【作者】 白利斌；

【导师】 巴信武；

【作者基本信息】 河北大学 ， 高分子化学与物理， 2012， 博士

【摘要】 高度支化结构的超支化聚合物由于具有高溶解性、低粘度、高流变性及大量可进一步功能化的官能团等优良性能,因此不管是对其合成还是功能方面的研究都受到了广泛的关注。尽管超支化聚合物的合成方法众多,然而人们从未停止对合成方法的探索,以期得到使用单体范围更广,反应条件更为温和,支化度更高的聚合方法。由于氧化还原法的反应条件温和、且氧化剂简单易得,所以该方法在制备接枝共聚物、嵌段共聚物方面受到了广泛的应用。然而由于氧化还原反应生成初级自由基的速率远远小于自由基的增长速率,导致氧化还原法在超支化合成方面受到了限制。因此,利用氧化还原反应生成自由基,通过可逆加成断裂链转移剂对自由基生长的控制,实现合成超支化聚合物是一个全新的课题。本文的研究主要与氧化还原反应密切相关。通过选择不同的氧化剂、还原性基团以及可逆加成断裂链转移剂,实现初级自由基的生成速率与增长速率相适应,从而制备出超支化聚合物。主要内容如下第一章：绪论。回顾了超支化聚合物的研究现状,并对其发展方向进行了预测。第二章：超支化聚丙烯酰胺的合成及表征。分别选择超常价态过渡金属Cu(Ⅲ)、Ni(Ⅳ)、Ce(Ⅳ)为氧化剂,丙烯酰胺为单体在无氧条件下探讨反应条件对支化度,分子量等物理参数的影响。选择超常价态过渡金属Ce(Ⅳ)为氧化剂,丙烯酰胺为单体在有氧条件下探讨反应条件对支化度,分子量等物理参数的影响。分别选择超常价态过渡金属Ce(Ⅳ)为氧化剂,丙烯酰胺为单体在可逆加成链转移试剂的作用下探讨反应条件对支化度,分子量等物理参数的影响。第三章：根据文献报道合成单烯键糖类,选择超常价态过渡金属Ce(Ⅳ)为氧化剂,在可逆加成链转移试剂的作用下探讨反应条件对支化度,分子量等物理参数的影响。第四章：选择超常价态过渡金属Ce(Ⅳ)为氧化剂,羟甲基丙烯酰胺为单体在可逆加成链转移试剂的作用下探讨反应条件对支化度,分子量等物理参数的影响。第五章：根据文献报道合成可进行乙烯基自缩合的单烯键糖类及可逆加成链转移试剂。更多还原

【Abstract】 Hyperbranched polymers are highly branched macromolecules with three-dimensional dentritic architecture. Due to their unique physical, for example, lower molecular size, lower intrinsic viscosity, lots of terminal groups and a lot of cavitations, interest in hyperbranched polymers is growing rapidly. Although, the synthetic techniques used to prepare hyperbranched polymers have been gradually enriched and ameliorated, using conventional free radical polymerization prepared hyperbranched polymers in a mild condition is an exciting subject. Redox system, such as Cu(III)/-OH, has been demonstrated that those system can high efficiently initiate graft or block copolymerization in a mild condition. Because the polymerization rate is much faster than the redox rate, which will lead to the polymer chain being linear. Thus, using redox system/ reversible addition fragmentation polymerization prepareing hyperbranched polymer is a novel subject.This article is divided into three chapters.In Chapter 1: Introduction. We briefly reviewed the status of hyperbranched polymers, and predicted the direction of their development.In Chapter 2: The synthesis and characterization of hyperbranched polyacrylamide. Cu(III) NI(IV) and Ce(IV) were selected as oxidant, and amide groups were selected as reductive agents.(i) The polymerization was carried out in nitrogen condition. The effects of the redox reaction on the degree of branch, conversion, molecular weight, and value were investigated.(ii) The polymerization was carried out in oxgen condition. The effects of the redox reaction on the degree of branch, conversion, molecular weight, and value were investigated.(iii) The polymerization was carried out using reversible addition fragmentation polymerization. The effects of the redox reaction on the degree of branch, conversion, molecular weight, and value were investigated.In Chapter 3: The synthesis and characterization of hyperbranched Poly(methyl-6-methacryloyl-a- D-glucoside). Ce(IV) were selected as oxidant, and hydroxy groups were selected as reductive agents. The polymerization was carried out using reversible addition fragmentation polymerization. The effects of the redox reaction on the degree of branch, conversion, molecular weight, and value were investigated.In Chapter 4: The synthesis and characterization of hyperbranched poly(N-hydroxymethyl acrylamide). Ce(IV) were selected as oxidant, and amide groups and amide groups were selected as reductive agents. The polymerization was carried out using reversible addition fragmentation polymerization. The effects of the redox reaction on the degree of branch, conversion, molecular weight, and value were investigated.In Chapter 5: According with the reports, the glucose monomer which can be used to prepare hyperbranched polymer via redox/self condensing vinyl polymerization and reversible addition fragmentation transfer agent were synthesized.更多还原