
Other investigators have also noted the importance o f the hemiacetal units in the
ceric oxidation o f cellulose, s3'71'96-1°° Taga and Inagaki l°l noted that blockage of
the reducing end group resulted in a decrease in the degree o f grafting, indicating
that although the C2-C3 glycol units do take part in the grafting reaction the end
groups were the preferred sites. As seen in Fig. 2, there was generally a rapid consump-
tion o f ceric ions initially which was followed by a slower reaction, s°-sa'l°°'l°2,103
The initial rapid reaction has been attributed to the reaction o f the ceric ion with
the hemiacetal unit. This assumption was supported b y the fact that the amount o f
easily reactive cellulose in a sample was proportional to the carbonyl content, s2'71
The amount o f ceric ions consumed was found b y some to be proportional to the
copper number, i.e. the reducing end groups, s°'1°° Neimo and Sihtola 96 found that
the copper number fell to zero more rapidly than anticipated during grafting (cf.
Fig. 4) implying that grafting occurred at the reducing endgroups. This also explains
why only limited levels o f grafting were attainable. The rapid reaction o f ceric ions
with cellulose has also been attributed to the oxidation o f the hydroxyls in the
amorphous areas. 83
In conclusion, it seems most likely that the oxidation and grafting o f cellulose
takes place predominantly at the reducing endgroup and the glycol units as opposed
Coppernumb~
1.2 //li 81eochedsulp~itepulp
i.o II /J
oa
o.e II
ii
I
/
iI !1~ .,.c~ ..~,.
o., /f - / 4 j
0
0 40 80 I00 F~c~ole cellulose
in gt'oft ca~ol~
FIG. 4. The relationship between copper number and cellulose content of the graft copolymet
(From reference 96).
to the C6 group. The extent of each should depend upon the reaction conditions,
the mol. wt of the sample and the accessibility of these groups.
2.4. Alternative mechanisms

An alternative mechanism for graft polymerization of polar vinyl (or electron
acceptor) monomers onto cellulosics was proposed by Gaylord and coworkers. 1°4-1°~
This mechanism is based on cellulose-monomer interaction and is applicable to
uncatalyzed grafting systems as well as ceric ion initiated systems. According to this
mechanism, the cellulose acts as a complexing agent for acceptor monomers which
causes a delocalization of electrons in the double bond, which in turn, increases the
electron accepting ability of the monomer. An uncomplexed monomer becomes a
donor relative to the complexed monomer and a donor-acceptor complex is
formed. The establishement of these complexes depends upon the electron donat-
ing ability of the uncomplexed monomer as well as the monomer's initial ability to
complex with the cellulose. Failure of electron donor monomers such as styrene
and butadiene to polymerize is attributed to their inability to complex with
cellulose.
The cellulose molecule also acts as a matrix for the alignment of donor-acceptor
complexes. A typical example of the alignment of monomer-cellulose-water-
donor-acceptor complexes is shown below.
X-C-o X.-C-O X-C.O X-C-O
(44)
~Xo..-"Xo...~k..o...~Xo
I I I I
H -,,CH H .-,.CH
i luloeo
CII ~,ellulose
Ceric ions, when present, form a complex anchored to the cellulose through an
interaction with the carbonyl groups. Typical examples of monomer interaction
with the anchored ceric ion are given below.
X'-C =O X"C=O X-C=O X-C=O

I ÷ I
I I i~ I I ~ I I '~I
(45)
I II I I
H C H .,-CH
I I
Cellulose CII lulose
CN CN CN CN
I I 14 I
R-C" "CH~R-C+ "CI~ R'C "CI'~RC* -Cl'~
I I~
~..,~
~c..c,R h e . . ~ ~ e ,
I
~% ..% ..~% ..%

I~ I / i: | I ~:
(46)
..,. f .., :
I II I I
H C H ,-CH
I I
Cel luloll Cellul0ee
These donor-acceptor complexes undergo spontaneous initiation or may be initiated

by oxygen or radicals formed on the cellulose backbone. This initiation step
involves a hydrogen abstraction from the monomer which takes place without
incorporation of the radical into the polymer chain. Radicals generated on cellulose
by ceric ions may result in direct grafting of the monomer; however, this is not con-
sidered to be the prominent reaction. More typically, these radicals initiate poly-
merization without chemical attachment of the monomer molecule to the cellulose
chain.
Propagation of the growing polymer chain takes place through the addition of
donor-acceptor complexes, not monomer molecules. Termination of the growing
polymer chain takes place either on the cellulose molecules, resulting in grafting,
or with other polymer or monomer units, forming homopolymer. Two possible
termination steps for ceric oxidized cellulose are as follows:
CH2 OH e' CH2 OH d CH20H

H o% 4" . o H ,~-0 O,V--
(47)
"~ ~ ~'. "'~" \ O H/ L,
P-M=
CH_OH CH_O.'I
(48)
OH OH OH
It has been noted by some investigators%'1°7 that grafted acrylamide might be

