丙烯酸接枝邻苯二酚衍生物的二次聚合

合成了2种聚合前驱体邻苯二丙烯酸酯(o-PDA)和2-甲氧基苯丙烯酸酯(2-MOPA), 分别通过与丙烯酸(AA)自由基共聚得到邻苯二丙烯酸酯-丙烯酸共聚物(O1)和2-甲氧基苯丙烯酸酯-丙烯酸共聚物(O2). 产物邻苯二酚(o-DHB)-O1(质量比1∶1)和1-羟基-2-甲氧基苯(HMOB)-O2(质量比1∶1)分别在乙腈/二氯甲烷-三氟化硼乙醚体系中直接阳极氧化聚合获得交联网状共聚物P1和P2. P1和P2均可溶于DMSO, 而难溶于ACN, DCM和THF等有机溶剂. 通过UV-Vis, FTIR和 1H NMR对交联共聚物膜的结构进行了表征. AA的引入不仅可以增加链的柔韧性, 而且提高了共聚物的力学性能. 而o-DHB/ HMOB的引入极大地减弱了单体的聚合位阻, 实现了单体的二次聚合, 同时也增强了单体及聚合物的电化学活性. 荧光光谱显示, 得到的2种交联共聚物膜分别在415和487 nm处有较强的发射峰, 表明共聚物仍具有良好的蓝色发光性能, 且聚丙烯酸结构的引入并没有对聚邻苯二酚(Po-DHB)和聚(1-羟基-2-甲氧基苯)(PHMOB)产生较大的荧光猝灭作用. 热重分析曲线(TGA)表明2种交联共聚物膜均具有较高的热稳定性.

Novel Copolymers Synthesis by Second Polymerization of Acrylate Acid Grafted 1,2-Dihydroxylbenzene Derivatives

Two novel acrylate functionalized monomers o-phenylene diacrylate(o-PDA) and 2-methoxyphenyl acrylate(2-MOPA) were designed and synthesized.Through radical copolymerization of o-PDA/2-MOPA with acrylic acid(AA),two precursor polymers,oligo(o-phenylene diacrylate-co-acrylic acid)(O1) and oligo(2-methoxyphenyl acrylate-co-acrylic acid)(O2) were obtained.Cross-linked poly(O1-co-o-dihydroxybenzene)(P1) and poly(O2-co-1-hydroxy-2-methoxybenzene)(P2) films were achieved by electrochemical polymerization of monomer mixtures of o-DHB-O1 and HMOB-O2,respectively.UV-Vis,FTIR and 1H NMR spectra were used to characterize the structures of the copolymers.Since AA and o-DHB/HMOB were introduced into the polymerization processes,the steric hindrance of the monomers were weakened extremely,and the copolymers were synthesized via two-step polymerization.The copolymers show good electrochemical activities and mechanical properties.According to the fluorescence spectra,the copolymers show strong emission peaks at 415 and 487 nm,indicating the good blue-light emmitting properties of the copolymers and that the introductions of polyacrylate structures into the copolymers have little negative effect on their fluorescence pro-perties.TGA analysis suggests that as-formed copolymers exhibit high thermal stability.