The photoinitiated free‐radical polymerization of 3,6‐dioxa‐1,8‐octanedithiol and bis(allyl) hydroquinone ether or ethylene glycol divinyl ether leads to poly(thioethers) having anti Markovnikov structure with number‐average molar mass M̄n: 14000, 12000 g/mol, respectively. The chain propagation is limited by disulfide propagation is limited by disulfide production (nearly 3%) and cycle production (nearly 4 %). Differential scanning calorimetry (DSC) investigations showed that the rate of polymerization decreases in the series vinyl ether ≫ allyl ether > 1‐alkene. The influence of the dithiol structure (β‐mercapto ether, thioglycolate, aliphatic thiols) is not dominant.
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Klemm et al. (1990) studied this question.