Basic and Applicative Studies on Controlled Radical Polymerization

[1]可控自由基聚合的机理和动力学本文从实验和理论两方面对可控自由基聚合（CRP）变体的机理和动力学进行了系统的研究。主要结果包括：(1)建立了两种通用的GPC方法来确定CRPs的活化速率常数。(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。特别地，证实了氮氧化物体系的热解离，PS-I和PS-SCSMe体系的交换链转移以及溴/CuBr体系的原子转移实际上是各自体系的唯一激活机制。(3)建立了描述CRP体系聚合速率的一般方程，并通过实验得到了部分证实[II]：用CRP精密合成新型高分子材料。(1)结构明确的低聚分散共聚物（无规共聚物、嵌段共聚物、高分子单体）和均聚聚合物（含葡萄糖残基苯乙烯类、丙烯酸酯类、甲基丙烯酸酯类、端富勒烯类聚合物）大部分是首次合成。(2)首次制备了结构均匀性优于常规聚合物的聚合物凝胶。(3)首次成功制备出链长可控、链长分布可控的聚合物刷，并将其密集接枝在硅片上。

[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.