Journal of Thermai Analysis, VoL 38 (1992) 267-275 THE THERMAL DEGRADATION KINETICS OF POLY(CHLORETI-1YLMETHACRYI_~TE S) L G. Popovic 1, L. Katsikas 2, K.A. Voloschuk 3, J. S. Velickovic 1 and W. Schnabel 1 1FACULTY OF TECHNOLOGY AND METAI~URGY, BELGRADE UNIVERSITY, KARNEGIJEVA 4, YU-11000BELGRADE, YUGOSLAVIA 2HAHN-MEITNER-INSTITUT BERLIN GMBH, BEREICH PHOTOCHEMISCHE ENERGIEUMWANDLUNG, GLIENICKER SIR. 100, D-1000 BERLIN 39, F.ILG. 3MOSCOW MENDELEEV INSTITUTE OF CHEMICAL TECHNOLOGY, MIUSSKAJA SO. 9, MOSCOW 125820, USSR .The thermal degradation kinetics of poly(2-mono-, 2,2-di- and 2,2,2-trichlorethyl methacrylate) and of the non-chlorinated poly(ethyl methaerylate) were studied by TG in the absence and presence of oxygen. The overall thermal degradation energy, determined by the Flynn-Wall method, increases with increasing chlorine content of the polymer when the degradation is performed in the absence of oxygen, while the trend "is reversed in the presence of oxygen. Competition between the two major non-oxidative thermolysis reactions, depolymerization and crosslinking, could be monitored by DTG. Generally, the thermal stability of the investigated polymers is reduced by oxygen. Keywords: kinetics:, poly(chlorethyl methacrylates) Introduction It is well known in the literature that poly(methacrylates) thermally decompose primarily by depolymerization [1]. In the case of poly(ethyl methacrylate) (PEMA) depolymerization is accompanied to a small extent by ester decomposition [2, 3]. The introduction of chlorine into the ester substituent affects the overall degradation mechanism. Some work on the thermal degradation of poly(ehlorethyl methacrylates) was done by Chien et aL [4-6]. These studies were based on the analysis of samples pyrolysed at 600 ~ Thermal degradation studies of poly(2-mono, 2,2-di- and 2,2,2- triehlorethyl methacrylate) (PMCMA, PDCMA and PTCMA), designed to analyse the initial and intermediate stages of the process, have shown that depolymerization remains the dominant thermolysis reaction [7, 8]. John Wl'Hley & Sons, Limited, Chichester AkadOniai Ka'ad6, Budapest