How can the thermal stability and crystallinity of oligomers be controlled? Four members of a homologous series of chlorinated poly(vinyl ester) oligomers from poly(vinyl acetate) to poly(vinyl stearate) with degrees of polymerisation of 10 and 20 were prepared by telomerisation with carbon tetrachloride. All oligomers are thermally degraded in two main steps, whereby HCl and side chains are lost before the backbone is degraded. The polymers with short side chains, up to poly(vinyl octanoate), are amorphous and show internal plastification, while those with long side chains are semi-crystalline due to side chain crystallisation. The glass transition and melting temperatures as well as the initial decomposition temperature are more strongly influenced by the side chain length than by the degree of polymerisation. Thermal stability is improved when both the size and the number of side chains increase, but only long side chains lead to a significant increase in decomposition resistance.
D. Heinze, T. Mang, C. Popescu, O. Weichold
Effect of side chain length and degree of polymerization on thedecomposition and crystallization behaviour of chlorinated poly(vinylester) oligomers
Thermochimica Acta 2016, 637, 143-153. http://dx.doi.org/10.1016/j.tca.2016.05.015
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