helically twisted about the cellulose chains with strong hydrogen bonds between
the cellulose hydroxyls and the amide groups of the polyacrylamide. This may
indicate some type of monomer-cellulose interactions, as mentioned above• Others
have proposed two polymerization mechanisms for cellulose grafting, l°a-m One is
the redox system mentioned earlier and the other a free radical mechanism based
on a Ce4+-monomer complex. The extent of reaction via the second mechanism
depends upon the electronic charge (e-value) of the monomer. Monomers having
higher e-values will have a higher reactivity, thus, the ceric-monomer complex is
more easily formed. These alternative methods although of considerable interest
need more experimental justification and, thus, are not generally accepted.
3. C O N D I T I O N S AFFECTING GRAFTING
This section reviews the general effects of various reaction conditions on the
extent of grafting. Due to the heterogeneous nature of the reaction, the number
of reaction variables, and the variability of the substrate, i.e. differences in lignin
content, fiber size and accessibility, these findings often appear contradictory.
Therefore, emphasis in this section is placed only on general trends obserable under
a variety of experimental conditions.
A
B
REACTION TIME
FIG. 5. Typical curves of percent graft as a function of reaction time.
3.1. Time
Percent graft increased with time 12,s°'61,62,72-74,76,78,8°'96,97,l°9,l12-13s and
generally followed one of the three curves given in Fig. 5. The behavior most often
observed was the eventual leveling off of grafting yields with time (cf. Fig. 5, curve
A). 12, 50,62,72-74, 76, 78,80,96,97,109,112-134 Although grafting yields continued to increase
with time for systems following curve B, the rate of grafting decreased gradually
and an eventual leveling off could be anticipated. The same behavior might also be
anticipated for the grafting results described by curve C, especially since a level-
ing off trend was observed for some of these systems at slightly higher tempera-
tures. 78,so,~14,12$
The decrease in grafting rates and eventual leveling off of grafting values have
been attributed to decreases in monomer and catalyst concentrations as well as to
the retardation of diffusion due to the formation of polymer at the cellulose sur-
face. Kulkarni and Mehta s° examining the percent graft as a function of reaction
time for several catalyst concentrations found that although the initial reaction
rates were similar, the subsequent decreases in reaction rates were greater at lower
catalyst concentrations. They attributed this to a rapid exhaustion of the initiator.
Another possible explanation for the leveling off of grafting values with time is the
reduction in the number of sites available for grafting. This idea was discussed
briefly in Section 2.4 (cf. Fig. 4).
Although no induction period was apparent with the majority of monomers
examined, an induction period was observed with some systems in which acrylate
monomers were grafted. 77J~4'127 It is possible that the induction period in the
other systems was too short to be measured by conventional techniques. For
example, using an unconventional technique, i.e. calorimetry, LePoutre and Hui ~28
were able to measure an induction period of approximately 10-20 seconds for the
grafting of acrylonitrile onto pulp.
INITIATOR CONCENTRATION
FIG. 6. A typical curve o f percent graft as a function of initiator concentration.
3.2. Initiator
The influence of initiator concentration on percent graft was examined
by a number of authors, with the prominent trend shown in Fig. 6. This
trend was observed for a variety of substrates, monomers and reaction con-
ditions, 12,s°'61,77,81'9~'96,l°2,l14'129-z3s'139-1'~ and was found to be more prevalent
with eerie ammonium nitrate (CAN) than eerie ammonium sulfate (CAS). The
eerie ion concentration which resulted in maximum graft depended uporl the type
of monomer, the substrate and the reaction conditions. For example, larger eerie
ion concentrations were needed to attain optimum grafting levels as the earbonyl
content of the cellulose increased. 9s
Other trends such as: (1) decreased grafting;97'14s (2) increased graft-
ing;62,'rz'73'76,sl't27-13°'13s'14°'l~-l~ (3) increased grafting with a leveling
off; ~s1,lls'14° and (4) little change in grafting values 14°'t49 have also been observed
with increases in eerie ion concentration.
The initial increase in percent graft with increased catalyst concentration may
either be due to catalyst exhaustion or an increase in rate of grafting at low concen-
trations, as discussed earlier (cf. Section 2.2). This increase in grafting rate with
eerie ion concentration at low catalyst concentrations was observed by some
investigators, 13s while others found little dependence between the two. 61 The
decrease in percent grafting at higher initiator concentrations could be due to a
decrease in the rate of polymerization as predicted earlier by eqs 35 and 38. At
higher eerie ion concentrations, an increase is expected in the reaaction steps involv-
ing eerie ions leading to an increase in number of cellulose radicals terminated prior
to monomer addition. Such a possibility has indeed been supported by increases
in the carbonyl content of the grafted cellulose at eerie ion concentrations above
which percent graft decreased. ~32 In addition, an increase in cellulose degradation
G R A F T I N G OF VINYL MONOMERS TO CELLULOSE 21
with ceric ion concentration has been reported) a9 Another factor contributing to
a decrease in grafting levels at higher initiator concentrations is an increase in
homopolymer formation s°'133,~3s which competes with the grafting reaction for
available monomer.
Several authors have examined the difference in grafting behavior of CAN and
CAS initiated systems, s°'sl'a21,12s'x4°'ls°']sl At low temperatures, CAN was a more
effective initiator than CAS, while at higher temperatures the reverse was found to
be true. t2's°'~2s This is presumably due to the greater stability of CAS. Enhanced
stability of CAS with time has also been observed. Mansour and Schurz ~s~ found
that ageing the CAN solution for one day decreased grafting by 50%; whereas, little
change in CAS activity was observed after ageing for one month. A similar loss in
activity of CAN with time was observed by others) 29
3.3. Acid
In Fig. 7 the general dependence of acid concentration of grafting is des-
cribed. 76's6'96,lll'l14'12s't32,la4'l~'lsl'ls2 The acid concentration or pH value for
which optimum grafting occurred was dependent upon the reaction conditions. It
was suggested that the initial increase in grafting with increased acid concentration
was due to a decrease in the termination rate of the growing polymer chain or an
increase in the initiation rate. However, at higher acid concentrations, decreases
in grafting were attributed to a corresponding reduction in the ceric-cellulose
complex formation as well as an increase in polymer termination rates. 76'n2'I~
These changes in reaction rates with acid concentration have been discussed earlier
(cf. Section 2.2) and are a result of the changes in concentration of the various ceric
species which are present. The equilibria between these ceric species are generally
I-
1
z
IAJ
ACID CONCENTRATION
FIG. 7. A typical curve o f percent graft as a function of acid concentration.

22 D.J. MeDOWALL, B. S. GUPTA and V. T. STANNETT
neglected under conditions of constant acid concentration. It has also been specu-
lated that the increase in termination may be due to an abundance of hydrogen
protons which act as free radical terminators. 114
The other types of grafting behavior which have been reported with increased
acid concentration include: (1) decreased grafting; 77'114'143'1s3 (2) increased graft-
ing;127,13s,147,1sl and (3) no dependence. 62'147 As noted earlier, Varma and Narasim-
han r7 felt that a decrease in grafting with acid concentration indicated a reversibility
in the initiation reactions (cf. eqs 26-28) since an increase in hydrogen ion concen-
tration would suppress these reactions if reversible. Mansour and Schurz lsl observed
different types of behavior with acid concentration depending upon the monomer,
ceric salt and ceric ion concentration employed. They concluded that with CAN
initiated systems, the nitrate ion concentration was the critical factor in deter-
mining conditions for optimum graft. This was due to an increased reduction of
ceric ions by the nitrate ions. For CAS initiated systems, they hypothesized that
changes in grafting were due to the equilibrium established between the hydroxyl
ion and the ceric ion concentration, as discussed by Ardon 16 and defined by the
reaction:
Ce4. + H20 ~ CeOHa÷ + H + (49)
The type of acid employed in a grafting system had an effect on the grafting
yields; with the acids corresponding to the grafting maxima generally ranked as:
HCIO4 > HNO3 >HC1 >H2SO4. "~'81'a6'114 Others have noted a different order
of acid ranking as well as its dependence upon the acid concentration. 114'1s4 For
example, Messiha and Nossier ls4 noted that grafting decreased in the following
order at 0.2 N acid concentration: HC1 > H2SO4 > HNO3 > HC104, while at 0.5 N
grafting was greater with HCIO4 than with HNO3. These variations in grafting due
to the type of acid employed have been attributed to the formation of different
complexes between ceric ions, acid ions and other substances. 76
3.4. Monomer
Percent graft generally increases with monomer concentration, lz so,72,73,76,81,9~,97,

114,121,128,130,134,144,147,149,150,155-158 This behavior was noted for a variety of
monomers and substrates initiated with either CAN or CAS. This type of behavior
could be anticipated from the kinetics (cf. eq. 36), and indeed as expected, the
percent graft was found to be proportional to the square of the monomer concen-
tration. 134 Others have observed increased grafting rates with monomer concen-
tration.SO, 121,128
Somewhat unusual behavior was observed for systems in which the cellulose was
pretreated with CAS and grafted in an organic solvent with limited monomer
solubility, za1'159 In these cases, with increases in monomer concentration percent
graft increased, reached a maximum, then decreased. This was presumably due to
the limited monomer solubility which would lead to a two phase system at higher
TABLE 6. A summary of monomer reactivities under various conditions
Order of reactivity Substrate Temperature (° C) Reference
EA > AN > AAt Cotton 30 140

