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Synt6hesis and Ring Opening-Closure Behavior of Polymers Containing a Five-Membered Lactone Unit

五元内酯单元聚合物的合成及开闭环行为

基本信息

批准号：
07651071
负责人：
KIMURA Takao
金额：
$ 1.41万
依托单位：
Utsunomiya 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

Bifunctional five-membered lactone monomers were prepared by the chemical transformation of t-butyl methacylate and dimethyl itaconate dimers telomerized using bromotrichloromethane. Polymerizations of these lactone monomers with some aliphatic and aromatic diamines and diols afforded polyamides, polyesters, polyamic acids, and polyimides. The polyamides prepared using aliphatic primary diamines had a high hydrophilicity owing to partial hydrolytic cleavage of the lactone moiety.The ring-opening and -closure reactions of condensation compounds of (2R^<**>,4S^<**>) -4-chloroformyl-2-chloroformylmethyl-2,4-dimenthyl-4-butanolide with monoamines and monools served to elucidate the ring-opening behavior of the resulting condensation polymers. The variation of ring-opening ratio with the passage of time was traced by the ^1H-NMR method. The behavior of model compounds was affected considerably by such factors as pH,solvent, structure of substrate, and so on. As these ring-opening and -closure reactions finally attain equilibrium, the ring-opening of the lactone moiety is presumed to be a reversible reaction. On the other hand, the ring-opening of lactone unit in the model compound derived from aliphatic primary amine proceeded completely in a phosphate buffer solution and it was independent of enzyme.Hydrolysis of titled polyamides is affected by the ring-opening ratio and aromatic site, and the results suggest the scission of end-type.

以甲基丙烯酸叔丁酯和衣康酸二甲酯二聚体为原料，溴三氯甲烷为调聚剂，通过化学转化反应合成了双官能五元内酯单体。这些内酯单体与一些脂肪族和芳香族二胺和二醇聚合得到聚酰胺、聚酯、聚酰胺酸和聚酰亚胺。由脂肪族伯二胺制备的聚酰胺由于内酯部分水解断裂而具有高的亲水性，（2 R ^**>，4S ^**>）-4-氯甲酰基-2-氯甲酰基甲基-2，4-二甲基-4-丁炔醇与单胺和单醇的缩合物的开环和闭环反应阐明了所得缩聚物的开环行为。通过^1H-NMR方法追踪开环率随时间的变化。模型化合物的行为受pH、溶剂、底物结构等因素的影响较大，当开环和闭环反应最终达到平衡时，内酯部分的开环被认为是一个可逆反应。脂肪族伯胺衍生的模型化合物的内酯单元在磷酸盐缓冲溶液中完全开环，不依赖于酶的催化作用，开环率和芳香位对水解有影响，说明开环过程中发生了端基断裂。