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ABSTRACT: Acrylic acid (AA) was grafted to cellulose by using ceric ammonium nitrate
(CAN) initiator in aqueous nitric acid solution at 30, 50, 70, and 907C during reaction
periods of 30 to 180 minutes. About 45% of the AA was polymerized at 907C after 180
minutes. The grafted polymer and homopolymer were isolated by acetone from the
reaction mixture, dried, and subjected to Soxhlet extraction with dioxane to separate
the homopolymer, poly(acrylic acid), from the graft copolymer. The water absorption
capacities and grafting values of grafted cellulose were also determined. The maximum
grafting yield was obtained at 307C. It was also observed that polyacrylic acid-grafted
cellulose produced at 307C had the highest water retention capacity. The time depen-
dence of AA conversion allowed calculation of first-order reaction rate constants. These
rate constants were then used to determine apparent activation energies. q 1997 John
Wiley & Sons, Inc. J Appl Polym Sci 66: 929–934, 1997
929
CH¤OH
When the ceric salts, such as ceric ammonium H
O
nitrate [Ce(NH4 )2 (NO3 )6 ], were used as an initi- O
H 1 Ce
41
ator on the graft copolymerization onto cellulose, OH H
it is proposed that a ceric ion–cellulose complex
is initially formed as a result of one electron trans- H
H OH
fer. Then the ceric ion is reduced to cerous ion,
and a free radical is created on the cellulose back- CH¤O ∫
bone, as shown in eq. (1).2 H
O
H O 31 1
OH H 1 Ce 1 H (3)
CH¤OH
H H
O H OH
H O 41
OH H 1 Ce
Another grafting site subsequently proposed 3
H OH involves the oxidation of the anhydroglucose unit,
∫ as shown in eq. (4).
CHOH
H CH¤OH
O H
H O 31 1 O
OH H 1 Ce 1 H (1) H O 41
OH H 1 Ce
H
H OH H
H OH
CH¤OH
The radical site on the cellulose then initiates H
O
graft copolymerization of a polar vinyl monomer, H O 31 1
which is present in the reaction mixture. H 1 Ce 1 H (4a)
CH C
H
∫ O OH
CHOH
H
O
H O CH¤OH
OH H 1 (n 1 1)CH¤®CH H
O
H COOH H H O 1 (n 1 1)M
H OH
CH Cı
COOH H
O OH
CH©CH¤©CH¤©CH¤COOH
n
CHOH CH¤OH
H H
O O
H O H H O (4b)
OH H (2)
CH C©M n H
H
H OH O OH
COOH COOH
The homopolymer formation during the copoly- Mn: ©CH¤©CH©CH¤©CH¤
merization is attributed to the chain transfer from n
CH¤OH CH¤OH
O∫ O©Mn
H H
OH H C®O 1 (n 1 1)M OH H C®O (5)
H H H H
H OH H OH
CH¤OH
O
H O 41
OH H 1 Ce
H H
H OH
CH¤OH CH¤OH
OH OH
H ∫ H
OH H C®O 1 (n 1 1)M OH H C©Mn (6)
H H O
H OH H OH
A lot of work has been reported on grafting of of monomer (AA) and FeSO4 /H2O2 and CAN initia-
various vinyl monomers onto cellulosic materials tors were studied. Satisfactory grafting yield with
using different types of initiators.4 – 20 According the FeSO4 /H2O2 initiator system could not be ob-
to the nature of the vinyl monomer grafted on tained. Therefore, the experiments in this work
cellulose, it gains different physical and/or chemi- were performed on the predetermined monomer
cal properties. To increase the hydrophilicity, the concentration with a CAN initiator.
monomers containing hydrophilic groups must be
grafted onto cellulose.
Although some research on acrylic acid (AA) EXPERIMENTAL
grafting onto cellulose, also involving preirradia-
tion techniques, has been carried out previously, Chemicals
relatively little has focused on the evaluation of
water retention capacities.14 – 21 The AA monomer was distilled under vacuum and
Lepoutre et al.4 obtained the sodium polyacry- stored at 087C until used. Ceric Ammonium Ni-
late–polyacrylamide grafted cellulose fibers by trate (Merck) was used as initiator. Cellulose was
hydrolyzing the poly(acrylonitrile)-grafted cellu- obtained from Sigma. The bidistilled water was
lose fibers and investigated the water and saline used. Nitric acid and acetone were reagent grade.
retention values. Williams and Stannett 16 investi- Nitrogen was purified by passing it through a
gated the water retention values of poly(acrylic freshly prepared alkaline pyrogallol solution and
acid) –grafted cellophane obtained by using concentrated sulfuric acid.
FeSO4 /H2O2 initiator. Okieimen and Ebhoaye 17,18
have investigated the water and saline retention
Graft Copolymerization Experiments
capacities of poly(acrylic acid) –grafted holocellu-
lose and obtained the maximal values of 9 and 7 Four grams of cellulose was added to 320 mL of
g g, respectively. 2.5 10 03 M HNO3 solution in a three-necked flask,
In the current work, the effects of reaction tem- then stirred and purged by passing nitrogen for
perature on the graft copolymerization of AA onto 30 min. CAN and 20 mL of AA were then added
cellulose using a ceric ammonium nitrate (CAN) into reaction mixture. Bubbling of nitrogen
initiator were investigated. The temperature is one through the reaction mixture was continued for
of the most important factors to affect the extent of the duration of reaction, which was carried out by
grafting. This effect depends upon the type of initia- placing the flask in a water bath at 30, 50, 70,
tor and monomer and their concentrations. In early and 907C and for 30 to 180 minutes. After the
laboratory experiments, the effects of concentration desired reaction time had elapsed, the polymer-
Table I Acrylic Acid Disappearance Rate (2) Grafting yield decreases as reaction tem-
Constants perature decreases.
