聚己内酯/聚磷酸酯嵌段共聚物的合成及胶束的制备  

Synthesis and Micellization of Poly(E-Caprolactone)/Poly(Ethyl Ethylene Phosphate)Block Copolymer

作　　者：吴秋华[1] 李冬[1] 张丹 宋溪明[1] 刘大亮[1] 张国林[1] 

机构地区：[1]辽宁大学化学院绿色合成与先进材料制备化学辽宁省重点实验室,辽宁沈阳110036 [2]抚顺高新技术产业开发区管理委员会,辽宁抚顺113004

出　　处：《高分子材料科学与工程》2013年第12期22-25,共4页Polymer Materials Science & Engineering

基　　金：辽宁省教育厅创新团队项目(LT2011001);辽宁大学创新人才培养基金资助

摘　　要：以辛酸亚锡为催化剂，N-叔丁氧羰基乙醇胺（Boc．NHCH2CH：OH）为引发剂引发ε-己内酯（ε-CL）开环聚舍制备了端羟基聚己内酯（Boc—PCL—OH），然后用Poe—PCL-OH引发磷酸酯（EEP）单体开环聚合制备了聚己内酯／聚磷酸酯（Poe．PCL—b—PEEP）嵌段共聚物。利用核磁共振（0H—NMR）和凝胶渗透色谱（GPC）对共聚物结构进行了表征。以芘作荧光探针，研究了嵌段共聚物胶束的形成及临界胶束浓度（CMC）），利用动态光散射（DLS）和透射电镜（TEM）分别研究了胶柬的粒径分布和形态。结果表明，POε-NHCH，CH，OH能够引发ε-CL得到Boc—PCL．OH，Poε-PCL．OH能引发EEP开环聚合得到相对分子质量分布在1．08～1．09的嵌段共聚物，在一定条件下嵌段共聚物能够形成单分散的100nm左右的球形胶束，临界胶束浓度（CMC）和胶柬粒径随着PEEP链段的增长而减小。ABSTRACT ：Hydroxyl terminated poly（ε-caprolactone） （Boe-PCL-OH） was prepared by ring-opening polymerization of ε-caprolactone （ε-CL） using N-Boc-ethanolamine （Boc-NHCH2CH2OH） as initiator and stannous octoate as catalyst. Poly （ ε-caprolactone）/poly （ ethyl ethylene phosphate） （Boc-PCL-b-PEEP） block copolymers were synthesized by ring-opening polymerization of ethyl ethylene phosphate （EEP） using Boc-PCL-OH as macroinitiator. The structures of the copolymers were determined by 1H-NMR and GPC analysis. Fluorescence measurements were applied to determine the critical micelle concentration （CMC） of the copolymer micelle solutions. The diameter and the distribution of micelles were characterized by dynamic light scattering （DLS） and the shape was perceived by transmission electron microscopy （TEM）. The results prove that Boc-PCL-OH, which was obtained by the ring opening polymerization of ε-CL with Boc-NHCH2CH2OH as initiator, could initiate the ring opening polymerization of EEP to get block copolymers. Molecular weight distribution of the copolymers is between 1.08--1.09. The copolymers can self-assemble into nano-micelles in aqueous solutions. TEM images demonstrate that all micelles are spherical. Critical micelle concentration（CMC） and the mean diameter of the micells decrease with the increase of the PEEP length.

关 键 词：嵌段共聚物 聚己内酯 聚磷酸酯 胶束 

分 类 号：TQ316.344[化学工程—高聚物工业]