新型结构的聚（γ-苄基-L-谷氨酸）-b-聚环氧乙烷-b-聚己内酯三嵌段共聚物的合成

Synthesis of a novel structural triblock copolymer of poly(gamma -benzyl-l-glutamic acid)-b-poly(ethylene oxide)-b-poly(epsilon-caprolactone).

作者信息

Deng Mingxiao, Wang Rong, Rong Guangzhuo, Sun Jingru, Zhang Xuefei, Chen Xuesi, Jing Xiabin

机构信息

State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022, PR China.

出版信息

Biomaterials. 2004 Aug;25(17):3553-8. doi: 10.1016/j.biomaterials.2003.10.018.

DOI:10.1016/j.biomaterials.2003.10.018

PMID:15020129

Abstract

A novel structural triblock copolymer of poly(gamma-benzyl-l-glutamic acid)-b-poly(ethylene oxide)-b-poly(epsilon-caprolactone) (PBLG-PEO-PCL) was synthesized by a new approach in the following three steps: (1) sequential anionic ring opening polymerization (ROP) of ethylene oxide and epsilon-caprolactone with an acetonitrile/potassium naphthalene initiator system to obtain a diblock copolymer CN-PEO-PCL with a cyano end-group; (2) conversion of the CN end-group into NH2 end-group by hydrogenation to obtain NH2-PEO-PCL; (3) ROP of gamma-benzyl-l-glutamate-N-carboxyanhydrides (Bz-l-GluNCA) with NH2-PEO-PCL as macroinitiator to obtain the target triblock copolymer. The structures from CN-PEO precursor to the triblock copolymers were confirmed by FT-IR and 1H NMR spectroscopy, and their molecular weights were measured by gel permeation chromatography. The monomer of Bz-l-GluNCA can react almost quantitatively with the amino end-groups of NH2-PEO-PCL macroinitiator by ROP.

摘要

通过一种新方法分三步合成了一种新型结构的聚（γ-苄基-L-谷氨酸）-b-聚环氧乙烷-b-聚己内酯（PBLG-PEO-PCL）三嵌段共聚物：（1）使用乙腈/萘钾引发剂体系对环氧乙烷和己内酯进行顺序阴离子开环聚合（ROP），以获得具有氰基端基的二嵌段共聚物CN-PEO-PCL；（2）通过氢化将CN端基转化为NH2端基，得到NH2-PEO-PCL；（3）以NH2-PEO-PCL作为大分子引发剂对γ-苄基-L-谷氨酸-N-羧酸酐（Bz-l-GluNCA）进行ROP，以获得目标三嵌段共聚物。通过傅里叶变换红外光谱（FT-IR）和1H核磁共振光谱（1H NMR）对从CN-PEO前体到三嵌段共聚物的结构进行了确认，并通过凝胶渗透色谱法测量了它们的分子量。Bz-l-GluNCA单体可以通过ROP与NH2-PEO-PCL大分子引发剂的氨基端基几乎定量地反应。