MA > EA > BA > MMA Cotton 30 77
MA > AN > MMA > ST Cotton 20 78
MA > AN = MMA > ST Cotton 40 78
MA > MMA > AN > ST Cotton 60 78
MA > EA > PA " BA Cotton 30 127
MA > AN > AMD Cotton 25 121
AN > ST > VA Cotton 20 161
MA ;* AN > MMA ~ EA Rayon * 132
EA > AN Rayon 25 135
BA > EA > MA Rayon 0 157
MMA > AN Jute 72, 73
EA > MMA > AN > AMD > ST Paper 25 12
MA > AN > AA Paper 25 112
BA > MMA > AN > AA > ST Pulp 35 129
MA > MMA > AN > VA > ST 88,147
tAMD - Acrylamide, AA - Acrylic Acid, AN - Acrylonitrile, BA - n-Butyl Acrylate, EA -

Ethyl Acrylate, MA - Methyl Acrylate, MMA - Methyl Methacrylate, PA - n-Propyl Acrylate,
ST - Styrene, VA - Vinyl Acetate.
*Grafted in the Vapor Phase.
m o n o m e r concentrations, reducing the effective m o n o m e r activity. M o n o m e r

aggregation m a y also o c c u r to some e x t e n t in a q u e o u s systems, thus, providing an
e x p l a n a t i o n for the leveling o f f o f grafting values observed in some systems. 12' 72,1ss
It was also n o t e d that graft p o l y m e r i z a t i o n in m o n o m e r alone was negligible. This
was p r e s u m a b l y due to the absence o f a swelling agent, such as water. 16°
M o n o m e r reactivity d e p e n d e d to a large e x t e n t on t h e grafting conditions
e m p l o y e d . The findings o f several investigators are summarized in Table 6. The
reactivities r e p o r t e d were generally for a q u e o u s systems as the relative m o n o m e r
reactivities changed w i t h solvent 123 and the grafting p r o c e d u r e used. F o r e x a m p l e ,
acrylonitrile was m o r e reactive t h a n e t h y l acrylate w h e n rayon was grafted in the
vapor phase, ~32 while the reverse was true w h e n grafting was carried out in the
liquid phase, t3s Variations in t e m p e r a t u r e where also shown to affect the m o n o m e r
reactivity. In the case o f grafting o n t o c o t t o n , the reactivity o f acrylonirile com-
pared w i t h m e t h y l m e t h a c r y l a t e was greater at 20°C, a p p r o x i m a t e l y t h e same at
4 0 ° C and less at 60°C. 78 In general, the rate o f p o l y m e r i z a t i o n w i t h acrylate
m o n o m e r s decreased with increasing alkyl length. 77'127'162 This was p r e s u m a b l y due
to changes in diffusion, steric hindrance, polarity and solubility w i t h increasing
m o n o m e r size. The low reactivity o f some m o n o m e r s , such as acrylic acid, and to a
lesser e x t e n t acrylonitrile, was a t t r i b u t e d to t h e s o r p t i o n o f ceric ions b y the graft
copolymer.112
S o m e investigators have e x a m i n e d m o n o m e r m i x t u r e s in an a t t e m p t to improve
the physical properties o f the resulting p r o d u c t . 12'~12'13s The various c o m o n o m e r s
24 D.J. McDOWALL,B. S. GUPTA and V. T. STANNETT
TABLE 7. A summary of the comonomer mixtures and the cellulosics onto which they have
been grafted
Comonomers Cotton Pulp Paper Rayon Cellulose

AMD : ANt. 130, 163
AMD:EA 130, 163
AMD:AN:EA 130, 163
AMD : MA 16 3
AMD : MMA 16 3
AA:AN 112
AA: MMA 164
AN : butylene dimethacrylate 165
AN: n-butyl methacrylate 166
AN:EA 130, 163 12,167 135
AN: EA: diallyl phtalate 12
AN: ethylene dimethacrylate 165
AN:MA 78 112
AN: MMA 78, 167 167
AN:ST 133 169
MA: glyeidyl acrylate 170,171
MA: MMA 78
MMA : ST 12
i'See Table 6 for definitions of abbreviations.
which have been grafted are summarized in Table 7. Grafting yields for comonomer
mixtures generally were between the yields obtained with the monomers individu-
ally, provided the overall monomer concentration was the same. t2,'~'~12,13s The
actual composition o f the resultant copolymer was found to be dependent upon the
reaction temperature and monomer ratios. 1~ Synergestic behavior was observed for
the grafting of acrylonitrile with acrylamide, tea styrene, ~33 methyl acrylate ~ and
methyl methacrylate. ~ To illustrate, the amount of acrylonitrile grafted was 19.0%
from 0.5 ml o f acrylonitrile ~and 17.0% from 0.5 ml o f acrylonitrile in a mixture
with 0.5 ml of methyl methacrylate while the amount of methyl methacrylate
grafted increased from 25.8% when used alone to 32.6% in the comonomer mix-
ture. ~ The presence o f acrylonitrile did not always enhance grafting; and indeed,
the grafting of ethyl acrylate was suppressed by the presence of acrylintrile. 1as
3.5. Temperature
The influence of temperature on grafting yields depended upon the type o f
initiator, its concentration and the monomer employed. With CAN, grafting gener-
ally followed the behavior depicted in Fig. 8. n'61,78,s°'l14,12s'l~ Other grafting
behavior observed with increasing temperature was: (1) decreased grafting;62'77
(2) increased grafting; ~' ~'129'137'1ss'144'147'173 and (3) no change in grafting
levels. ~'~zs'14° Increased grafting with temperature was more predominant with
less reactive monomers, such as styrene. ~'n9'147 With CAS, grafting was also found
G R A F T I N G OF VINYL MONOMERS TO CELLULOSE 25
¢.9
i-
z
TEMPERATURE
FIG. 8. A typical curve of percent graft as a function of reaction temperature.
to increase and subsequently decrease with an increase in temperature. 12'13~ The

