Development of Polycondensation via Chain Reaction

链式反应缩聚的发展

基本信息

批准号：
07805084
负责人：
YOKOZAWA Tsutomu
金额：
$ 1.28万
依托单位：
Kanagawa University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

It is difficult to obtain molecular weight-controlled polymers with narrow molecular weight distribution in polycondensation, which proceeds in a step polymerization manner. If polycondensation proceeds in a chain-growth reaction manner from an initiator like the polymerization of vinyl monomers or cyclic monomers, polymers having a defined molecular weight and narrow molecular weight distribution would be produced though essentially stable propagating end groups. We study two types of polycondensations which proceed via chain polymerization (condensative cahin polymerization) on the basic strategy that the electrophilic site of monomers having necleophilic and electrophilic sites becomes more reactive after the nucleophilic site reacts with another monomer.The first type of polycondensation is fluoride ion-catalyzed polycondensation of 4-trimethylsiloxybenzoyl chloride derivatives. The model reaction showed the propagating acid chloride was more reactive than the acid chloride of monomer. In the polymerization, however, polymer was precipitated during reaction because of low solubility of polymer. Therefore the chain polymerization behavior was not evaluated.The second type of polycondensation is palladium-catalyzed CO insertion polycondensation of 4-bromophenol derivatives. The model reaction showed that the model of propagating end were more reactive than the model of monomer electrophilic site. However, ester exchange reaction occurred. The polymerization was carried out in the presence of bromobenzene with the electron-withdrawing group as a initiator to yield low-molecular weight polymer, the GPC curve of which showed that polymerization took place via chain polymerization manner from the initiator in the initial stage.

很难获得多敏的分子量分布分子分布窄的分子量控制聚合物，这是以阶级的聚合方式进行的。如果多浓度以链生长反应的方式进行，例如乙烯基单体或环状单体聚合物，尽管基本稳定的传播最终组，但将产生具有定义的分子量和狭窄的分子量分布的聚合物。我们研究了两种类型的多降压，它们是通过链聚合（凝结的Cahin聚合）进行的，即基本策略，即具有坏死性和亲电的单体的亲电位点在亲核位点与另一种单体反应后，偶氮内纤维化型多钙化型二氧化量剂量促成型多钙化量后，核仁位点反应型。 4-三甲基氧基苯甲酰氯化物衍生物。模型反应表明，传播酸比单体的酸氯化物更具反应性。然而，在聚合中，由于聚合物的溶解度低，聚合物在反应过程中被沉淀。因此，未评估链聚合行为。第二种类型的多限度是钯催化的4-溴苯酚衍生物的插入插入多头敏。模型反应表明，传播端的模型比单体亲电位点的模型更具反应性。但是，发生了酯交换反应。在溴苯存在的情况下与电子吸引者组作为引发剂作为产生低分子量聚合物的引发剂进行聚合，其GPC曲线表明，在初始阶段的引发剂中，聚合是通过链聚合方式进行的。