Zn^(2+)-光预聚丙烯酸酯弹性体的配位机理及其力学性能研究  

Research on Metal-ligand Mechanism and Mechanical Properties of Zn^(2+)-UV Precuring Acrylate Elastomer

作　　者：蔡永祺 梅启林[1] 姜端洋 徐建蓉 高琳沁 丁国民 CAI Yong-qi;MEI Qi-lin;JIANG Duan-yang;XU Jian-rong;GAO Lin-qin;DING Guo-min(School of Materials Science and Engineering,Wuhan University of Technology,Wuhan 430070,China)

机构地区：[1]武汉理工大学材料科学与工程学院,武汉430070

出　　处：《高分子通报》2024年第11期1608-1619,共12页Polymer Bulletin

基　　金：湖北省自然科学基金面上项目(基金号2022CFB384);国家自然科学基金(基金号52003120);武汉理工大学自主创新研究基金(基金号2022IVA004)。

摘　　要：为了同时提高聚丙烯酸酯弹性体的强度和变形能力,通过光预聚工艺制备了不同黏度的液态丙烯酸酯树脂,使用过氧化苯甲酰(benzoyl peroxide,BPO)和N,N-二甲基苯胺(N,N-dimethylaniline,DMA)作为固化体系并提供配位原子与锌离子(Zn^(2+))产生金属配位键,增加分子链间的相互作用以提高聚合物的力学性能。研究发现在固化过程中树脂由淡黄色变为紫色,固化完全后最终变为绿色。深入探究了此体系颜色变化的原因,进而揭示Zn^(2+)与聚合物分子链的配合机理:Zn^(2+)同时与DMA中的N原子和BPO中的O原子产生配位键,当N、O上带有自由基时体系表现出紫色,无自由基时则表现为绿色。基于以上配位机理,Zn^(2+)与分子链产生的配位键位于链端,极大地提高了弹性体的断裂伸长率,使制备的金属配位丙烯酸酯弹性体的断裂伸长率可从基体的630%提升至7400%。基于金属配位键的弱键特点,研究发现适当的热处理可调节配位键的数量,经过150℃加热处理后,相比于无配位体系,Zn^(2+)配位丙烯酸酯弹性体的拉伸强度提高了28.6%,并且断裂伸长率提高了39.3%,即可同时提升弹性体的强度和变形能力。该研究为金属配位丙烯酸酯弹性体、高延伸丙烯酸酯弹性体的制备提供新思路,制备的弹性体可作为密封件、柔性传感器基体等在对材料的延展率有高要求的应用场景下使用。In order to improve the strength and deformation of acrylate elastomer simultaneously,the liquid acrylate resin with different viscosities was prepared through the UV precuring process,then benzoyl peroxide(BPO)and N,N-dimethylaniline(DMA)were used as the curing system,which provided N,O atom coordinating with Zn^(2+),so that the interaction between molecular chains was increased to enhance the mechanical properties of the elastomer.In the curing process,resin turned from light yellow to purple,and became green eventually after curing completely.The causes of the color change and the mechanism of Zn^(2+)with the molecular chain of polymer were revealed:when N,O atoms provided by BPO and DMA,respectively,with free radicals coordinated with Zn^(2+),the system became purple;the system turned green when the free radicals faded away completely.According to the coordination mechanism,metal coordination bonds generated between Zn^(2+)and the molecular chains were located at the end of the chain,which greatly increased the elongation at break of the elastomer,so that the elongation at break of Zn^(2+)-acrylate elastomer increased to 7400%from 630%.Because of characteristics of the metal coordination bonds,we found that appropriate heat treatment can adjust the number of coordination bonds.After 150℃treatment,the tensile strength and the elongation at break of Zn^(2+)-acrylate elastomer increased by 28.6%and 39.6%,respectively,compared to those of the pure acrylate elastomer.In other words,both the tensile strength and elongation at break of Zn^(2+)-acrylate elastomer increased.This study provides a strategy for metal coordination with acrylate polymer,which is expected to play a significant role in the research of high elongation acrylate elastomer.The elastomer prepared can be used as seals,flexible sensor substrates in scenarios requiring the high extension rate materials.

关 键 词：光预聚 丙烯酸酯弹性体 金属配位机理 大变形能力 

分 类 号：TQ334[化学工程—橡胶工业]