temperature for which maximum grafting was attained was higher with CAS than
CAN, lz presumably due to the greater stability of CAS. Others, using CAS, have
noted that grafting simply increased with temperature, s° Changes in grafting
behavior with temperature were also found to be dependent upon the concentration
of CAS. t4° For example, a decrease followed by an increase in grafting with an
increase in temperature was observed at lower initiator concentrations, while a
continuous decrease in grafting with temperature was observed at higher con-
centrations.
The changes in grafting with temperature are due to a variety of temperature
dependent factors such as diffusion, adsorption of monomer into the substrate,
and changes in the rates of initiation, propagation, termination and homopoly-
merization. Increases in grafting yield with temperature were accompanied by
increases in the rate of polymerization. Decreases in grafting were accompanied by
decreased rates of polymerization, implying changes in the rates of initiation,
propagation and termination with temperature. ~s Increased grafting with tempera-
ture has also been attributed to increased monomer solubility. For example, the
enhanced reactivity of styrene at higher temperatures was attributed to its increased
water solubility, t29 However, this was not true for all monomers. To illustrate,
acrylonitrile which exhibits improved solubility in water at higher temperatures 1~
generally gave an increase followed by a decrease in grafting with increased tem-
perature ?a'so (cf. Fig. 8). The decrease experienced in grafting at higher tempera-
tures has been attributed to the instability of the initiator, particularly CAN, at
elevated temperatures, ~2 an increased rate of termination so'sn and the more rapid
formation of aldehydes from free radicals produced by hydrogen abstraction 6: as
outlined below:
H
I
-t~HOH + - C = O + H" (50)
and
OH H H
I I I
-~ -c~l -~+~-+H" (51)
OH H 0 O
The combined effect o f all o f these factors will influence the changes in grafting
behavior with temperature.
3.6. Substrate
The effects o f accessibility and crystallinity o f the substrate on grafting have
been examined b y several investigators. Generally, increases in accessibility, or
decreases in crystallinity, increased grafting, s°'97,1°°'lls'12s'j49,]s6,173'lTs-177 This
could be anticipated on the basis o f increased sites available for grafting and
enhanced diffusion o f b o t h the monomer and the initiator. A linear increase in
grafting with accessibility was observed under the following reaction conditions:
(1) excess monomer; (2) suppression o f homopolymer formation b y using separate
initiation and grafting steps; and (3) utilization o f a nitrogen atmsophere to retard
the oxygen induced inactivation o f the radicals, which was more pronounced with
substrates of greater accessibilitys°'12s (cf. Fig. 9). Others noted decreases in graft-
120
moo
D •
80
n,-
W 60 2
=E
40
20
0
I0 20 30 40 50 60 TO 80
% ACCESSIBILITY
FIG. 9. Relationship between maximum graft yields and accessibility of different substrates:
( - - ) percent PAN grafted; ( - - - ) percent homopolymer formed in solution; (A) native
cotton; (.) NaOH - cotton; (o) EDA - cotton; (X) ZnC12 - cotton; (•) hydrocellulose; (.)
viscose; (o) ramie. Curve 1 is grafting procedure discussed; curve 2 is with air instead of nitro-
gen; curve 3, cellulose was presoaked in monomer then CAN added; curve 4, cellulose was
added to a solution of CAN and AN. [CeIv] = 0.006 M in 1% HNO3; cellulose, I g; tempera-
ture 40°C; reaction time 3hr. Acrylonitrile: (1,2) 15 ml., (3,4) 1 ml. (From reference 80).
ing due to a reduction in substrate accessibility caused by drying of the substrate

prior to grafting. ~24'~2a This decrease in accessibility resulted from the collapse of
fiber structure which leads to an increase in hydrogen bonding. Increases in grafting
were not always observed with increases in substrate accessibility. For example,
cotton pretreated with sodium hydroxide 8~ and ethylene diamine 1~ produced
lower grafting yields than untreated cotton, even though these treatments reportedly
increase accessibility. This observation has been attributed to an accompanying
increase in disproportionation and coupling reactions (cf. eqs 19 and 33) as a result
of the increased accessibility of the hydroxyl groups.
Grafting increased with a decrease in the degree of polymerization of the cellu-
lose material. 124 This finding was consistent with the results of the ceric ion con-
sumption which indicated that the increase in grafting was probably due to the
presence of additional end groups which have been shown to be more reactive (cf.
Section 2.3).
Hebeish and Mehta 79 noted that the large surface area on cellulose was not the
primary reason for grafting since silica spheres of the same surface area grafted to a
much lesser extent. They concluded that the reducing action of the cellulose was
the main reason for the higher grafting rates. However, increases in the surface area
of cellulosic samples have been shown to increase grafting rates as well as grafting
yields. H2,~,~Ts,~79 This may be a result of grafting occurring more readily at the
surface. A study has also shown grafting to be independent of the surface area 97
while another, by Mansour and coworkers, 124 has shown grafting yields to decrease
with increased surface area. The latter authors attributed their result to an increase
in the availability of hydroxyl groups with an increase in surface area. This resulted
in a larger population of radicals (as indicated by an increased ceric ion consump-
tion) leading to an increase in the coupling and disproportionation reactions (cf.
eqs 19 and 33).
The type of pulp employed in a grafting system has been shown to influence the
grafting behavior. ~2°'~22'~24'~ These changes were more noticeable with certain
monomers. 1~ The differences in grafting with various pulps have been attributed to
their different lignin compositions. ~22 The hemicellulose content of a pulp also
influenced the grafting behavior, for example, a paper grade spruce sulphite pulp,
high in hemicellulose, was more reactive than an acetate grade spruce sulphite pulp,
low in hemicellulose, s36 Percent graft was also found to depend upon the degree of
beating of the pulps. ~6'~8°
It is generally agreed that percent graft increased as the lignin content de-
creased 72,Ta'l°2,122,lTa'lal For example, grafting decreased from 74.6% to 25.5%
when the lignin content changed from 2.1% to 15.7%. During these reactions,
homopolymer was seen to increase from 57.9% to 85.7%. ~ Changes in grafting with
lignin content also depended upon the type of pulp. 122 Pulps containing more
than 1% lignin required a finite induction period ~22 and a certain minimum ceric
ion concentration to initiate the grafting reaction. 61'~°2'12a A possible reason for
this result is the reduction of ceric ion by the lignin and other impurities.
28 D.J. McDOWALL, 13. S. GUPTA and V. T. STANNETT
3.7. Other variables

Various techniques have been employed to graft onto cellulosics with the
typical procedure utilized being a solution grafting system where the cellulose was
either treated first with monomer and then with the initiator solution, or vice versa.
The order of monomer and catalyst addition has been examined and it has been
reported that, with CAN, grafting yields were lower when the catalyst was added
first. ~2,12s'ls2 This difference in yield was more pronounced as the time between
catalyst and monomer addition increased. With CAS, the trend was reversed, pre-
sumably due to the greater stability of CAS. is° Other variations in initiator and
monomer addition have included a two step addition of catalyst solution, lss'161
ageing the ceric-monomer-HNOs solution to increase grafting by forming a ceric-
monomer complex as discussed previously I°9-111'119'1a3 (cf. Section 2.4), and pre-
treating the substrate with a ceric solution, removing excess ceric solution and then
adding monomer. 49's°'131'1s9.ls4-1s7 This latter technique has been used for suppress-
ing the formation of homopolymer.
Although most grafting has been performed in an aqueous system, some organic
solvents have also been employed. Mixtures of organic liquids and water were used
to increase the monomer solubility; x2'129'143'161'185 however, the results were not
always favorable. Emulsion polymerization techniques were also employed when
the monomer solubility was limited) 2'127'16s Others have carried out grafting in
organic liquids to suppress homopolymer formation) al'lsg'xss Generally, grafting
decreased in nonaqueous systems; however, the reverse was observed with acrylic
acid presumably due to the solubility of polyacrylic acid in water. 12a Another
technique used for the suppression of homopolymerization was grafting in the
vapor phase; 121'132'14~'1a9-194 however, in some cases pronounced degradation of
the cellulose was observed) 9a
Intense agitation during the grafting reaction was found to decrease grafting
yields. 7a This was presumably due to a decrease in the propagation rate since
higher ceric ion consumption was observed under intense agitation. A decrease in
grafting with increases in the intensity of agitation might also result from the
incorporation of oxygen into the reaction system.
Grafting was found to be dependent upon the composition of the reaction vessel.
For example, the use of a glass reaction vessel gave higher grafting yields than a
stainless steel vessel. Is° This was attributed to an inhibiting effect of stainless steel
which may act as a transition metal cation.
The inclusion of air in a grafting system generally caused a decrease in grafting
yield 12,Ts,12a'lal'xa2,141,lag'173 due to the inhibiting effect of oxygen. Longer induc-
tion periods have also been observed when the reactions were carried out in the
presence of oxygen. 12t However, some investigators found that grafting with certain
monomers such as acrylonitrile under certain conditions was unaffected by the
presence of oxygen s°'12s'132 and reagent purity. 12s In the grafting of acrylic acid,
however, the yield increased with monomer purity. 131
Treatments such as preoxidation, irradiation and ultrasonics generally accelerated

