锌、铝配合物的合成、表征及催化环酯开环聚合
发布时间：2018-12-08 08:32
【摘要】：脂肪族聚酯如聚己内酯(PCL)、聚丙交酯(PLA)、聚丁内酯(PHB)及其共聚物,因具有良好的生物相容性、生物降解性和渗透性而被广泛应用于生物、医药、材料领域,金属催化环酯开环聚合是合成这些聚合物的有效方法。单活性位点催化剂因其在酯开环聚合中良好的反应活性和可控性得到了广泛的研究,可以从链末端机理和活性基团控制机理阐述具体的聚合过程。可以通过精心设计配体、选择中心金属、引发剂从而精确调控聚合速率、聚合物分子量、聚合物分子量分布以及聚合的立构选择性。第一章阐述可降解脂肪族聚酯研究背景,环酯单体开环聚合的机理研究,重点介绍丙交酯的选择性聚合,并详细介绍了各种开环聚合的金属催化体系。第二章描述一系列卡宾配位的锌配合物的合成、表征及其对外消旋丙交酯(rac-LA)开环聚合的催化作用。在苄醇的存在下,所有的锌催化剂都能够有效地催化外消旋丙交酯开环聚合,聚合物的分子量可控,分子量分布窄,聚合反应有活性聚合的特征。第三章介绍了含氮杂环卡宾的C,N,O-三齿配体稳定的锌配合物的合成、表征及其对rac-LA开环聚合的催化作用。催化剂具有高活性、可控性好的特征。第四章介绍了含吡咯基配体([2-{5-R'2NCH2(C4H2N)}]2CR2)配位的双核和三核锌配合物的合成、表征及催化研究。配体的取代基位阻决定配合物的结构,当R为乙基时得到三核锌配合物,当R为芳基如苯基和1,1'-联苯-2,2'-二取代基时,产生双核配合物。三核锌配合物不稳定,实际引发聚合过程的活性物种较复杂,聚合可控性较差,动力学实验表明聚合对单体的浓度既不是一级也不是二级反应。相同条件下双核锌的催化活性和可控性都较好,聚合对单体的浓度是一级反应。第五章介绍了含邻菲罗啉配体配位的N,N,O-三齿铝配合物的合成、表征及催化环酯开环聚合作用研究。在苄醇的存在下,该催化体系能有效催化ε-己内酯、rac-丙交酯、β-丁内酯开环聚合。配体上取代基对聚合活性有显著影响,该催化体系能有效地催化ε-CL开环聚合,所得聚合物的分子量可控,分子量分布窄。丙交酯开环聚合得到等规倾向的PLA,动力学研究揭示聚合对于单体浓度和催化剂浓度都是一级反应。聚合丁内酯,可控性较差,得到无规聚合物。利用聚合反应的活性特征也得到一些嵌段聚合物。
[Abstract]:Aliphatic polyester, such as polycaprolactone (PCL), polylactide (PLA), polybutyllactone (PHB) and its copolymers, have been widely used in the fields of biology, medicine and materials because of their good biocompatibility, biodegradability and permeability. Metal-catalyzed ring-opening polymerization of cycloesters is an effective method for the synthesis of these polymers. Single active site catalyst has been widely studied for its good reaction activity and controllability in the ring-opening polymerization of ester. The polymerization process can be explained from the chain end mechanism and the active group control mechanism. The polymerization rate, molecular weight distribution and structural selectivity of polymers can be precisely regulated by carefully designed ligands, selection of central metals and initiators. In the first chapter, the research background of degradable aliphatic polyester, the mechanism of ring opening polymerization of cycloester monomer, the selective polymerization of lactide and the metal catalytic system of ring opening polymerization are introduced in detail. Chapter 2 describes the synthesis and characterization of a series of carbine-coordinated zinc complexes and their catalytic effects on ring-opening polymerization of racemic lactide (rac-LA). In the presence of benzyl alcohol, all zinc catalysts can effectively catalyze the ring-opening polymerization of racemic lactide, the molecular weight of the polymer is controllable, the molecular weight distribution is narrow, and the polymerization has the characteristics of active polymerization. In chapter 3, the synthesis, characterization and catalytic effect of C ~ (2 +) N _ (10) O ~ (3 +) -tridentate ligand stabilized zinc complex on rac-LA ring opening polymerization were introduced. The catalyst has the characteristics of high activity and good controllability. In chapter 4, the synthesis, characterization and catalytic study of binuclear and trinuclear zinc complexes with pyrrole ligand ([2- {5-R'2NCH2 (C4H2N)}] 2CR2) were introduced. The structure of the complexes is determined by the substituent steric hindrance of ligands. The trinuclear zinc complexes are obtained when R is ethyl, and binuclear complexes are produced when R is aryl such as phenyls and 1tau-1, biphenyls, 2o 2o 2 or disubstituted groups. The complex of trinuclear zinc complex is unstable, the active species that actually initiated the polymerization process are more complex, and the polymerization controllability is poor. The kinetic experiments show that the polymerization concentration to the monomer is neither a first-order nor a second-order reaction. The catalytic activity and controllability of binuclear zinc were good under the same conditions, and the concentration of monomers was the first order reaction. In chapter 5, the synthesis, characterization and catalytic ring-opening polymerization of ring opening polymerization of cycloester were studied. In the presence of benzyl alcohol, the system can effectively catalyze the ring-opening polymerization of 蔚 -caprolactone, rac- lactide and 尾 -butyrolactone. The ligand substituents have a significant effect on the polymerization activity. The catalyst system can effectively catalyze the ring-opening polymerization of 蔚-CL. The molecular weight of the obtained polymer is controllable and the molecular weight distribution is narrow. The PLA, kinetic study of isotactic tendency obtained by ring-opening polymerization of lactide shows that the polymerization is a first-order reaction for monomer concentration and catalyst concentration. Polymerization of butyrolactone, poor controllability, a random polymer. Some block polymers were also obtained by using the active characteristics of the polymerization reaction.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O643.36;O631.5
