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Synthesis of Poly( -ketone) Using New Polymerization Reaction

利用新型聚合反应合成聚酮

基本信息

批准号：
62470098
负责人：
KOBAYASHI Shiro
金额：
$ 3.52万
依托单位：
TOHOKU 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 1988
项目状态：
已结题

项目摘要

Poly(beta-ketones) are a class of biologically important polymers having keto groups alternatively in the carbon-carbon main chain. They are called "poly-ketides" or "acetogenins", which are involved as precursor in the biosynthesis of aromatic natural products in plants. The present study deals with synthesis of poly (beta-ketones) having a well-defined structure by a new method of polymerization followed by acid-hydrolysis of the product polymers.Isopropoxyacetylene is polymerized in the presence of transition metal catalyst such as WCl_6 and MoCl_5 to give brownish materials. The structure of the isolated polymers has been confirmed as poly(isopropoxyacetylene) by NMR and IR spectroscopy. The polymerization of t-butoxyacetylene by WCl_6 catalyst gave polymer containing a small amount of an isomerized unit. The less acidic catalysts, W(OCH_6)_nCl_<6-n> (n=4,5), however, yielded desired polymer almost exclusively. The hydrolysis of poly(t-butoxyacetylene) was carried out in a mixture of hydrochloric acid and dioxane at room temperature. The IR spectrum of the product indicated that poly(t-butoxyacetylene) was easily hydrolyzed to afford the corresponding poly(beta-ketone) efficiently. On the other hand, poly (isopropoxy acetylene) was less reactive toward the acid hydrolysis.

聚（β -酮）是一类具有重要生物学意义的聚合物，在碳-碳主链上具有酮基团。它们被称为“聚酮”或“醋酸原”，它们作为前体参与植物中芳香天然产物的生物合成。本研究是用一种新的聚合方法合成结构明确的聚（β -酮），然后对产物聚合物进行酸水解。异丙氧基乙炔在过渡金属催化剂WCl_6和MoCl_5的存在下聚合，得到褐色材料。经核磁共振和红外光谱分析证实，所分离的聚合物为聚异丙氧基乙炔。用WCl_6催化剂聚合t-丁氧基乙炔，得到了含有少量异构化单元的聚合物。而酸性较弱的催化剂W(OCH_6)_nCl_<6-n> (n=4,5)几乎完全可以得到所需的聚合物。在盐酸和二恶烷的混合物中，对聚t-丁氧基乙炔进行了室温水解。产物的红外光谱分析表明，聚t-丁氧基乙炔容易水解生成相应的聚-酮。另一方面，聚异丙氧基乙炔对酸水解反应较弱。