the grafting reaction, a6,ag'l°a'12°'tgs'196 Some investigators noted that the effect
of irradiation with UV light on grafting yield depended upon the nature of the
cellulose. 12°
4. C H A R A C T E R I Z A T I O N OF GRAFTED PRODUCTS
The characterization of grafted cellulose is important in that the changes in
physical properties will result from the changes in the morphology and structure of
the fiber due to grafting. This section examines the work in the literature on the
morphology and structure of the grafted polymer and that on the determination of
factors such mol. wt of the grafted side chains, grafting frequency and proof of
grafting. A review of literature dealing with the characterization of grafted cellu-
losics by initiation methods other than ceric ion is outside the scope of this paper,
and thus, is not covered.
4.1. Proof o f grafting

Proof of grafting has generally been indicated by changes in solubility and the
infrared spectra. These were often compared to those obtained from physical
mixtures of cellulose and polymer. The IR spectra of grafted cellulose has been
examined by several investigators, s°'Ta'96'19~'lga For example, the IR spectra of
acrylonitrile grafted jute did not show a carbonyl peak which was present in the
physical mixture indicating that grafting had occurred at this point, ra Kulkarni
and Mehta s° examining the IR spectra of acrylonitrile grafted chains, after removal
of the cellulose backbone, found an additional peak characteristic of a
- O - C - ester group indicating the presence of cellulose fragments. However, Morris
II
O
et al. 199 using similar techniques, observed no absorption bands which could be
attributed to cellulose residues. It is possible that the latter result was due to a low
concentration of cellulose chain fragments. A similar study was carried out by
Guthrie 139 on polyvinyl chloride grafted cellulose, using both chromatography ant
a C-14 labeled cellulose. In both cases hydrolysis of the cellulose backbone gave a
glucose residue indicating that a covalent bond had formed between the PVC side
chains and the cellulose backbone.
Another technique often employed to verify actual grafting is to observe the
change in the insolubility of the grafted product in solvents such as cuene and
cupriethylene diamine which otherwise dissolve cellulose. 121,134,1aa,149,161,2°°-2°3
This change in solubility was found to be dependent upon the grafting
level. 1a4'149'2~2°3 In other solubility studies, where the cellulose substrate and
homopolymer were both soluble, the grafted cellulose was completely dissolved in
a cuprammonium solution. The solution was acidified, precipitating the cellulose
and grafted polymer while leaving the homopolymer in solution. 7~s~'2°4 The
amount of the material recovered was greater than both the cellulose component in
the grafted polymer and the amount recovered from dissolution of a physical
mixture. The changes in solubility, IR spectra and the appearance of cellulose
residues on the polymer chains indicate that a covalent linkage has formed between
the grafted polymer and the cellulose.
4.2. Fine structure and morphology

Changes in the fine structure of cellulose as a result of grafting have been examined
by several investigators. 62,97,17s'176,197,2°2,2°s-213 Grafting is generaUy believed to take
place in the noncrystalline regions of the substrate material. 97'169'17s'176'2°1'2°9-211,
214-2~6 X-ray analysis of the grafted cellulose showed little change in crystal-
linity, 62,97,ls2,lTs'21°'214,216 however, increases in background scatter as well as
decreases in orientation were observed. Is%ITs'21° Large decreases in crystallinity
have been observed at very high grafting levels. 217 Decreases in orientation with
grafting were observed from birefringence studies 1s2 indicating a disruption of order
in the noncrystalline regions. This might be due to hindrances produced by the
graft on the formation of ordered domains in the amorphous regions, resulting in
the transformation of the cellulose to a pseudo-swollen state. This hypothesis was
supported by the decreases observed in the substrate density) s2,212,21s'2~8 The
occurrence of grafting primarily in the amorphous or accessible regions was also sup-
ported by hydrolysis studies. 169'216'219 For example, hydrolysis of 10% of the cellu-
lose resulted in a 50% loss of the grafted polymer. 216 As noted earlier (cf. Section
3.6), grafting was found to decrease with an increase in crystallinity, thus sup-
porting the hypothesis of grafting in the noncrystalline regions.
Examination of the morphology of ceric grafted cellulose has generally indicated
that grafting, proceeds from the substrate surface inward. 62,~Sa'2~s Hori and co-
workers x76 noted that polymer was more readily formed at the surface of cello-
phane film. They found that at low yields, grafting was predominantly at the sur-
face, while at high yields, there was a uniform deposition of polymer throughout
the cross-section. 2~7 In cotton, ceric ions reacted mainly in the primary wall, 22°
therefore, grafting would be anticipated to take place predominantly there. While
in rayon, polymer filled the voids and surface irregularities. 22~ Kaizerman et al. ~2~
noted polymer penetration throughout the fiber with a heavier deposition at
the surfaces. A few studies have reported uniform distributions of polymer through-
out the substrate. 211'222
In summary, it appears that grafting occurs more readily at the surface. Also, it
occurs in the amorphous areas of the fiber and tends to change the orientation of
the crystallites. In some systems where grafting was substantial, crystallite fracture
was also noted. 2°s These changes in the fiber structure, as expected, depended upon
the grafting conditions. 2°s'2°6,~la
4.3. Molecular structure

The mol. wt, or degree of polymerization, of the grafted side chain and the
number of grafted chains have been determined by several authors, s°' s2,6x,7~,~,a9,93,
96-98,100,102,103,109,116,117,120,128,129,132,142,143,14S,155,l'F2,194,199,202,211,219,223-228Molecu-
lar weights ranged from approximately 0.03 to 11 x l0 s and grafting frequency
from approximately 0.02 to 3 grafted chains per cellulose chain. The values of these
parameters depended upon the grafting conditions as well as the substrate and the
monomer employed. The number average mol. wt, Mn, of the grafted side chains
has been derived using the kinetic scheme presented earlier 71 (eqs 26-34).
1 ICe4÷] [ k't'kd K [Cell-H] ]
Mn - kp [M] kt + ki {[M] + (ko/ki) [Ce*÷]}J (52)
Assuming as before (ko/ki) [Ce4+] >~ [M], eq. 52 becomes:

