Abstract
AbstractPoly(N‐vinylcarbazole) (PVK) samples were found to exhibit up to three glass transition temperatures Tg, corresponding to the whole chain and the syndiotactic and isotactic stereoblocks. An increasing tendency to multiple Tgs, and hence to phase separation, was observed with increasing isotacticity. Limiting values at infinite molecular weight for syndiotactic and isotactic PVK were obtained from correlations of the Tgs corresponding to the syndiotactic and isotactic stereoblocks with their respective average stereoblock lengths derived from 13C NMR measurements. They were found to be 549 and 399 K, respectively. The conventional Tg for PVK was found to exhibit the following dependence upon the syndiotactic dyad mole fraction Xs: The molecular weight dependences of the conventional Tgs for several fractionated PVK samples obeyed a Fox–Flory‐type relation with values of −dTg/d(1/M) varying between 7.6 × 103 for isotactic PVK and 2.7 × 105 for Luvican M 170.
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