Enzymatic Polymerization - Development of New Area in Polymer Chemistry -

已经开发了由酶催化的聚合（“酶促聚合”）。甲壳素的首次化学合成是通过甲壳素酶催化壳二糖恶唑啉衍生物的聚合来实现的。观察到片状α-甲壳素单晶的形成。晶体聚集，生长成球晶。采用酶法合成了6-O-甲基化纤维素和纤维素-木聚糖杂化聚合物（含有葡萄糖-木糖重复单元的多糖）两种非天然多糖，系统研究了脂肪酶催化内酯开环聚合反应，发现酶对单体环的大小与聚合性之间存在特异性的催化作用。取代内酯与非取代内酯进行对映选择性共聚反应，得到光学活性聚合物。以脂肪酶为催化剂，实现了末端功能化聚酯的合成。二羧酸和乙二醇的聚合甚至在无溶剂的情况下进行。甘油与二乙烯基酯的区域选择性聚合生成反应性聚酯;对于多环芳烃的酶促合成，氧化还原酶及其模型复合物诱导酚类的区域选择性聚合。本文首次采用过氧化物酶催化苯酚在甲醇水溶液中聚合的方法合成了可溶性多酚，并通过改变溶剂组成来控制聚合物的结构。本文采用酶法合成了具有甲基丙烯酰基和乙炔基的交联多酚，并对其进行了热硬化和光化学硬化。漆酚衍生物在漆酶催化下固化，可获得表面光泽度高的光亮漆膜。

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.