1 _ kt ICe4÷] +k't'kdK[Cell-H] (53)
Mn k x, [Ml kpko [M]
The number of grafted chains is proportional to Rv/Mn; therefore, using eq. 35 for
Rp and 53 for 1/Mn:
R v _ kdK[M] [kok~[Ce4÷l
+
(k~k't'~+ kikt ]1 tCell-HI +
Mn ko
kik't' +__k_.._K[Cell-HI
d 2]
(54)
ktk o [Ce 4÷] J
A linear relationship was found by Ogiwara et al. 71 between l/Mw and the mono-
mer concentration. This dependence can be predicted from eq. 53 assuming it was
also valid for Mw. Others have also noted increases in the degree of polymerization
of the side chains with monomer concentration. 96'~°9'12a A linear relationship was
also found beteen 1/Mw and the total carbonyl content as anticipated by eq. 53.
The relationships between the number of grafted chains and both the ceric salt
concentration and the total carbonyl content were linear, indicating that the third
term in eq. 54 was negligible. 71 However, others have observed a decrease in the
number of grafted chains with increasing carbonyl content) sa
A number of workers have examined the effect of ceric ion concentration on
these two parameters. Molecular weight decrease with initiator concentration 7~'96'
~oo,14s,22a as anticipated from eq. 53. Others noted that this decrease was followed
by increases in mol. wt. t29,132,lss Molecular weight has also been found by some 61'~4s
to be independent of the initiator concentration; however, others found that this
behavior held only up to certain concentrations after which mol. wt decreased) 28
Grafting frequency, on the other hand, generally increased with initiator concen-
tration. 71,96,lo2,12a'la2,lss This was often followed by either a decrease la2'lss or no
change in the grafting frequency at higher concentrations. 71 This increase with
32 D.I. McDOWALL,B. S. GUPTAand V. T. STANNETT
initial ceric ion concentration would be anticipated from eq. 54 assuming that the
third term in the equation was negligible.
The effects of other variables on mol. wt and frequency of graft have been
examined. Grafting frequency 1°3'12°'1s4 and mol. wt 1°9'132'223'227generally increased
and leveled off with time. Likewise, mol. wts ~°3'1°9'2~7 and the number of grafted
chains H6 were found to increase with grafting yields. Changes in the concentration
of nitric acid have also been reported to affect the degree of polymerization and
the grafting frequency. ~°9'132'143'223'226 Generally, the degree of polymerization
decreased while the grafting frequency increased and leveled off with acid concen-
tration. This behavior was also observed for sulfuric, hydrochloric and perchloric
acids. 226 Other variables such as temperature, 6~'1~ oxidation prior to grafting, s9'~°3
lignin content, 1°2 degree of beating a pulp ~8°'2~9and irradiation of the system ~2°'226
were found to have an effect on these parameters.
Little work has been done on the changes in the degree of polymerization of the
cellulose substrate due to grafting. However, decreases in the degree of polymer-
ization with ceric oxidation have been reported~ ~s7,2~3 (cf. Fig. 3). Some studies
have been done on the composition of the grafted copolymer after removal of all
ungrafted cellulose and ungrafted polymer, s6,~as'~28 Generally, in these experiments,
the amount of polymer present was greater than the cellulose, indicating perhaps
long polymer chains attached to comparatively short cellulose chains.
5. PROPERTIES OF THE GRAFTED PRODUCTS

The focus of this review has been mainly on the grafting method and the influ-
ence of a number of factors on grafting. However, since the changes in physical
properties are often the impetus for grafting, this area is briefly touched in this
section. A number of general reviews on grafting have also included some discussion
on the changes in physical properties. 1's'9'229 Some other reviews dealing with cer-
tain properties and applications, such as sorbancy2a° and ion exchange properties, 231
are also available.
5.1. Mechanical properties

The mechanical properties of grafted pulp and paper have been summarized in
Table 8 and those of natural and regenerated cellulosics in Table 9 and Table 10,
respectively. Indications of general trends are given in these tables. Although many
of these results appear contradictory it must be noted that the changes in mech-
anical properties depend greatly upon the reaction conditions ~a4 and thus, depend-
ing upon these conditions, a variety of trends could be expected.
5.2. Water sorption and penetration

Grafting has often been employed to change the moisture absorption and trans-
TABLE 8. C h a n g e s i n t h e m e c h a n i c a l properties o f p u l p s a n d p a p e r s as a r e s u l t o f g r a f t i n g
Monomer Substrate Tensile strength Elongation Tear Fold Burst strength Abrasion Stiffness
resistance endurance resistance
Dry Wet Dry Wet Dry Wet
acrylamide paper t 12 NC 12 NC 12 t 12 t 12 t 12 t 12
pulp t 188, 232,233 t 232 t 188,233 t 188. 232 O
216 NC 188 O
233
acr yionitrile paper t 12,134,200 t 12,136,200 NC12 t12 ~. 12,200 NCI2 t 12,200 t 200 t 12,200 t 12,200,218 ,<
136,218 234 ~ 136,200
pulp t 193 t 136,193 NC 193 t 193 t 193
.~ 136, 141 I 136. 141 J. 136 ~ 136 t"
methyl
methacrylate paper J. 12,218 t12 NCI2 tt2 ~.12 *12 t12 112 t 12,218 0
pulp 141,216, 233 t 233 .233 Z
J. 144 0
methyl acrylate paper t36 K
ethyl acrylate paper 12 t 12 t 12 t 12 t 12 t12 ~12
136
butyl acrylate paper t 12 ! 12 ~ 136 t 235
acrylic acid paper t 234 ©
vinyl acetate pulp t 236-241 239, 240 ~ 141
141
vinyl chloride pulp 61 .t61
styrene pulp 141 141
C
t Increases; NC No change; ~ Decreases t"
O
r~
TABLE 9. Changes in the mechanical properties of natural fibers as a result of grafting
Monomer Substrate Tensile Elongation Initial Tear Abrasion resistance Wrinkle recovery Stiffness
strength modulus strength
Flat Flex Dry Wet
acrylamide cotton fabric NC 76, 121 t 76 NC 76 # 121 t 130 I 130 ? 130

