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.%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-eo-acrylic acid) (01) and oligo (2-methoxyphenyl acrylate-co-acrylic acid ) ( 02 ) were obtained. Cross-linked poly ( O1-co-o-dihydroxy-benzene)(Pl) and poly(O2-co-l-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 properties. TGA analysis suggests that as-formed copolymers exhibit high thermal stability.
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