超支化聚合物的合成和自组装研究  

Synthesis and Self-assembly of Hyperbranched Polymers

作　　者：戚美微[1] 黄卫[1] 肖谷雨[1] 朱新远[1] 高超[2] 周永丰[1] Mei-wei Qi Wei Huang Gu-yu Xiao Xin-yuan Zhu Chao Gao Yong-feng Zhou(School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240 Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027)

机构地区：[1]上海交通大学化学化工学院,上海200240 [2]浙江大学高分子科学与工程系,杭州310027

出　　处：《高分子学报》2017年第2期214-228,共15页Acta Polymerica Sinica

基　　金：国家重点基础研究发展计划(973计划;项目号2013CB834506);国家杰出青年科学基金(基金号21225420);国家自然科学基金(基金号21404070;91527304)资助项目

摘　　要：超支化聚合物作为树形聚合物的一种,具有独特的结构和性能,受到了科学界和工业界的广泛关注.本文简要总结了研究者们在超支化聚合物的合成、组装及应用方面的部分工作成果.主要包括以下3方面的内容:第一部分介绍了超支化聚合物的合成方法;第二部分介绍了超支化聚合物多维多尺度的自组装结构和组装机理,包括纳米球形胶束,纳米、微米级囊泡,大的复合囊泡,纳米纤维,纳米、微米及宏观管和多孔膜等;第三部分介绍了超支化聚合物在生物医药、细胞模拟及纳米粒子模拟制备等方面的应用.Hyperbranched polymers（HBPs）, comprising of dendritic units, linear units and terminal units, are highly branched macromolecules with three-dimensional dendritic globular architecture. Compared with linear polymers, HBPs have shown the characteristics of a large population of terminal functional groups, low or no chain entanglement, small hydrodynamic diameter, low solution or melt viscosity and good solubility. Due to these characteristics, HBPs have attracted global interest from science to industry. In this paper, we review some progress in the synthesis, self-assembly and application of HBPs. The paper includes three parts. In the first part, a short history on the development of HBPs focusing on the introduction of ＂couple-monomer methodology（CMM）＂ to prepare HBPs was discussed. A typical example of CMM named as ＂AA, ＋ B,B2＂ method was described. In addition, the synthesis of a hyperbranched oxetanemethanol through ring-opening polymerization was also presented. In the second part, the self-assembly of amphiphilic HBPs was summarized according to the morphology of the self-assemblies from the spherical micelles, the vesicles, the sheets or films, the fibers or tubes, to complex supramolecular structures. The mechanism for the self-assembly of the micelles from HBPs was discussed in details. HBPs form unimolecular micelles（UMs） around 10 nm below the critical micellar concentration（CMC）. Above the CMC, there are two possibilities for the formation of micelles： one is that HBPs undergo microphase separation and then form micelles with the diameter of the length of two HBPs（around 20 nm or larger）, which is named as ＂microphase-separated small micelles＂（ms-SMs） and similar to the star micelles of linear block copolymers in structure; the other is that HBPs form multimolecular micelles（ 50 nm） through a mechanism of ＂multimicelle aggregate＂（MMA）. The MMA mechanism can also be divided into two mechanisms of ＂unimolecular micelle aggregate＂（UMA） and ＂sm

关 键 词：超支化聚合物 自组装 药物传输 胶束 囊泡 

分 类 号：O631[理学—高分子化学]