Polymer Structure Control by Topochemical Polymerization of Diene Monomers

通过二烯单体的拓扑化学聚合控制聚合物结构

基本信息

批准号：
11650911
负责人：
MATSUMOTO Akikazu
金额：
$ 1.98万
依托单位：
OSAKA CITY UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650911/
关键词：
polymer crystal engineering polymer structure control radical polymerization organic crystals topochemical polymerization stereoregular polymer solid-state organic synthesis crystal structure analysis 固相合成

项目摘要

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

我们研究了固态中烷基粘液酸盐衍生物的光反应以及拓制性聚合反应性和晶体结构之间的关系。卤素取代的二苯二唑酮衍生物也与乙基酯类似地拓位聚合。此外，我们已经成功地确定了（Z，Z）和（E，E） - 核酸的一系列苄基酯的单晶结构。 X射线结构分析表明，单体的二烯平面的堆叠影响了晶体状态下光聚合的反应性。通过引入1-萘基 - 甲基铵部分作为1，3-二烯单核 - 单二羧酸盐替代的1-萘基 - 甲基铵部分。聚合不仅用于（Z，Z） - 核酸衍生物，而且还用于（E，E） - 糖和山梨酸衍生物。萘甲基铵组适合形成柱状STR…更加倾向，这对于拓制性聚合是有利的。从对聚合物链结构的分析中也揭示了中二异构聚合物，无论单体的构型如何。拓扑化学聚合过程中所得聚合物的立体尺寸与单体晶体中的分子填料密切相关。其他甲贝酸酯衍生物也通过拓扑化学机制聚合了聚合。该聚合物被证实为立体和高分子量聚合物。聚合物的主链结构是红色 - 脱节型Trans-2，5结构。基于单晶体结构分析确定的晶体结构，我们讨论了适合托拓聚合化的单体的分子堆积。我们还使用晶体状态下的自由基聚合物合成了梯子聚合物的合成。 p-氧二二氨二氨基异源性是双功能单体通过拓扑化学聚合有效聚合的。基于单晶体结构分析和ESR光谱的结果，也揭示了聚合机制。较少的