ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 10, Number 1
JKCSEZ 10(1)
February 20, 1966 

It is well known that the coloration and structural changes in thermal treatment of polyacrylonitrile are due to the formation of partly hydrogenated naphthylidine-type ring involving the pendant nitrile groups. Any quantitative study of the reaction, in the sense of kinetics and/or statistics, however, has never been reported. This paper presents that, at first, the disappearance of the nitrile groups follows the first order kinetics, which indicates clearly that nitrile groups do not disappear by a long chain reaction-the kinetic chain length is very short. This observation rules out the long intramolecular and intermolecular propagation chain through which most of the nitrile groups disappear. From the evidence that a similar reaction occurs in propylene carbonate solutions without gel formation, one may conclude that the coloration and structural changes are not necessarily intermolecular reaction. Secondly, a finite amount of nitrile groups remains unreacted at the extrem of reaction-not contributed to the formation of naphthylidine-type ring. The concentration of this unreacted nitrile groups is 19∼22% which is good agreement with the statistically calculated value of 19.2%