新型不饱和聚磷酸酯的易位合成及交联与杂化纳米结构的研究

In the view of the status of international academic research on unsaturated polyphosphoesters via acyclic diene metathesis (ADMET) polymerization has just started, but has not yet carried out in the domestic. From the excellent comprehensive performance of polyphosphoester itself, we proposed the idea of this topic, and would carry out the fundamental studies about the synthesis of functional polymers with different topologies via ADMET polymerization. The research will reveal the mutual relationship between the topological structure of polymer and enhance the functionality from four aspects, as synthesis of functional diene monomers, the investigation of ADMET polymerization reaction and kinetics, the study on synthesis and propertyies of different structure polyphosphoester, and the construction, morphologies and propertyies of crosslinked unimolecular functional polymer nanoparticles and hybrid nanomaterials. Optimizing combinations of the components in reaction system and reaction conditions, a series of functional unsaturated polyphosphoesters would be obtained. On this basis, the effective functionalization of unsaturated polyphosphaters by a controlled intramolecular crosslinking process, to form finially unimolecular functional polymer nanoparticles and hybrid nanomaterials with high stability. The study is expected to perfect ADMET polymerization method, improve the structures, morphologies and properties of metathesis polymer, enrich research content of metathesis polymers, and exploit application field of polymeric material. It has the high academic value and strongly applied prospect for developing the researched new field in olefin metathesis polymerization.

鉴于国际上对不饱和聚磷酸酯易位合成的学术研究刚刚起步而国内尚未开展的现状，从聚磷酸酯本身拥有优良的综合性能出发，拟开展关于ADMET聚合合成不同拓扑结构的功能性易位聚合物的基础研究。从多功能二烯烃单体合成、ADMET聚合反应与动力学考察、不同结构聚磷酸酯的易位合成与性能研究、交联的单分子易位聚合物纳米颗粒及其杂化纳米材料的构建、形态和性能四个方面，揭示易位聚合物的拓扑结构与增强功能性之间的相互关系；通过优化反应体系各组分的搭配和反应条件，获得一类新型功能性不饱和聚磷酸酯；在此基础上，对不饱和聚磷酸酯有效的功能化，开展分子内交联反应的研究，制备单分子易位聚合物纳米颗粒，同时赋予纳米颗粒新的功能性，进一步合成稳定的杂化纳米材料。本课题旨在完善ADMET聚合方法，改善易位聚合物的结构、形态和性能，丰富易位聚合物的研究内容，开拓易位聚合材料的应用领域，具有重要的学术价值和应用前景。

该项目基于聚磷酸酯本身优良的综合性能和非环二烯烃易位（ADMET）聚合反应，进行探索和创新研究。设计合成了三种不同电子效应的、含磷酸酯功能基的二烯烃单体，对其在不同反应条件下的ADMET（共）聚合反应进行系统研究，全面揭示反应条件、单体性质和烯烃电子种类等因素对聚合反应的影响、反应宏观动力学和微观特征等基本规律。经过积极探索，成功地实现了利用烯烃易位聚合反应制备嵌段、交替等线性共聚物和刷形、星形、支化、环状、梯形、桥状等非线性聚合物，研究聚合物的拓扑结构与增强功能性之间的相互关系。在此基础上制备了含丙烯酸酯和巯基的分子内交联聚合物纳米颗粒，与金纳米粒子进一步合成了稳定的杂化纳米材料，研究纳米结构的形态和性能。该项目完善了ADMET聚合方法，改善了易位聚合物的结构、形态和性能，丰富了易位聚合物的研究内容，开拓了易位聚合材料的应用领域。