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Precise Synthesis of Functional Polymers Utilizing Cl Resources.

利用Cl资源精确合成功能聚合物。

基本信息

批准号：
12650866
负责人：
NOZAKI Kyoko
金额：
$ 2.24万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2001
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12650866/
关键词：
Cl resources Carbon monoxide Carbon dioxide Olefin Epoxide Asymmetric polymerization Palladium Zinc

项目摘要

Aiming at the synthesis of functionalized polymers with precise control of structure and molecular weight, introduction of functional groups into the polymers have been examined, especially utilizing the easily available Cl resources, such as carbon monoxide and carbon dioxide. The two major subjects are, (i) asymmetric alternating copolymerization of olefins and carbon monoxide ; and (ii) asymmetric alternating copolymerization of meso-epoxide and carbon dioxide. The achievements are summarized as follows.(i) Asymmetric alternating copolymerization of olefins and carbon monoxideUsing a palladium complex of chiral phosphine-phosphite ligand BINAPHOS, alternating copolymerization of CO with perfluoroalkyl substituted olefins were examined. The isotactic copolymerthus obtained exhibited high water repellent property. Also, side-chain liquid crystalline polyketones were successfully produced.(ii) Asymmetric alternating copolymerization of meso-epoxide and carbon dioxideCompletely alternating copolymerization of cyclohexene oxide with carbon dioxide was achieved using a zinc complex of chiral amino alcohols. The polymerization proceeded in a highly enantioselective manner and thus, highly enantioselective alternating copolymerization has been performed for the first time. One of the unique features of the current study is that the enantiomeric excess of each of the chiral unit could be determined unambiguously. Because the polycarbonate can be hydrolyzed under alkali conditions, degradation of the polymer gave us the chiral diol unit whose enantiomeric excess was determined to be 70 % by chiral GLC analysis. Further studies on the catalyst revealed that the active species is a dimeric zinc complex. Isolation of the pure dimeric complex enabled us to disclose the reaction mechanism as well as elevate the enantiomeric excess finally up to 80 %.

为了合成具有精确控制结构和分子量的功能化聚合物，已经研究了向聚合物中引入官能团，特别是利用容易获得的Cl资源，如一氧化碳和二氧化碳。两个主要的主题是，（i）烯烃和一氧化碳的不对称交替共聚;和（ii）内消旋环氧化物和二氧化碳的不对称交替共聚。取得的成就概述如下。(i)烯烃与一氧化碳的不对称交替共聚合研究了手性膦-亚磷酸酯配体BINAPHOS的钯配合物催化CO与全氟烷基取代烯烃的交替共聚合反应。所得全同立构共聚物具有高的拒水性能。此外，侧链液晶聚酮被成功地生产。(ii)内消旋环氧化合物与二氧化碳的不对称交替共聚合用手性氨基醇锌配合物实现了环氧环己烷与二氧化碳的完全交替共聚合。聚合反应以高对映选择性方式进行，因此，首次进行了高对映选择性交替共聚。本研究的一个独特之处是可以明确地确定每个手性单元的对映体过量。因为聚碳酸酯可以在碱性条件下水解，聚合物的降解给我们提供了手性二醇单元，其对映体过量通过手性GLC分析测定为70%。对催化剂的进一步研究表明，活性物种是二聚锌络合物。分离的纯二聚体复合物，使我们能够揭示的反应机理，以及提高对映体过量最终高达80%。