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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

我们研究了粘康酸烷基酯衍生物的固态光反应以及拓扑化学聚合反应活性与晶体结构之间的关系。与乙酯类似，卤素取代的粘康酸二苄酯衍生物也进行局部化学聚合。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晶态光聚合的反应活性。通过在1, 3-二烯单羧酸酯和二羧酸酯衍生物中引入1-萘基甲基铵部分作为抗衡阳离子，有效地诱导了拓扑化学聚合。不仅(Z,Z)-粘康酸衍生物进行聚合，而且(E,E)-粘康酸和山梨酸衍生物也进行聚合。萘甲基铵基团适合形成柱状结构，有利于拓扑化学聚合。对聚合物链结构的分析还表明，无论单体的构型如何，都会产生内消旋二等规聚合物。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制聚合。证实该聚合物是有规立构的高分子量聚合物。该聚合物的主链结构为赤式双全同立构反式2,5结构。基于单晶结构分析确定的晶体结构，我们讨论了适合拓扑化学聚合的单体的分子堆积。我们还成功地利用结晶态自由基聚合合成了梯形聚合物。对二甲苯二山梨酸二铵作为双功能单体通过拓扑化学聚合有效地聚合。基于单晶结构分析和ESR光谱的结果也揭示了聚合机理。较少的