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Citation: CHENG CHUNG-HAN, CHIEN PAO-KUNG. THE THERMAL OXIDATION OF cis-1,4-POLYBUTADIENE——Ⅳ. THE KINETICS OF EFFECTIVE CHAIN-BRANCHING REACTION IN THE PROCESS OF AUTOCATALYZED OXIDATION[J]. Acta Polymerica Sinica, ;1964, 6(4): 279-289. shu

THE THERMAL OXIDATION OF cis-1,4-POLYBUTADIENE——Ⅳ. THE KINETICS OF EFFECTIVE CHAIN-BRANCHING REACTION IN THE PROCESS OF AUTOCATALYZED OXIDATION

1．On the basis of the mechanism of degenerate chain—branching reaction in the pro-cess of autoxidation of olefine，and taking account of the fact that(a)decomposition of hydroperoxide would produce either free radicals or stable products，and(b)as a charac-teristic of polymer reaction in solid state chain termination could take place by uniradical reaction，the present authors derived the following equation describing the kinetics of oxygen—absorption by the polymer at a given temperature： 1n Vt/Vco-1-Vt/Vco=(ak3No-yk5)t+C where a=xk7——xk7+(1-x)k8 X and y一the fractions of chainbranching reaction and uniradical termination respectively；Vt-the volume of oxygen absorbed by the polymer at time t(cc 02／g polymer)；Voo一the limiting volume of oxygen absorbed by the polymer during the whole process (cc O2／g polymer)；K7 and k．s--rate constants for decomposition of hydroperoxide into free radicals and stable products respectively；
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