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Enzymatic Polymerization - Development of New Area in Polymer Chemistry -

酶促聚合-高分子化学新领域的发展-

基本信息

批准号：
08102002
负责人：
KOBAYASHI Shiro
金额：
$ 89.6万
依托单位：
KYOTO UNIVERSITY (1997-1999)Tohoku University (1996)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Specially Promoted Research
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1999
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08102002/
关键词：
Enzymatic Polymerization Polysaccharide Polyesters Polyaromatics Hydrolase Oxidoreductase キチンラクトン

项目摘要

Polymerizations catalyzed by enzymes ("enzymatic polymerizations") have been developed. First chemical synthesis of chitin was achieved by chitinase-catalyzed polymerization of a chitobiose oxazoline derivative. Formation of plate-like single crystals of α-chitin was observed. The crystals aggregated, growing up to spherulites. Non-natural polysaccharides, alternatingly 6-O-methylated cellulose and a cellulose-xylan hybrid polymer (polysaccharide having a glucose-xylose repeating unit), were enzymatically synthesized.Systematic investigation on lipase-catalyzed ring-opening polymerization of lactones showed specific enzymatic catalysis in the relationships between the monomer ring-size and polymerizability. Substituted lactones were enantioselectively copolymerized with non-substituted lactones to give optically active polymers. Facile synthesis of end-functionalized polyesters was achieved by using lipase as catalyst. The polymerization of dicarboxylic acid and glycol proceeded even without solvents. The regioselective polymerization of glycerol with divinyl esters produced the reactive polyesters.As to enzymatic synthesis of polyaromatics, oxidoreductase enzymes and their model complexes induced the regioselective polymerization of phenols. A solubie polyphenol was first synthesized by peroxidase-catalyzed polymerization of phenol in an aqueous methanol and the polymer structure could be controlled by changing the solvent composition. Crosslinkable polyphenols having methacryloyl and ethynyl groups were enzymatically synthesized, which were subjected to thermal and photochemical hardening. Urushiol derivatives were cured by laccase catalyst to give the brilliant film with high gloss surface.

由酶催化的聚合（“酶促聚合”）已经发展起来。通过几丁质酶催化聚合甲壳糖恶唑啉衍生物，首次实现了几丁质的化学合成。观察到α-几丁质形成片状单晶。这些晶体聚集起来，长成球晶。非天然多糖，交替6- o甲基化纤维素和纤维素-木聚糖杂交聚合物（多糖具有葡萄糖-木糖重复单元），被酶合成。对脂肪酶催化内酯开环聚合的系统研究表明，单体环大小与聚合率之间存在特异性的酶促作用。取代内酯与非取代内酯对映选择性共聚得到光学活性聚合物。以脂肪酶为催化剂，实现了端功能化聚酯的简易合成。二羧酸和乙二醇的聚合在没有溶剂的情况下进行。甘油与二乙烯基酯的区域选择性聚合制备了反应性聚酯。在多芳烃的酶合成中，氧化还原酶及其模型配合物诱导了苯酚的区域选择性聚合。通过过氧化物酶催化苯酚在甲醇水溶液中聚合，首次合成了一种可溶解多酚，通过改变溶剂组成可控制聚合物结构。采用酶促法合成了具有甲基丙烯酰基和乙基的交联多酚，并对其进行了热和光化学硬化。漆酚衍生物在漆酶催化下固化，得到表面光泽度高的亮膜。