论文总字数：20860字

摘 要

聚偏氟乙烯作为广泛应用的含氟聚合物，不仅耐化学腐蚀性、耐高温性、耐氧化性、耐射线辐射等性能良好，而且在压电、介电、热电性能上也有优异表现。但通常有难溶于水和有机溶剂，结晶度和结晶温度高，疏水性强，熔点较高，润适度和表面强度较低等缺点。故在聚合过程中需对其进行改性，以达到易于加工的目的并增强其漆膜附着力，提高功能和相容性等性能。光诱导聚合在时间和空间控制方面有着独特优势故而越来越受研究人员的重视。光诱导的RDRP在合成定制聚合物、获得性能良好的均聚物和序列控制聚合物等方面也取得了很大进展。本实验主要是通过选取丙烯腈为功能化单体，以P(VDF-co-CTFE)为大分子引发剂进行研究，具体研究以P(VDF-co-CTFE)为大分子引发剂的接枝聚合的效果；考察了Photo-induced ATRP反应的动力学过程，揭示聚合机理。同时考察接枝产物的粘接性能、漆膜附着力等，以应用于太阳能背膜粘接层，拓展有机催化原子转移自由基聚合在制备功能化含氟聚合物中的应用。本文的实验过程分为两个阶段，第一阶段首先配置引发剂溶液，第二阶段合成P(VDF-co-CTFE)-g-PAN接枝共聚物。原料主要有大分子引发剂聚(乙烯基氟乙烯-氯三氟乙烯)(P(VDF-co-CTFE))和单体丙烯酸(AN)，表征技术主要有红外光谱分析、差示扫描量热分析、热分解分析和体积排除色谱分析。由红外光谱分析对结构以及官能团变化以及用核磁共振波谱法进行的表征可预测到，PAN成功接枝到聚合物 P(VDF-co-CTFE)上；由差示扫描量热分析和热分解分析可预测接枝产物的介电性能、储能性能等有所提高。

关键词: 光诱导 接枝改性 RDRP 含氟聚合物

Photoinduced RDRP grafting modified PVDF - based fluoropolymer

Abstract

As a widely used fluorinated polyethylene polymer, the PVDF has not only good chemical corrosion resistance, high temperature resistance, oxidation resistance, weather resistance and β radiation resistance. In addition, it also has properties such as piezoelectric, dielectric and thermoelectric properties. However, defects usually exist, such as low solubility of water and organic solvents, high crystallization and crystallization temperature, high hydrophobicity, high melting point, low humidity and low surface strength.Therefore, in the polymerization process, it needs to be modified to facilitate processing and enhance the adhesion of the varnish layer, and improve performance such as functionality and compatibility.Photoinduced polymerization is more and more popular because of its unique advantages in time and space control.Photoinduced RDRP has also made remarkable progress in the synthesis of customized polymers, homopolymers with high performance and sequence controlled polymers.The main purpose of this experiment is to study the graft polymerization of P (VDF-co-CTFE) as a macromolecular initiator and to select acrylonitrile as a functional monomer. The effect of graft polymerization using P (VDF-co-CTFE) as a macroinitiator was specifically studied; the kinetic process of the Photo-induced ATRP reaction was investigated, and the polymerization mechanism was revealed.At the same time, the adhesive properties of the grafted products, the adhesion of the paint film, etc. were investigated to apply to the solar back film adhesive layer, to expand the application of organic catalytic atom transfer radical polymerization in the preparation of functionalized fluoropolymers.The experimental process in this paper is divided into two stages. In the first stage, the initiator solution is prepared first, and in the second stage, P (VDF-co-CTFE) -g-PAN graft copolymer is synthesized.The raw materials mainly include macromolecular initiator poly (vinyl fluoride-chlorotrifluoroethylene) (P (VDF-co-CTFE)) and monomer acrylic acid (AN),Characterization techniques mainly include infrared spectroscopy, differential scanning calorimetry, thermal thermogravimetric analysiss,nuclear magnetic resonance spectroscopy and size exclusion chromatography.nfrared spectroscopy analysis of structural and functional group changes and characterization by nuclear magnetic resonance spectroscopy can predict the successful grafting of PAN onto polymer P (VDF-co-CTFE);The differential scanning calorimetry analysis and thermal decomposition analysis can predict the improvement of the dielectric properties and energy storage properties of the graft products.

Key Words: photoinduced; graft modification; RDRP; fluoropolymer;

目 录

摘要 Ⅰ

Abstract Ⅱ

第一章 绪论 1

1.1前言 1

1.2聚偏氟乙烯(PVDF)概述 1

1.3丙烯腈概述 3

1.4 PVDF基含氟聚合物的接枝改性 3

1.5本实验研究目的与内容 10

1.5.1研究内容与方法 10

1.5.2研究目的 10

第二章 总体方案设计 11

2.1实验原料与仪器设备 11

2.1.1实验原料 11

2.2.2实验仪器 11

2.2 制备式样 11

2.3性能测试与表征 13

2.3.1傅里叶红外光谱分析(FT-IR) 13

2.3.2核磁共振分析(NMR) 13

2.3.3差示扫描量热分析(DSC) 14

2.3.4 体积排除色谱(SEC) 14

2.3.5热分解分析(TGA) 15

第三章 预测结果与讨论 17

3.1核磁共振氢谱分析(¹H NMR) 17

3.2红外光谱分析（FT-IR） 18

3.3体积排除色谱(SEC) 18

3.4热分解分析(TGA)与差示量热扫描分析(DSC) 19

第四章 预测结论与展望 21

4.1结论 21

4.2展望 21

参考文献 22

致谢 24

绪论

1.1前言

在含氟烯烃中，PVDF有良好的耐辐射性、耐化学腐蚀性、耐氧化性等。不仅如此，聚偏氟乙烯还具有压电、介电和热电性等优异性能，因此广泛应用于诸多领域^[1]。用可控/活性自由基聚合对含氟单体进行改性是一种高效的手段^[2]。目前PVDF在涂料，软质氟树脂Cefral Soft，PVDF纤维，通风系统电缆，半导体加工等方面都有广泛应用，尤其是PVDF超滤膜被广泛用在水处理方面，且效果卓越。PVDF的压电性在光、热、声传感器方面付诸的应用也越来越大^[3]。

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