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Synthesis of Functional Polymers with Well-defined Chain Structure by Means of Anionic Living Polymerization

阴离子活性聚合合成具有明确链结构的功能聚合物

基本信息

批准号：
62550665
负责人：
TAKENAKA Katsuhiko
金额：
$ 1.09万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1988
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62550665/
关键词：
Anionic Living Polymerization Protecting Groups Functional Polymers 脱保護

项目摘要

Anionic polymerizations of styrene and 1,3-butadiene derivatives containing functional groups were carried out under various conditions. In the anionic polymerization of styrene containing alkyl carboxylate function (I), stable living polymer was formed when it was polymerized in THF at -95 C with potassium as a counterion. In the case of lithium counterion, no polymerization took place. The quantitative hydrolysis of ester function in the resulting polymer was achieved by the treatment with trimethylsilyl iodide under neutral condition to give poly(4-vinylbezoic acid) having well-defined chain structure. With monomers bearing alkyl sulfonamide (II) and alkyl sulfonate (III) groups, polymers with narrow molecular weight distributions were obtained quantitatively regardless of the counterion used. In some cases, precipitation of polymers were observed during the course of polymerization. This was presumably due to the aggregation of active chainend species.The anionic polymerizations of 1,3-butadiene containing formyl (IV) and hydroxy (V) groups protected with acetal functions resulted in the formation of polymers of controlled molecular weights with narrow molecular weight distributions when they were prepared in THF at -78 C with sodium and/or potassium counterion. The microstructure of the resulting polymers were mainly 1,2- and 3,4-, which was close to the structures of polyisoprene prepared in polar solvent.

在不同条件下进行了苯乙烯和含官能团的1，3-丁二烯衍生物的阴离子聚合。在含羧酸烷基酯官能团苯乙烯的阴离子聚合中，以钾为配位剂，在THF中于-95 ℃聚合，可形成稳定的活性聚合物。在锂离子的情况下，没有发生聚合。在中性条件下，用三甲基碘硅烷处理聚合物，使聚合物中的酯官能团发生定量水解，得到具有明确链结构的聚4-乙烯基苯甲酸。与带有烷基磺酰胺（II）和烷基磺酸盐（III）基团的单体，聚合物具有窄的分子量分布定量得到，无论使用的counterparts。在某些情况下，在聚合过程中观察到聚合物沉淀。当它们在THF中在-78 ℃下与钠和/或钾络合剂制备时，含缩醛官能团保护的甲酰基（IV）和羟基（V）的1，3-丁二烯的阴离子聚合导致形成具有窄分子量分布的受控分子量的聚合物。所得聚合物的微观结构主要为1，2-和3，4-结构，与极性溶剂中制备的聚异戊二烯结构接近。