I 130 121,130 * 121 NC 76
acrylonitrile cotton fabric t 121, 165 t 76, 243. 244 ~ 244 121,130,211 t 121,211 t 130, 211 ? 130,165 t 139
NC10 ~ 211,242 121,165 NC 2 1 1 , 2 4 4 NC 165 O
130, 242-244
cotton yarn t 134 t 197 149 211
>
J. 149,197, 2 1 1 , 2 4 3 NC211
149. 243
cotton fiber ~ 242
jute J. 73 t 73
methyl
methacrylate cotton fabric t 165 ? 244 .t 244 ? 165 ? 130 ? 127, 1 3 0 , 2 4 4 t 127. 130
J. 1 2 7 , 1 3 0 , 2 4 4 ~ 127 127,130 165
cotton yarn * 152 ,t 152 ~. 152
jute fiber # 245
methylacrylate cotton fabric ? 127, 165 t 127, 165 1 2 1 , 1 2 7 , 1 3 0 , 246 ~ 121 t130 t127.130,246 t 127,130,246 t127
>
NC 121 J~ 1 2 1 , 1 2 7 . 1 6 5 NC165 NC165
.t 130 e~
cotton yarn ~ 152 t 152 ~ 152
ramie NC 93 .<
ethyl acrylate cotton fabric f 127, 165 t 127, 165 ? 127, 130, 246 t 127,130 t127,130,246 t127,130,246 f127
I 130 165 NC 165 NC 165
cotton yarn I 152 t 152 ~ 152
ramie ~. 93 t 93 >
n-butylacrylate cotton fabric ~ 127 t 127 127,246 127 ? 127.246 t 127,246 ~ 127
cotton yarn # 152 J~ 152 ~ 152
ramie ~ 93 Z
t 93
iso-butylacrylate cotton fabric .t 127 * 127 J~ 127 t 127 ? 127 ..4
propyl acrylate cotton fabric I 127 t 127 J~ 127 127 t 127 t 127 NC 127
styrene cotton fabric i 127 t 127 I 127 ? 127 t 127
t Increases; NC No Change; ~, Decreases.
TABLE 10. Changes in the mechanical properties of regenerated cellulose as a result of grafting
Monomer Substrate Tensile strength Elongation Initial Elastic Tear strength Abrasion Burst Impact
modulus recovery resistance strength strength
Dry Wet Dry Wet Wet Dry
acrylamide cellophane t 217, 247 247 217 ,t 247 t 247

film
O
acrylonitrile rayon fabric ~. 121 121 .t 121 NC 121 t 121 <
rayon fibers NC 132 t 132 t 132
methyl rayon fibers NC 132 t 132 t 132 7~
methacrylate # 245 245
rayon nonwoven t"
webs ~. 248 t 248 t 248
methyl acrylate rayon fibers NC t 32 t 132,251 ~ 132,249 t 250 0
249 Z
rayon nonwoven 0
web t 248 t 248 t 248
ethyl acrylate rayon fiber NC 132 t 132, 156, I 5 7 , 2 2 1 , 2 5 0 ~ 132, 156 t 156, 157,250
156,157,221
butyl acrylate rayon fibers t 250 t 250
rayon nonwoven
web t 248 NC 248 t 248 0
acrylic acid rayon fibers ~ 81 181 8l NC 81 NC 81
rayon nonwoven
web NC 248 NC 248 NC 248
2-vinyl rayon fibers J~ 81 ~81 81 t 81 ~ 81
pyridine
glycidyl 0
methacrylate rayon fibers I 62 62 NC 62 t62 r.~
t Increases; NC No Change; ~ Decreases.

TABLE 11. A summary o f the various monomer and cellulosic substrates which have been grafted via ceric ion initiation
Monoraer Cotton Pulp Paper Rayon Jute Ramie Cellophane Cellulose
acrylamide (AMD) 76, 130, 184 75, 96, 129 12,167 81 108-111,144,176, 97, 88
188, 203, 216, 183,204,208,215,
232,233, 262 217,247
acrylic acid (AA) 81,140, 150, 159, 234, 251, 112, 234 81,131,248 259
151,184,269 257,258,260,
261
acrylonitrile (AN) 50, 79, 80, 107, 113, 104, 122, 124, 12, 112,136, 80,113,121,125, 73 80, 110,186 53, 74, 88,
118,119,121,124, 128,129,136, 167,200,218, 132,135,172, 125, 123,137,146,
125,130, 134, 140, 141,161,168, 234 187,206,212, 172 147,189-191,
149-151,165, 168, 179, 181,193, 213 194,205,214
172, 192, lO3, 195, 197,201,224, ©
197,199, 202, 206, 234,255
211-213, 222, 224, >
242, 243, 245
allylmethacrylate 114
p-benzoyloxy styrene 272
c~-bromo acrylic acid 154
n-butyl acrylate 77, 127,152, 162, 129 136, 236 157,162,206, 93 146,173
206,210, 246 248,250
iso-BA 127
n-butyl methacrylate 248 >
cellulose acrylate 165
#-chloroethyl acrylate 177 177 177 ex
#-chloromethacrylate 177 177 177 .<
cyanoethyl acrylate 165
deciyl acrylate 162 162
diacetone AMD 253 254 ,..q
diallyl phthalate 12 >
dimethyl acrylate 269 269 269 Z
dimethyl amino Z
ethylmethacrylate 81
divinyl benzene 12 ,-4
,..q
ethyl acrylate 77, 107, 124, 127, 124, 181 12, 136,167 132,135,156, 93 74,123
130,140, 150-152, 157,221,250
165,192, 210, 246
2-ethyl
hexyl acrylate 165 136
glycidyl acrylate 170, 171
glycidyl MA 126,188
heptyl acrylate 162 162
hexyl acrylate 162 162
2-hydroxyethyl
methacrylate 254
T A B L E 11. Continued
Monomer Cotton Pulp Paper Rayon Jute Ramie Cellophane Cellulose
isoamylacrylate 162 162

methacrylic acid 251
methyl acrylate 77, 78, 107, 121 261 121, 136 132,157,207, 93 88,142,146,
(MA) 127, 130, 152, 209,248-250 147, 191,225,
165,192,210, 263
246 C3
met hacrylonitrile 104 >
methylene
bisacrylamide 12 252
methyl 52,77,78,118-120, 52,71,100,102,103, 12,67,217 132,196,206, 72, 88,89,101, 7~
methacrylate 127,130,143, 116,117,120,129, 245,248 245 138,146,147, ~3
(MMA) 152,165,192, 141,148,155,180, 158,160,175, ©
206,210,244, 198,203,216,219, 178,214,223
267,269 226-228,233,256 <
N-methylol 7~
acrylamide 270 ,<
N-methyl-4-vinyl r-
pyridiniumtoluene-
p-sulphonate 81 0
methyl vinyl
pyrrolidine 0
88
nonyl acrylate 162 162
octyl acrylate 162 162
n-propyl acrylate 127
propylene 0
dimethacrylate 268 268 268
stearyl MA 165
styrene 78, 115, 127, 129,141,145, 12 86 91,92,185 88,146,147
133, 143,269 161
tetrahydrofurfuryl
acetate 270, 271 0
tetrahydrofurfuryl
methacrylate 270, 271
vinyl acetate 141,161,178, 12 88,146,147,
236-241,264, 153
265
vinyl chloride 139 61 186 139
2-vinyl pyridine 81
4-vinyl pyridine 81
N-vinyl pyrrolidine 110
port properties of cellulosic materials. Generally, increases in moisture sorption and

retention were noted when hydrophillic monomers such as acrylamide, 12'216'227
acrylic acid 2sl and methacrylic acid 2sl were grafted. N,N-methylene bisacryl-
amide, 12'2s2 diacetone acrylamide 2s3 and 2-hydroxyethyl methacrylate 2s4 were also
found to increase the water sorption of cellulose. Grafting of hydrophobic mono-
mers such as acrylonitrile 12'1°7'141'149'172'218'255 methyl methacrylate, 1°7'127'141'152,
216,219,227 methyl acrylate 93,127,152 ethyl acrylate, 12,93,107,1S2 butyl acrylate,93' 127,152
isobutyl acrylate, 127 styrene, 127'141 vinyl acetate 141 and vinyl chloride 61 resulted in
a decrease in water sorbancy, as expected. Several authors have obtained increases
in the water retention values of cellulose by first grafting with acrylonitrile or
ethyl acrylate and then hydrolyzing the grafted product. 1°7'16s,201,2ss Changes in the
binding of water to cellulose have also been examined. 2s6
5.3. Ion exchange and membrane properties