(3) High temperatures favor homopolymeriza-
Temperature k tion more than grafting.
(7C) (min01 ) r2
(4) The step determining the overall activa-
30 0.018 0.98
tion energy is the propagation step.
50 0.022 0.98
70 0.030 0.97
90 0.033 0.97
REFERENCES
onto cellulose was the apparent first-order AA dis- 1. N. Geacintov, V. Stannett, E. W. Abrahamson,
appearance rate constants. Results are summa- and J. J. Hermans, J. Appl. Polym. Sci., 7, 54
rized in Table I. These rate constants were then ( 1960 ) .
used to determine apparent activation energy. 2. G. Mino and S. Kaizerman, J. Polym. Sci., 31, 242
The overall activation energy (E) for polymeriza- (1958).
3. N. Gaylord, J. Polym. Sci., 37, 153 (1972).
tion can be expressed with eq. (7), which is the
4. P. Lepoutre, S. H. Hui and A. A. Robertson, J.
difference between the sum of the activation ener- Appl. Polym. Sci., 17, 3143 (1973).
gies for propagation (Ep ) and decomposition of ini- 5. K. Bardhan, S. Mukhopadhyay, and A. R. Chat-
tiator (Ed ) and the activation energy of termina- terjee, J. Polym. Sci., Polym. Chem. Ed., 15, 141
tion (Et ) (1977).
6. B. N. Misra, J. K. Jassal, and C. S. Pande, J.
E Å Ep / Ed /2 0 Et /2 (7) Polym. Sci., Polym. Chem. Ed., 16, 295 (1978).
7. B. N. Misra, R. Dogra, I. Kaur, and J. K. Jassal, J.
These values for the peroxide systems have Polym. Sci., Polym. Chem. Ed., 17, 1861 (1979).
been given as Ed Å 30 – 40 kcal mol, Ep Å 5 – 10 8. B. N. Misra, R. Dogra, and J. K. Mehta, J. Polym.
kcal mol, and Et Å 2 – 5 kcal mol. E consisting Sci., Polym. Chem. Ed., 18, 749 (1980).
mainly of Ed and Et has a small effect on E . 9. M. J. Fernandez, I. Casinos, and G. M. Guzman, J.
The decomposition reaction of initiator for this Polym. Sci., Polym. Chem. Ed., 28, 2293 (1990).
system is an ionic reaction, and the activation 10. M. J. Fernandez, I. Casinos, and G. M. Guzman,
Makromol. Chem., 191, 1287 (1990).
energy for the decomposition has a small value;
11. M. J. Fernandez, I. Casinos, and G. M. Guzman, J.
therefore, the step determining the overall acti- Polym. Sci., Polym. Chem. Ed., 28, 2275 (1990).
vation energy is the propagation step. In this 12. M. A. Shah, M. A. Majid, and M. A. Bari, Chitta-
study, the overall activation energy in the graft gong Univ. Studies, 15, 31 (1991).
copolymerization of AA onto cellulose for the 13. Y. Huang, B. Zhao, G. Zheng, S. He, and J. Gao,
first-order reaction was found to be 2.313 kcal J. Appl. Polym. Sci., 45, 71 (1992).
mol. It is known that the value of overall activa- 14. A. H. Zahran, J. L. Williams, and V. T. Stannett,
tion energy ( E ) is determined mainly by the J. Appl. Polym. Sci., 25, 535 (1980).
activation energy of decomposition. But since 15. J. L. Williams and V. T. Stannett, J. Appl. Polym.
decomposition activation energies for ionic reac- Sci., 23, 1265 (1979).
tions is small, the activation energy ( E ) calcu- 16. J. L. Williams and V. T. Stannett, U.S. Pat.
4,036,588 (1977).
lated from AA disappearance rate constants rep-
17. E. F. Okieimen and J. E. Ebhoaye, J. Macromol.
resents mainly the activation energy of propaga- Chem., 23, 349 (1986).
tion. Apparent first-order rate constants with 18. E. F. Okieimen and J. E. Ebhoaye, J. Appl. Polym.
satisfactory regression constant yielded a low Sci., 31, 1275 (1986).
activation energy of 2.3 kcal mol. 19. S. Mukhopadhyay, J. Prasad, and S. R. Chatterjee,
Die Makromol. Chem., 176, 1 (1975).
20. J. T. Guthrie, M. B. Huglin, and G. O. Phillips, J.
CONCLUSIONS Polym. Sci., 37, 205 (1972).
21. G. Gürdağ, M. Yaşar, and M. A. Gürkaynak, Paper
(1) Monomer conversion increases as reaction presented at the 35th IUPAC Congress, Istanbul,
temperature increases. Turkey, 14–19, Aug. 1995.