本文编号：2368042
[Abstract]:Aliphatic polyester, such as polycaprolactone (PCL), polylactide (PLA), polybutyllactone (PHB) and its copolymers, have been widely used in the fields of biology, medicine and materials because of their good biocompatibility, biodegradability and permeability. Metal-catalyzed ring-opening polymerization of cycloesters is an effective method for the synthesis of these polymers. Single active site catalyst has been widely studied for its good reaction activity and controllability in the ring-opening polymerization of ester. The polymerization process can be explained from the chain end mechanism and the active group control mechanism. The polymerization rate, molecular weight distribution and structural selectivity of polymers can be precisely regulated by carefully designed ligands, selection of central metals and initiators. In the first chapter, the research background of degradable aliphatic polyester, the mechanism of ring opening polymerization of cycloester monomer, the selective polymerization of lactide and the metal catalytic system of ring opening polymerization are introduced in detail. Chapter 2 describes the synthesis and characterization of a series of carbine-coordinated zinc complexes and their catalytic effects on ring-opening polymerization of racemic lactide (rac-LA). In the presence of benzyl alcohol, all zinc catalysts can effectively catalyze the ring-opening polymerization of racemic lactide, the molecular weight of the polymer is controllable, the molecular weight distribution is narrow, and the polymerization has the characteristics of active polymerization. In chapter 3, the synthesis, characterization and catalytic effect of C ~ (2 +) N _ (10) O ~ (3 +) -tridentate ligand stabilized zinc complex on rac-LA ring opening polymerization were introduced. The catalyst has the characteristics of high activity and good controllability. In chapter 4, the synthesis, characterization and catalytic study of binuclear and trinuclear zinc complexes with pyrrole ligand ([2- {5-R'2NCH2 (C4H2N)}] 2CR2) were introduced. The structure of the complexes is determined by the substituent steric hindrance of ligands. The trinuclear zinc complexes are obtained when R is ethyl, and binuclear complexes are produced when R is aryl such as phenyls and 1tau-1, biphenyls, 2o 2o 2 or disubstituted groups. The complex of trinuclear zinc complex is unstable, the active species that actually initiated the polymerization process are more complex, and the polymerization controllability is poor. The kinetic experiments show that the polymerization concentration to the monomer is neither a first-order nor a second-order reaction. The catalytic activity and controllability of binuclear zinc were good under the same conditions, and the concentration of monomers was the first order reaction. In chapter 5, the synthesis, characterization and catalytic ring-opening polymerization of ring opening polymerization of cycloester were studied. In the presence of benzyl alcohol, the system can effectively catalyze the ring-opening polymerization of 蔚 -caprolactone, rac- lactide and 尾 -butyrolactone. The ligand substituents have a significant effect on the polymerization activity. The catalyst system can effectively catalyze the ring-opening polymerization of 蔚-CL. The molecular weight of the obtained polymer is controllable and the molecular weight distribution is narrow. The PLA, kinetic study of isotactic tendency obtained by ring-opening polymerization of lactide shows that the polymerization is a first-order reaction for monomer concentration and catalyst concentration. Polymerization of butyrolactone, poor controllability, a random polymer. Some block polymers were also obtained by using the active characteristics of the polymerization reaction.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O643.36;O631.5
【参考文献】
相关博士学位论文 前3条
1 麻文安;铝、锌、锡配合物的合成、表征及催化环酯开环聚合[D];中国科学技术大学;2011年
2 张成;铝、锌、钴、镍络合物的合成及催化作用研究[D];中国科学技术大学;2008年
3 齐春艳;含新型膦亚胺配体的锂、镁、铝、锡（Ⅱ）和锌化合物的合成、表征及其催化环酯开环聚合研究[D];中国科学技术大学;2006年
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