Synthesis and Micellization Properties of Double Hydrophilic A2BA2 and A4BA4 Non-Linear Block Copolymers
Synthesis and Micellization Properties of Double Hydrophilic A2BA2 and A4BA4 Non-Linear Block Copolymers
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DOI：
10.1021/ma061934w
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发表时间：
2006-10
期刊：
影响因子：
5.5
通讯作者：
Jian Xu;Zhishen Ge;Zhiyuan Zhu;Shi-zhong Luo;Hewen Liu;Shiyong Liu
中科院分区：
文献类型：
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作者：
Jian Xu;Zhishen Ge;Zhiyuan Zhu;Shi-zhong Luo;Hewen Liu;Shiyong Liu
我们描述了第一个帐户的合成和有趣的胶束化性能的非线性双亲水性嵌段共聚物（DHBCs）的A2 BA 2和A4 BA 4类型。以丙烯酸羟乙酯和缩水甘油为引发剂，分别与市售的端二胺型聚环氧丙烷（PPO）反应，然后与过量的2-溴异丁酰溴或2-溴丙酰溴酯化，合成了两个和四个引发位点的大分子引发剂。然后通过使用制备的大分子引发剂在40 ℃下在2-丙醇中经由ATRP聚合甲基丙烯酸2-（二乙基氨基）乙酯（DEA）来制备定义明确的非线性DHBC，（PDEA）2 PPO（PDEA）2（H形）和（PDEA）4PPO（PDEA）4（星形-b-线性-b-星星），其中PDEA是聚（甲基丙烯酸2-（二乙基氨基）乙酯）。用1H NMR和凝胶渗透色谱（GPC）对所得非线性共聚物的结构进行了表征。采用动态激光光散射（LLS）和荧光技术研究了（PDEA 10）2 PPO（PDEA 10）2和（PDEA 11）4PPO-（PDEA 11）4的pH和温度响应性胶束化行为。与线性嵌段共聚物相比，非线性嵌段共聚物表现出复杂而有趣的胶束化性质。
We describe the first account of the synthesis and intriguing micellization properties of nonlinear double hydrophilic block copolymers (DHBCs) of the A2BA2 and A4BA4 type. Atom transfer radical polymerization (ATRP) macroinitiators with two and four initiating sites at both ends of poly(propylene oxide) (PPO) chain were synthesized via reacting 2-hydroxyethyl acrylate and glycidol with commercially available diamine-terminated PPO, respectively, followed by esterification with excess 2-bromoisobutyryl bromide or 2-bromopropionyl bromide. Well-defined nonlinear DHBCs, (PDEA)2PPO(PDEA)2 (H-shaped) and (PDEA)4PPO(PDEA)4 (star-b-linear-b- star), were then prepared by polymerizing 2-(diethylamino)ethyl methacrylate (DEA) via ATRP in 2-propanol at 40 °C using the prepared macroinitiators, where PDEA was poly(2-(diethylamino)ethyl methacrylate). The structures of the resulting nonlinear shaped copolymers were characterized by 1 H NMR and gel permeation chromatography (GPC). The pH- and thermoresponsive micellization behavior of (PDEA10)2PPO(PDEA10)2 and (PDEA11)4PPO- (PDEA11)4 was then investigated by a combination of dynamic laser light scattering (LLS) and fluorescence techniques. Compared to the linear counterpart, the nonlinear block copolymers exhibited complex and interesting micellization properties.