酶催化法一步合成聚(对二氧环己酮-co-丁二醇-co-丁二酸)共聚酯  

One-pot enzymatic synthesis of poly(p-dioxanone-co-butylene-co-succinate)

作　　者：聂武成 党海春[1] 宋飞[1] 汪秀丽[1] 王玉忠[1] 

机构地区：[1]四川大学化学学院,环保型高分子材料国家地方联合工程实验室,成都610064

出　　处：《中国科技论文》2015年第6期633-637,共5页China Sciencepaper

基　　金：高等学校博士学科点专项科研基金资助项目(20120181110049)

摘　　要：选择结构单元中具有醚键,水解速率较快的对二氧环己酮（PDO）作为第三单体,以Novozym 435为催化剂,将PDO与丁二醇、丁二酸二乙酯进行共聚,通过一步法合成了聚（对二氧环己酮-co-丁二醇-co-丁二酸）共聚酯（PPBS）。研究了反应温度和反应时间对PPBS分子量的影响,在70℃反应72h的条件下,获得的PPBS共聚酯的重均分子量达到23 000g/mol,多分散系数（PDI）在1.7~2.6之间。采用核磁共振光谱仪对共聚酯的结构以及共聚酯中PDO单元的含量进行了确认。利用TGA和DSC对PPBS的热稳定性和热转变行为进行了研究,发现其热稳定性与纯PBS类似,好于PPDO;PPBS共聚酯的熔融温度为77.2℃,明显低于PPDO和PBS,且其结晶能力较差,较弱的结晶能力预示着共聚物有较快的生物降解速率。由于没有使用任何金属催化剂,所制备的PPBS共聚酯更适合作为生物医用材料使用。Aliphatic copolyester was successfully synthesized via a combined lipase-catalyzed ring-opening and polycondensation polymerization.Copolymerization of p-dioxanone（PDO）with diethyl succinate（DES）and 1,4-butanediol（BD）in the presence of Novozym 435 was successfully carried out and poly（p-dioxanone-co-butylene-co-succinate）（PPBS）was obtained.The effect of reaction temperature and time on the molecular weight of PPBS was investigated.The maximum weight-average molecular weight（Mw）of PPBS was obtained（23 000g/mol）at 70℃for 72 h.The chemical structure and the real content of PDO unit in PPBS was determined by ^1 H-NMR.The thermal stability of PPBS was investigaged by TGA,and found that its thermal stabiliy was as good as PBS.The melting temperature of PPBS was found at 77.2 ℃,which was obviously lower than that of PPDO and PBS.Because of the random structure,the crystallization ability of PPBS was low,suggesting that PPBS copolyester had fast degradation rate.This novel alphatic copolyester had great potential in biomedical application due to no metal ions residues.

关 键 词：酶催化 共聚酯 对二氧环己酮 丁二醇 丁二酸二乙酯 

分 类 号：O633.14[理学—高分子化学]