论文总字数：15074字

摘 要

RAFT（Reversible Addition-fragmentation Chain Transfer，可逆加成-断裂链转移）聚合，这是迄今为止，在可逆失活自由基聚合方面国际上应用频率最多的一种技术。对于可逆失活自由基聚合技术而言，涵盖了原子转移自由基聚合（ATRP）、氮氧稳定自由基聚合（NMP）与RAFT聚合等。和前两者比较起来，后者在反应条件与单体方面范围要更宽一些。除此之外，RAFT聚合还拥有着诸如包括实验操作简单，可行性较高，活性可控，末端保真度较高等很多优点，目前已被广泛应用来控制自由基聚合。而在2015年，学者Kotaro Satoh和Masami Kamigaito将RAFT反应机理运用到阳离子聚合中，提出了阳离子RAFT机理。相较于传统自由基聚合，阳离子RAFT聚合显得更加活性可控并且在聚合反应中显示出了极强的控制性。与此同时，由于阳离子RAFT聚合和普通的自由基RAFT聚合机理并不相同，所以阳离子RAFT聚合同时还可以胜任普通自由基聚合无法完成的乙烯基单体例如异丁基乙烯基醚。

本文主要介绍了RAFT聚合的反应机理、阳离子RAFT试剂的选择、阳离子RAFT试剂的合成以及阳离子RAFT聚合的应用等。本文中我们成功合成了RAFT试剂。基于阳离子RAFT试剂被成功地合成，我们进行了阳离子RAFT聚合，得到聚合产物。通过核磁共振氢谱、碳谱以及GPC（凝胶渗透色谱）对聚合物进行表征。实验结果证明对应聚合物的合成，这种RAFT聚合试剂可以有效地控制阳离子RAFT聚合。

关键词：RAFT试剂 阳离子RAFT聚合

RING

ABSTRACT

RAFT (Reversible Addition-fragmentation Chain Transfer) polymerization, which is one of the most widely used reversible deactivated free radical polymerization technologies in the world. Reversible free radicals besides RAFT polymerization The polymerization technique also includes nitrogen-oxygen stable radical polymerization (NMP) and atom transfer radical polymerization (ATRP), but compared to nitrogen-oxygen stable radical polymerization (NMP) and atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer polymerization (RAFT) is applicable to a wider range of monomers and reaction conditions. In addition, RAFT polymerization also has simple experimental procedures, high feasibility, controllable activity and any other advantages, such as higher end fidelity.Now ,RAFT polymerization have been widely used to control free radical polymerization. In 2015, scholars Kotaro Satoh and Masami Kamigaito applied the RAFT reaction mechanism to cationic polymerization, and proposed a cationic RAFT mechanism. Compared to ordinary free radical polymerization and ring-opening polymerization, cationic RAFT polymerization appears to be more active and controllable and shows strong controllability in the polymerization reaction, at the same time, due to cationic RAFT polymerization and ordinary free radical polymerization technologies has different mechanism, so the cationic RAFT polymerization is completely suitable for the vinyl monomer which cannot be produced by ordinary radical polymerization.

This paper mainly introduces the reaction mechanism of RAFT polymerization, the selectivity of cationic RAFT reagent, the synthesis of cationic RAFT reagent and the application of cationic RAFT polymerization. In this paper, we successfully synthesized a reagent and in the second reagent, because one of the intermediate products has no double bond, the transfer rate cannot be measured, which affects the experimental process. After we successfully synthesized this cationic RAFT reagent, we characterized it by 1H NMR and 13C NMR NMR, and then characterized it by means of GPC (gel permeation chromatography). This product is successfully produced,and according ro the reasult of the experiment we can conclude that this RAFT polymerization reagent is very effective in controlling RAFT polymerization.

Keywords: RAFT reagent;cationic RAFT synthesis.

目 录

摘 要 I

ABSTRACT II

第一章 前 言 1

1.1 RAFT聚合 1

1.1.1 什么是RAFT聚合 1

1.1.2 RAFT聚合的组成： 1

1.1.3 RAFT聚合的机理 2

1.2 RAFT试剂选择 3

1.2.1 Z基团的选择 4

1.2.2 RAFT试剂中R基团的选择 4

1.3 阳离子RAFT聚合 5

1.4 RAFT试剂的合成 6

1.4.1 二硫代甲酸盐与烷基化试剂反应 6

1.4.2 通过稀属双键对二硫代酸加成 7

1.4.3 由自由基诱导的双（硫代酰基）二硫化物的分解 7

1.5 阳离子RAFT聚合相较于其他自由基聚合 7

1.6 RAFT聚合的应用 8

1.6.1 智能材料和生物应用 8

1.6.2 应用于嵌段聚合物之中 9

1.7 课题研究的目的和意义 9

1.8 课题采用的研究手段： 10

第二章 实验部分 11

2.1 仪器与试剂 11

2.2 实验试剂的合成 12

2.2.1 试剂产物1的合成 12

2.2.2 试剂产物2,6的合成 12

2.2.3 试剂产物3,7的合成 13

2.2.4 试剂产物5的合成 13

2.3 阳离子RAFT聚合步骤 13

2.4 实验检测及表征方法 14

2.4.1 ¹H NMR 的核磁共振 14

2.4.2 ¹³C NMR 的核磁共振 14

2.4.3 尺寸排阻色谱法（SEC） 14

第三章 结果与讨论 15

3.1 实验结果与讨论 15

3.2 实验结语 17

3.3 实验展望 18

参考文献 19

第一章 前 言

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