A New Type of Ring-Opening Polymerization via pi-Allyl Complexes

一种新型的π-烯丙基配合物开环聚合

基本信息

批准号：
62470105
负责人：
SAEGUSA Takeo
金额：
$ 3.9万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1989
项目状态：
已结题

项目摘要

A new field, which is still developing, in ring-opening polymerization has been established on the basis of a new concept that useful reactions via pi-allyl palladium intermediates create new polymerization chemistry. Cyclic monomers, which have an appropriate group to accept oxidative addition of Pd(O) at the allylic position, have been accurately designed for this new type of ring-opening polymerization with contemplation of elemental organ reations. Some of them successfully polymerized with the aid of a palladium catalyst via pi-allyl palladium complexes as the key-intermediates.Vinyl cyclopropane derivatives having two electron-withdrawing substituents such as ester, cyano, and sulfone at alpha-position of the vinyl group polymerized to give the polymer connecting at 1.5-position. The polymerization proceeds according to a novel inter-molecular proton-transfer mechanism. Cyclic carbonate, 5,5-dimethyl-4-vinyl-1,3- dioxan-2-one, polymerized with releasing carbon dioxide in the presence of a Pd catalyst and diethylzinc/ethanol as the initiator to produce polyether. This monomer produced an alternating copolymer with cyclic acid anhydrides. Cyclic carbamate, perhydro-5,5-vinyl- 1,3-oxazin-2-one and perhydro-5-methylene-1,3-oxazin-2-one, also polymerized to give dendriform polyamine, which consisted of primary (terminals), secondary (non-branching points), and tertiary (junctions) amino moieties and incorporated the initiator, i.e., benzylamine residue as the core. The polymerization mechanism is quite interesting: the propagating end is a N-H group, which multiplies with progress of the polymerization to produce the dendriform polymers. We termed this quite new polymerization Multi-Branching Polymenzation. Additionally, these two monomers produced graft copolymers having the highly branched polyamines as the graft chains, when their polymerization was initiated with aminomethylated polystyrene.

开环聚合中的一个仍在发展的新领域已经建立在一个新概念的基础上，即通过π-烯丙基钯中间体进行有用的反应创造了新的聚合化学。环状单体具有适当的基团，可以在烯丙基位置接受 Pd(O) 的氧化加成，经过精确设计，可用于这种新型开环聚合反应，并考虑到元素器官反应。其中一些以p-烯丙基钯配合物为关键中间体，在钯催化剂的帮助下成功聚合。在乙烯基的α位上具有酯、氰基、砜等两个吸电子取代基的乙烯基环丙烷衍生物进行了聚合得到在1.5位连接的聚合物。聚合根据新颖的分子间质子转移机制进行。环状碳酸酯，5,5-二甲基-4-乙烯基-1,3-二恶烷-2-酮，在钯催化剂和二乙基锌/乙醇作为引发剂的存在下聚合并释放二氧化碳，生成聚醚。该单体与环状酸酐产生交替共聚物。环状氨基甲酸酯、全氢-5,5-乙烯基-1,3-恶嗪-2-酮和全氢-5-亚甲基-1,3-恶嗪-2-酮也聚合得到树枝状多胺，其由伯（末端）组成）、仲（非支化点）和叔（连接点）氨基部分，并引入引发剂，即苄胺残基作为核心。聚合机理非常有趣：增长末端是一个N-H基团，它随着聚合反应的进行而倍增，产生树枝状聚合物。我们将这种全新的聚合称为多支化聚合。另外，当用氨甲基化聚苯乙烯引发聚合时，这两种单体产生具有高度支化多胺作为接枝链的接枝共聚物。