Basic and Applicative Studies on Controlled Radical Polymerization

[I]可控自由基聚合反应机理与动力学本文对可控自由基聚合反应机理和动力学进行了系统的理论和实验研究。主要结果包括：（1）建立了两种测定CRPs活化速率常数的通用GPC方法。(2)将GPC方法应用于各种CRP体系，建立了活化速率常数和活化机理。特别是，它被证实，热分解的氮氧自由基系统，交换链转移的PS-I和PS-SCSMe系统，和溴/CuBr系统的原子转移几乎是唯一的机制激活各自的系统。(3)[II]通过CRP精确合成新的聚合物材料（1）首次合成了具有明确结构的低多分散性共聚物（无规、嵌段、聚合大分子单体）和均聚物（带有葡萄糖残基的苯乙烯类、丙烯酸酯类和甲基丙烯酸酯类、富勒烯封端的聚合物）。(2)首次制备了结构比常规凝胶均匀得多的聚合物凝胶。(3)首次成功地制备了具有可控链长和链长分布的聚合物刷，并将其致密地接枝到硅片上。

[I] Mechanisms and Kinetics of Controlled Radical PolymerizationsThe mechanisms and kinetics of variants of controlled radical polymerization (CRP) were experimentally and theoretically studied and systematized. Main results include :(1) Two general GPC methods for determining the rate constants of activation in CRPs were established.(2) The GPC methods were applied to various CRP systems, and the activation rate constants and activation mechanism were established. In particular, it was confirmed that the thermal dissociation for the nitroxide system, the exchanging chain transfer for the PS-I and PS-SCSMe systems, and the atom transfer for the bromide/CuBr system are virtually the only mechanism of activation for the respective systems.(3) A general equation describing the polymerization rates of CRP systems was developed and partly confirmed by experiments[II] Precision Synthesis of New Polymer Materials by CRPs(1) Low-polydispersity copolymers (randoms, blocks, polymacromonomers) and homopolymers (glucose residue-carrying styrenics, acrylates and methacrylates, fullerene-terminated polymers) with well-defined structure were synthesized mostly for the first time.(2) Polymer gels, structurally much more homogeneous than conventional ones, were prepared for the first time.(3) Polymer brushes with controlled chain length and chain length distribution, densely grafted on a silicon wafer, were successfully prepared for the first time.