Yuan Weizhong, Yuan Jinying, Zhang Fengbo, Xie Xuming
Department of Chemistry, Tsinghua University, Beijing 100084, People's Republic of China.
Biomacromolecules. 2007 Apr;8(4):1101-8. doi: 10.1021/bm0610018. Epub 2007 Feb 28.
Well-defined ethyl cellulose-graft-poly(epsilon-caprolactone) (EC-g-PCL) graft copolymers were successfully synthesized via ring-opening polymerization (ROP) of epsilon-caprolactone (CL) with an ethyl cellulose (EC) initiator and a tin 2-ethylhexanoate (Sn(Oct)2) catalyst in xylene at 120 degrees C. Then, novel ethyl cellulose-graft-poly(epsilon-caprolactone)-block-poly(L-lactide) (EC-g-PCL-b-PLLA) graft-block copolymers were prepared by ROP of L-lactide (L-LA) with a hydroxyl-terminated EC-g-PCL macroinitiator and Sn(Oct)2 catalyst in bulk at 120 degrees C. Various graft and block lengths of EC-g-PCL and EC-g-PCL-b-PLLA copolymers were obtained by adjusting the molar ratios of CL monomer to EC and the L-LA monomer to CL. The thermal properties and crystalline morphologies of EC-g-PCL and EC-g-PCL-b-PLLA copolymers were different from those of linear PCL. The in vitro degradation rate of EC-g-PCL-b-PLLA was faster than those of linear PCL and EC-g-PCL due to the presence of PLLA blocks.
通过在120℃下,以乙基纤维素(EC)为引发剂、2-乙基己酸亚锡(Sn(Oct)2)为催化剂,在二甲苯中引发ε-己内酯(CL)的开环聚合(ROP)反应,成功合成了结构明确的乙基纤维素接枝聚(ε-己内酯)(EC-g-PCL)接枝共聚物。然后,通过在120℃下,以羟基封端的EC-g-PCL大分子引发剂和Sn(Oct)2催化剂,在本体中引发L-丙交酯(L-LA)的ROP反应,制备了新型乙基纤维素接枝聚(ε-己内酯)-嵌段聚(L-丙交酯)(EC-g-PCL-b-PLLA)接枝-嵌段共聚物。通过调整CL单体与EC的摩尔比以及L-LA单体与CL的摩尔比,获得了不同接枝和嵌段长度的EC-g-PCL和EC-g-PCL-b-PLLA共聚物。EC-g-PCL和EC-g-PCL-b-PLLA共聚物的热性能和结晶形态与线性PCL不同。由于存在PLLA嵌段,EC-g-PCL-b-PLLA的体外降解速率比线性PCL和EC-g-PCL更快。