First Disyndiotactic Polymer from a 1,4-Disubstituted Butadiene by Alternate Molecular Stacking in the Crystalline State

We report the first synthesis of a disyndiotactic polymer through topochemical polymerization using di(4-methoxybenzyl)muconate as the 1,3-diene dicarboxylate monomer. It provides a tritactic polymer under photoirradiation in the crystalline state, as a result of the alternate molecular stacking in a column formed in the crystals with aid of weak hydrogen bonds such as CH/π and CH···O intermolecular interactions.

我们首次报道了以粘康酸二(4-甲氧基苄基)酯（di(4-methoxybenzyl)muconate）为1,3-二烯二羧酸酯单体，通过拓扑化学聚合（topochemical polymerization）合成双全间同立构聚合物（disyndiotactic polymer）的研究。该聚合体系在晶态光辐照条件下可生成三立构规整聚合物（tritactic polymer），其形成机制为：晶体中借助CH/π与CH···O等分子间弱氢键相互作用形成柱形分子堆积结构，其内分子呈现交替堆叠模式。