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 6(4):279-289(1964)
DOI:
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 6(4):279-289(1964)DOI:
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;