Polymer Structure Control by Topochemical Polymerization of Diene Monomers

我们研究了烷基偏酸盐衍生物在固体状态下的光反应，以及拓扑聚合反应活性与晶体结构的关系。与乙酸乙酯类似，卤素取代的二苄基偏酸盐衍生物也进行了局部化学聚合。此外，我们还成功地测定了(Z，Z)-和(E，E)-弱酸的一系列苄酯的单晶结构。X-射线结构分析表明，单体二烯平面的堆积影响了结晶状态下的光聚合反应活性。通过在1，3-二烯单羧酸酯和二元酸的衍生物中引入1-萘甲基铵作为反阳离子，可以有效地引发拓扑聚合。聚合反应不仅适用于(Z，Z)-弱酸衍生物，也适用于(E，E)-弱酸和山梨酸的衍生物。萘甲基铵基团适合于柱状…的形成较多的结构，有利于拓扑化学聚合。聚合物链结构的分析还表明，无论单体的构型如何，都会产生介观-全同立构聚合物。在拓扑聚合过程中得到的聚合物的立体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进行了聚合。证实了该聚合物是一种立体规则的高相对分子质量聚合物。聚合物的主链结构为赤二异构型-反式-2，5-结构。在单晶结构分析确定的晶体结构的基础上，讨论了适合于拓扑聚合的单体的分子堆积。我们还成功地利用结晶状态下的自由基聚合法合成了梯形聚合物。以对二甲基二胺为双官能团单体，采用拓扑聚合的方法进行了高效聚合。根据单晶结构分析和ESR波谱分析结果，揭示了聚合反应机理。较少

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