论文总字数：25349字

摘 要

单电子转移活性自由基聚合（SET-LRP）是近年来发展的一类新型活性自由基聚合技术。SET-LRP由于具有反应条件温和，催化剂用量低且不受含氮溶剂及配体的限制等优势，引起了越来越多的研究兴趣。

本实验通过单电子转移活性自由基聚合（SET-LRP）机理，以聚偏氟乙烯-三氟氯乙烯（P(VDF-CTFE)）作为大分子引发剂，零价铜Cu(0)作为催化剂，三（2-二甲氨基乙基）胺（Me-TREN）作为配体，二甲基亚砜（DMSO）作为溶剂，丙烯晴AN作为单体，在常温合成了P(VDF-CTFE)-g-PAN接枝共聚物。分别利用红外吸收光谱（FT-IR）、核磁共振氢谱（¹H-NMR）以及差示扫描量热法（DSC）对产物进行了表征，证实了接枝结构的成功构筑。同时考察了反应条件（不同反应温度，催化剂浓度，以及配体含量）对聚合反应速率的影响。研究发现，随着反应温度的升高（30 ^oC、40 ^oC、50 ^oC），接枝聚合反应速率显著加快；在相同反应温度下，降低催化剂的浓度(由[I]:[C]:[M]=1:0.25:20降至[I]:[C]:[M]=1:0.125:20)，接枝速率保持不变，进一步降低催化剂浓度(由[I]:[C]:[M]=1:0.125:20降至[I]:[C]:[M]=1:0.06:20)，接枝速率大幅下降；改变配体的含量，对反应速率的影响不显著。

研究结果表明，通过SET-LRP可以成功的对P(VDF-CTFE)进行接枝改性，通过改变反应条件，可以对反应速率以及产物的接枝量进行调控。相较于传统原子转移自由基聚合（ATRP），SET-LRP可以大幅降低催化剂的用量，使最终产物中的金属残留量大幅降低。

关键字：SET-LRP、氟聚物、丙烯晴、接枝共聚物、P(VDF-CTFE)-g-PAN

Preparation of PVDF-g-PAN by SET-LRP

ABSTRACT

Single-Electron Transfer mediated Living Radical Polymerization (SET-LRP) is one of the most versatile tools in preparing functional polymer. Due to the mild reaction conditions, low catalyst consumption and no nitrogen containing solvents and ligands, SET-LRP has attracted more and more research interests.

In this experiment, Poly(vinylidene fluoride-chlorotrifluor ethylene)-graft-acrylonitrile P(VDF-CTFE)-g-PAN graft copolymer was successfully synthesized via SET-LRP process initiated by P(VDF-CTFE) as macroinitiator in the presence of trace amount Cu(0)/ tris(2(dimethylamino)ethyl)amine (Me₆-TREN) in dimethyl sulfoxide (DMSO) at ambient temperature. The typical side reactions happened on P(VDF-CTFE) in atom transfer radical polymerization process could be avoided in SET–LRP process by using the mild reaction conditions. Well-controlled polymerization features were observed under varied reaction conditions including the different reaction temperature, catalyst concentration, as well as ligand amount in feed. The influences of reaction conditions (different reaction temperature, catalyst concentration, and ligand concentration) on the polymerization rate were also carefully investigated. It was found that the polymerization rate of the graft polymerization was significantly accelerated with the elevating of the reaction temperature. The polymerization rated exhibit little change by reducing the catalyst concentration (from[I]:[C]:[M]=1:0.25:20 to I]:[C]:[M]=1:0.125:20), which dropped by sharply decrease the concentration of catalyst (from[I]:[C]:[M]=1:0.125:20 to [I]:[C]:[M]=1:0.06:20) The products were characterized by infrared absorption spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (H-NMR) and differential scanning calorimetry (DSC), which confirmed the successful construction of the graft structure.

The results show that the grafting modification of P (VDF-CTFE) can be successfully carried out by SET-LRP, by changing the reaction conditions, the reaction rate and the grafting amount of the product can be controlled. Compared to conventional atom transfer radical polymerization (ATRP), SET-LRP can significantly reduce the amount of catalyst, so that the final product of the metal residues in a significant reduction.

KEY WORDS: SET-LRP、Fluorine polymer、acrylonitrile、graft copolymer、P(VDF-CTFE)-g-PAN

目录

摘要 I

ABSTRACT II

第一章 文献综述 1

1.1 活性自由基聚合 1

1.1.1 活性自由基聚合的产生背景 1

1.1.2 活性自由基聚合的分类 1

1.2 单电子转移活性自由基聚合（SET-LRP） 2

1.2.1 SET-LRP的现状 2

1.2.2 SET-LRP的反应体系 2

1.3 PVDF基含氟聚合物 3

1.3.1 PVDF基含氟聚合物的结构特点 3

1.3.2 PVDF基含氟聚合物的发展现状 3

1.3.3 PVDF基含氟聚合物的应用及前景 4

1.3.4 PVDF基含氟聚合物的改性 4

1.4 本课题的研究背景、目的以及内容 4

1.4.1 研究背景 4

1.4.2 研究目的 5

1.4.3 研究内容 5

第二章 SET-LRP接枝改性PVDF基含氟聚合物 6

2.1 引言 6

2.2 实验试剂和仪器 7

2.3 样品的制备 8

2.3.1 P(VDF-CTFE)-g-PAN的制备 8

2.3.2 温度变量实验 9

2.3.3 催化剂变量实验 10

2.3.4 配体变量实验 11

2.4 试样表征 11

2.4.1 核磁共振表征 11

2.4.2 傅里叶红外光谱表征 12

2.4.3 差示扫描量热分析表征 13

第三章 反应条件对聚合反应速率的影响 15

3.1 反应温度对接枝反应速率的影响 15

3.2 相同反应温度下催化剂含量对接枝反应速率的影响 17

3.3 相同反应温度下配体含量对接枝反应速率的影响 18

第四章 结论与展望 21

致谢 22

参考文献 23

第一章 文献综述

1.1 活性自由基聚合

1.1.1 活性自由基聚合的产生背景

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