Abstract
The thermoreversible gelation of chlorinated polyethylene has been described. Polymers with a large range of crystallinities, including noncrystalline materials, were studied. Solutions of all the polymers exhibited thermoreversible gelation. Gels of the noncrystalline polymers showed equilibrium properties in that the sol-gel and gel-sol transitions occurred at the same temperature. Crystalline polymers produced nonequilibrium gels. The gel-sol transition occurred 10–20° above the sol-gel transition and ageing phenomena were observed. The gelation enthalpy was determined from the concentration dependence of the gelation temperature. A linear relationship between the heat of gelation and the solid state crystallinity was observed. The plot extrapolated to 24 kJ/mol at zero crystallinity in accord with the observed gelation enthalpies of the noncrystalline polymers which were less than 24 kJ/mol. This result is interpreted as evidence that at least two processes contribute to gel formation, viz network formation by chain associations in both crystalline and non crystalline polymers and, in the case of crystalline polymers, network stabilization by formation of microcrystallites.
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