论文总字数：18350字

摘 要

氮丙啶是环氧化物的含氮类似物，是现代合成化学中最有价值的三元环系统之一。与发展良好的环氧化物开环聚合（ROP）相反，氮丙啶的ROP限于阳离子机理，其缺点为反应不受控制，并导致支化或超支化的聚（乙烯亚胺）的生成。目前，只有磺酰基活化的氮丙啶可以进行阴离子开环聚合。这是由于磺酰基具有强的吸电子能力，促进开环反应中亲核进攻的发生并抑制链支化。几乎所有N-磺酰基氮丙啶的阴离子开环聚合都被限制在使用金属引发剂，这往往造成金属离子的残留。所以我们需要去探索拓展现有的有机催化剂体系。有机超强碱是最重要的有机催化剂之一，并且通常在质子交换过程中具有良好的动力学活性。强碱性以及低亲核性使得有机超强碱极易将引发剂去质子化得到带负电的引发剂，从而催化N-磺酰基氮丙啶的活性阴离子开环聚合。MTBD作为一种常用的有机碱催化剂，在阴离子开环聚合中具有较好的活性。因此，本文合成了2-甲基-N -对甲苯磺酰基氮丙啶（TsMAZ）单体，采用MTBD作为有机碱催化剂，对以上单体进行阴离子开环聚合，合成聚（2-甲基-N -对甲苯磺酰基氮丙啶）（pTsMAZ）。对所制得的产物使用核磁和SEC进行结构表征。

关键词：MTBD阴离子开环聚合有机超强碱聚（N-磺酰基氮丙啶）

MTBD catalytic functionalized aziridine ring-opening polymerization

Abstract

Aziridine is a nitrogen-containing analogue of epoxides and represents one of the most valuable three-membered ring systems in modern synthetic chemistry. In contrast to the well-developed epoxide ring opening polymerization (ROP), the ROP of aziridine is limited to cationic, with the disadvantage of being uncontrolled and leading to branched or hyperbranched poly(ethyleneimine).So far, only the sulfonyl-activated aziridine can be anionically polymerized because the sulfonyl group has a particularly strong electron-withdrawing ability, promotes nucleophilic ring opening and inhibits chain branching. However, almost all AROPs of N-sulfonyl aziridine are limited to the use of metal initiators, often containing metal ion residues.So we need to explore the catalytic potential of organic catalyst systems. Organic superbase is one of the most important organic catalysts and usually has good kinetic activity during proton exchange.Strong basicity and low nucleophilicity make the organic superbase very promising to obtain deprotonated secondary sulfonamides as initiators for the active AROP of N-sulfonyl aziridine. As a commonly used organic base catalyst, MTBD has good activity in anion ring-opening polymerization.Therefore, we first synthesized 2-methyl-N-toluenesulfonyl aziridine(TsMAZ).Then using MTBD as an organic base catalyst, anion ring-opening polymerization of the monomer respectively.So that the poly(2-methyl-N-p-toluenesulfonyl aziridine) (pTsMAZ) were synthesized.The structures of the TsMAZ and pTsMAZwill be characterized by¹H NMR and SEC.

KeyWords:MTBD; AROPN–sulfonylaziridine; Poly(N–sulfonylaziridine)

目 录

摘要 Ⅰ

Abstract Ⅱ

第一章 绪论 1

1.1前言 1

1.2 氮丙啶阳离子开环聚合机理 2

1.3氮丙啶阴离子开环聚合 2

1.3.1 背景 2

1.3.2机理 3

1.4有机碱催化剂 4

1.5本文的研究目的及内容 4

第二章 2-甲基-N -对甲苯磺酰基氮丙啶的合成 5

2.1反应原理 5

2.2实验材料 5

2.2.1实验试剂 5

2.2.2实验仪器 6

2.3实验装置 6

2.4实验方法 6

2.5实验结果与讨论 7

第三章 聚（2-甲基-N -对甲苯磺酰基氮丙啶）的合成 9

3.2实验材料 9

3.2.1实验试剂 9

3.2.2实验仪器 9

3.3实验装置图 10

3.4实验方法 10

3.5实验结果与讨论 10

第四章 结论与展望 14

4.1结论 14

4.2展望 14

参考文献 16

致 谢 19

第一章 绪论

请支付后下载全文，论文总字数：18350字