Polymer Structure Control by Topochemical Polymerization of Diene Monomers

研究了粘康酸烷基酯衍生物在固态下的光聚合反应，以及其拓扑化学聚合反应活性与晶体结构的关系。卤素取代的粘康酸二苄酯衍生物也局部化学聚合，类似于乙酯。此外，我们还成功测定了一系列（Z，Z）-和（E，E）-粘康酸苄酯的单晶结构。X-射线结构分析表明，单体二烯平面的堆积影响了结晶态光聚合反应的活性，在1，3-二烯单羧酸和二羧酸衍生物中引入1-萘基甲基铵作为抗衡阳离子可有效地引发局部化学聚合。不仅对（Z，Z）-粘康酸衍生物进行聚合，而且对（E，E）-粘康酸和山梨酸衍生物进行聚合。萘基甲基铵基团适合于形成柱状晶 关于我们 结构，这有利于局部化学聚合。从聚合物链结构的分析中还发现，无论单体的构型如何，都产生了内消旋双等规聚合物。拓扑化学聚合过程中所得聚合物的立构规整性与单体晶体中的分子堆积密切相关。一些烷基山梨酸铵衍生物也通过拓扑化学机理聚合。证实该聚合物是一种有规立构的高分子量聚合物。聚合物的主链结构为赤式-双同立构-反式-2，5-结构。根据单晶结构分析确定的晶体结构，我们讨论了适合于局部化学聚合的单体的分子堆积。我们还成功地在梯形聚合物的合成中使用自由基聚合在结晶状态。作为双官能单体的对苯二甲撑二铵二山梨酸盐通过局部化学聚合有效地聚合。单晶结构分析和ESR谱的结果也揭示了聚合机理。少

We investigated the photoreaction of alkyl muconate derivatives in the solid state and the relationship between the topochemical polymerization reactivity and crystal structure. The halogen-substituted dibenzyl muconate derivatives also topochemically polymerized, similarly to the ethyl ester. Furthermore, we have successfully determined single crystal structures of a series of the benzyl esters of (Z, Z)- and (E, E)-muconic acid. X-ray structure analysis has revealed that the stacking of the diene plane of the monomer influences the reactivity of the photopolymerization in crystalline state.Topochemical polymerization was efficiently induced by the introduction of 1-naphthyl-methylammonium moiety as the countercation into 1, 3-diene mono- and dicarboxylate derivatives. The polymerization proceeded for not only the (Z, Z)-muconic acid derivatives, but also the (E, E)- muconic and sorbic acid derivatives. The naphthylmethylammonium group is suitable for the formation of the columnar str … More ucture, which is advantageous for topochemical polymerization. It was also revealed from the analysis of the polymer chain structure that the meso-diisotactic polymers were produced, irrespective of the configuration of monomers. The stereoregularity of the resulting polymers during topochemical polymerization is closely related to the molecular packing in the monomer crystals.Some alkylammonium sorbate derivatives were also polymerized via a topochemical mechanism. The polymer was confirmed to be of a stereoregular and high molecular weight polymer. The main chain structure of the polymer was erythro-disotactic-trans-2, 5-structure. Based on the crystal structure determined by single crystal structure analysis, we discussed the molecular packing of the monomers appropriate for topochemical polymerization. We also succeeded in a ladder polymer synthesis using radical polymerization in the crystalline state. p-xylylenediammonium disorbate as the bifunctional monomer was efficiently polymerized by topochemical polymerization. The polymerization mechanism has also been revealed based on the results of the single crystal structure analysis and ESR spectroscopy. Less