Acrylonitrile Polymerization by Ceric Ion-Primary Alcohol Redox Systems in Aqueous Nitric Acid

[en] The polymerization of acrylonitrile (AN) initiated by CeIV-primary alcohol redox systems has been studied in aqueous nitric acid under nitrogen in the temperature range 0 to 45° C. Taft's correlation can be applied to fit the kinetic results relative to a series of differently substituted primary alcohols. The polymerization is initiated by primary radicals formed in water from the dismutation of the CeIV -alcohol complex. This process has a high activation energy (21 kcal/mol) and gives rise to an induction period at temperatures lower than 40° C. PAN chains containing the alcohol residue are terminated predominantly on metal ions. The alcohol enhances the AN solubility in water and accordingly influences the polymerization kinetics. Variations in temperature and concentration of both components of the redox system allow control of the polymerization rate and of the molecular weight of the resulting PAN. © 1981, Taylor & Francis Group, LLC. All rights reserved.

Disciplines :

Chemistry

Author, co-author :

Renders, G.; Laboratory of Macromolecular Chemistry, Organic Catalysis, University of Liege, Sart-Tilman B6, 4000 Liege, Belgium

Broze, Guy ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie des macromolécules et des matériaux organiques (CERM)

Jérôme, Robert ; Université de Liège - ULiège > Département de chimie (sciences) > Département de chimie (sciences)

Teyssié, Philippe ; Université de Liège - ULiège > Relations académiques et scientifiques (Sciences)

Language :

English

Title :

Acrylonitrile Polymerization by Ceric Ion-Primary Alcohol Redox Systems in Aqueous Nitric Acid

Publication date :

1981

Journal title :

Polymer Preprints

ISSN :

0032-3934

Publisher :

American Chemical Society

Volume :

Issue :

Pages :

1399-1412

Available on ORBi :

since 11 January 2020

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Bibliography

G. Odian, Principles of Polymerization, McGraw-Hill, New York, 1970, p. 189.
R. Buvet, J. Neel, and P. Sigwalt, Chimie Macromoléculaire I, Hermann, Paris, 1970, p. 90.
K. Kaeriyama, Polymer, 10, 11 (1969).
M. Mohanty, B. Pradhan, and M. C. Mohanta, Eur. Polym. J., 15, 743 (1979).
A. A. Katai, V. K. Kulshrestha, and R. H. Marchessault, J. Polym. Sci., C, 2, 403 (1963).
R. K. Samal, M. C. Nayak, and P. L. Nayak, J. Macromol. Sci.-Chem., A12, 815 (1978).
D. Pramanick, Colloid Polym. Sci., 257, 41 (1979).
H. Kinshi and M. Nishio, J. Chem. Ind., Tokyo, 67, 1476 (1964).
G. S. Misra and G. P. Dubey, Polym. Bull., 1, 671 (1979).
P. L. Nayak, R. K. Samal, M. C. Nayak, and A. K. Dhal, J. Macromol. Sci.-Chem., A13, 261 (1979).
S. V. Subramanian and M. Santappa, J. Polym. Sci., A1, 6, 493 (1968).
S. S. Hariharan and M. Maruthamuthu, Makromol. Chem., 180, 2031, 2175, 2513 (1979).
N. C. Pati, S. Lenka, P. L. Nayak, and T. R. Mohanty, J. Polym. Sci., Polym. Chem. Ed., 16, 343 (1978).
A. Rout, S. P. Rout, N. Mallick, and B. C. Singh, Ibid., 391 (1978).
P. L. Nayak, R. K. Samal, and M. C. Nayak, J. Macromol. Sci.-Chem., A12, 827 (1978).
A. K. Roy, S. Pattnaik, R. K. Samal, and P. L. Nayak, Ibid., A12, 1241 (1978).
V. Desreux and J. Bisschoff, Bull. Soc. Chim. Belg., 59, 93 (1950).
J. Brandrup and E. H. Immergut, Polymer Handbook, Wiley, New York, 1975.
G. Mino, S. Kaizerman, and E. Rasmussen, J. Polym. Sci., 38, 393 (1959).
F. R. Duke and R. F. Bremer, J. Am. Chem. Soc., 73, 5179 (1951).
M. Ardon, J. Chem. Soc., p. 1811 (1957).
S. K. Saba and A. K. Chaudhuri, J. Indian Chem. Soc., 42, 735 (1965).
M. S. Newman, Steric Effects in Organic Chemistry, Wiley, New York, 1956, Chap. 13.
N. B. Chapman and J. Shorter, Advances in Linear Free Energy Relationships, Plenum, New York, 1972, Chap. 2.
F. S. Dainton, P. H. Seaman, D. G. L. James, and R. S. Eaton, J. Polym. Sci., 34, 209 (1959).