星型聚合物具有支化的分子结构、低的溶液和熔体粘度和丰富的功能。但是，星型聚合物在“改变溶剂质量”的溶液体系中的自组装过程和原理尚未有系统的研究。本申请项目旨在利用高分子/多酸杂化材料作为模型体系来研究星型聚合物的自组装：一、合成与表征一系列多酸基树枝状分子，其中多酸通过共价键连接到聚苄基醚型树枝状分子的末端。二、通过带阳离子端的聚苯乙烯链和这一系列多酸基树枝状分子的静电自组装，制备得到一系列以多酸基树枝状分子为核，以聚苯乙烯为支链的超分子星型聚合物。三、在“改变溶剂质量”的溶液体系中，系统研究这些星型聚合物之内/之间的高分子链段间相互作用和自组装行为。澄清核尺寸、支链分子量、溶剂分子、浓度等对自组装结构的影响，阐释这一系列超分子星型聚合物在“改变溶剂质量”的溶液体系中的自组装规律。这一研究的成功实施将为星型聚合物的实际应用提供重要的实验基础和理论依据。

Star polymers have branched molecular structure, low viscosities in their solution and melt states, and various functionalities. However, the self-assembled process and mechanism of star polymers in solvents of variable quality have not been addressed in detail. In this proposal, polymer/polyoxometalate hydrid materials have been regarded as a model of star polymers to study their self-assembly behaviors. Firstly, a series of poly(polyoxometalate) dendrimers are synthesized and characterized in detail. The polyoxometalates are connected to the periphery of polyaryl ether dendrimers by covalent force. Then, the electrostatic combination of poly(polyoxometalate) dendrimers with cationic terminated poly(styrene) chains yields a series of supramolecular star polymers containing poly(polyoxometalate) dendrimers core and poly(styrene) chains arms. Finally, intra- and inter-star interactions and self-assembled behaviors of star polymers in solvents of variable quality have been studied systematically. And therefore, we will clarify the effect of core size, molecular weight of chains, solvent, concentration on the self-assembly structure, and thus reveal the self-assembled behaviors of supramolecular star polymers in solvents of variable quality. The successful implementation of this research will provide an important experimental foundation and theoretical basis for practical application of star polymers.