Several authors have discussed the ion exchange potentials and membrane
properties of ceric ion grafted cellulosics. 62,112'~sg'17°'171'las'193,201,257-261 Various
ion exchange properties have been shown to be possible depending upon the grafted
polymer. An interesting study was performed on glycidyl methacrylate (GMA)
grafted rayon, 62 a system in which it was possible to attain cation exchange fibers
by adding sulfonic, mercapto or carboxyl groups to the GMA, and anion exchange
fibers by adding quaternary ammonium hydroxide. Silver ion exchange capability
could also be achieved through the addition of hydrogen sulfide.
5.4. Other properties

The transverse dimensions, i.e. thickness and denier, of the cellulose substrate
were examined by a number of authors. These dimensions generally increased with
grafting. 12,62,149,152,167,23a
Changes in the thermal stability of grafted cellulose have been examined by
several workers and found to depend upon the monomer grafted. 77'186'18s'216;262
Other thermal properties examined were changes in the glass transition tem-
perature 162'2sl thermosetting behavior, 127 and the thermoplastics nature of the
product.263,264, 26s
The dimensional stability of paper grafted with acrylonitrile, methyl methacrylate
and ethyl acrylate increased with grafting, apparently due to the hydrophobic
nature of these monomers. 12'2°°'21s Shrinkage of textile products grafted with
acrylonitrile 121'266 and methyl methacrylate 267,z6s was also found to decrease.
Improvements in acid resistance were noted for cellulose grafted with acryloni-
trile, 1°7'2°°'242 methyl methacrylate, ethyl acrylate and mixtures of acrylonitrile
and ethyl acrylate. 12 Increases in base resistance were also noted for methyl meth-
acrylate and mixtures of acrylonitrile and ethyl acrylate. 12 The resistance of cellu-
losics to microbiological attack was significantly improved by grafting acryloni-
trile, 12'121'134'2°° methacrylonitrile,137/3-chloroethylacrylate,177/3-chloroethyl meth-

acrylate, 177 dimethacrylate, 26a and propylene dimethacrylate. 26a
The dyeability of grafted cellulose has been examined along with the corres-
ponding lightfastness and washfastness. 62'ra'1°7'126'1~'216'269 Changes in the affinity
of cellulosics to printing, with both dyes and inks, have also been examined.27°'271
Improvements in UV light stability have also been observed. 166'~77'~6a'272
In conclusion, improvements in a variety of properties have been possible and
have depended upon the choice of monomer, grafting condition and the nature of
the after treatment, if any. However, a desirable change in a specific property
was often accompanied by changes in other properties, which sometimes were
undesirable.
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Prog, Polym. Sci., Vol. I0, pp. 1-50, 1984 0079-6700/84 $0.00 + .

GRAFTING OF VINYL MONOMERS TO

D. J. McDOWALL, B. S. GUPTA and V. T. STANNETT

School o f Textiles, North Carolina State University, Raleigh, NC 2 7650, USA

properties including elasticity, sorbancy, ion exchange capabilities, thermal resis-

2.1. Ceric oxidation

CeAX4 + A ~ CeA2X2 + 2X (2)

k'= kd K[A] (9)

240 280 320 360 40O O

TABLE 1. Equilibrium constants for ceric-alcohol complex formation in

Substrate K (l/mol) Reference

2.2. Graft polymerization

A'+ M ~ - M' (14)

Ce(IV) + M - ~ M" + Ce(III) + H+ (15)

A" + Ce(IV) - ~ Oxidation products + Ce(IIl) + H + (18)

d [M] k.--E [M]2 {k~ + kdK[A] ) (20)

of ceric oxidation and polymerization.14-16' 18,22-27,29, 31,33,37-39,41,42,44-46, 54, 5'7, 59,64

Ce4+ + HSO7~ ~ CeSO~+ + H ÷ (22)

Cell" + M ~ Cell-M' (27)

Ce(IV) + M ~ M" + Ce(III) + H + (28)

CeI1-Mn + M ~ Cell-Mn+ I (29)

Mm + Ce(IV)k_~ Mm + Ce(Ill)+ H+ (32)

Cell-Mn + Cell" ~ Stabilization (33)

Cell" + Ce(IV) ~-~ Oxidation products + Ce(lll) + H+ (34)

This indicates a decrease in the rate of polymerization as ceric ion concentration

TABLE 2. Redox polymerization of styrene

Alcohol Polymer yield

2.3. Oxidation site

TABLE 3. Relative rates of oxidation of cellulose model com-

Substrate Relative rate

TABLE 4. Grafting of methyl methacrylate onto polymers containing sugar

Backbone polymer Grafting Weight

Substrate Model for Relative rates

*Concentration based on anhydro-D-glucose units.

Oxidation of Schardinger/~-dextrin and cellulose by cerium(IV)yielded erythrose

FREE-RADICAL " Ce0-91 FAS1

1.2 //li 81eochedsulp~itepulp

2.4. Alternative mechanisms

X-C-o X.-C-O X-C.O X-C-O

X'-C =O X"C=O X-C=O X-C=O

~% ..% ..~% ..%

These donor-acceptor complexes undergo spontaneous initiation or may be initiated

CH2 OH e' CH2 OH d CH20H

It has been noted by some investigators%'1°7 that grafted acrylamide might be

FIG. 6. A typical curve o f percent graft as a function of initiator concentration.

FIG. 7. A typical curve o f percent graft as a function of acid concentration.

Percent graft generally increases with monomer concentration, lz so,72,73,76,81,9~,97,

TABLE 6. A summary of monomer reactivities under various conditions

Order of reactivity Substrate Temperature (° C) Reference

EA > AN > AAt Cotton 30 140

tAMD - Acrylamide, AA - Acrylic Acid, AN - Acrylonitrile, BA - n-Butyl Acrylate, EA -

m o n o m e r concentrations, reducing the effective m o n o m e r activity. M o n o m e r

Comonomers Cotton Pulp Paper Rayon Cellulose

i'See Table 6 for definitions of abbreviations.

FIG. 8. A typical curve of percent graft as a function of reaction temperature.

to increase and subsequently decrease with an increase in temperature. 12'13~ The

ing due to a reduction in substrate accessibility caused by drying of the substrate

3.7. Other variables

Treatments such as preoxidation, irradiation and ultrasonics generally accelerated

4.1. Proof o f grafting

4.2. Fine structure and morphology

4.3. Molecular structure

Assuming as before (ko/ki) [Ce4+] >~ [M], eq. 52 becomes:

5. PROPERTIES OF THE GRAFTED PRODUCTS