大分子ATRP引发剂α-卤烷基聚苯乙烯的合成及其引发的丙烯酸丁酯接枝聚合

通过酰基化、还原、酯化和卤代反应 ,在聚苯乙烯上引入α 卤烷基 ,使用FTIR、1 H NMR、1 3C NMR和GPC对产物进行表征 ,结果表明基团转化可以完全进行 ,整个过程中无交联等副反应 .其中α 溴乙基聚苯乙烯可作为原子转移自由基聚合的多功能度引发剂 ,由此引发丙烯酸正丁酯聚合生成梳状聚 (苯乙烯 g 丙烯酸正丁酯 )

SYNTHESIS OF MULTIFUNCTIONAL ATRP MACROINITIATOR a-HALOALKYL POLYSTYRENE AND ITS GRAFT POLYMERIZATION OF BUTYL ACRYLATE

Polystyrenes (PS) with α-bromoethyl groups(PS-CH(CH 3)Br) and bromobenzyl groups (PS-CH(Ph)Cl) have been successfully prepared and the former with low substitute degree was used to initiate ATRP of n-butyl acrylate (MA).In order to avoid the crosslinking reaction during the preparation,the following steps were adopted:the acetylation of PS with acetyl chloride,the reduction of acetylated polystyrene (PS-COCH 3) with NaBH 4,the esterification of α-hydroethylated polystyrene (PS-CH(CH 3)OH) with acetyl anhydride and the bromination of α-acetoxylethylated polystyrene (PS-CH(CH 3)OCOCH 3) with HBr.As for PS-CH(Ph)Cl,PS-CH(Ph)OH was directly chlorinated with SOCl 2.Haloalky polystyrenes and the intermediates were characterized by FTIR, 1H-NMR, 13C-NMR and GPC and their substitution degrees were determined from the integral height of phenyl protons at δ6.54 and that of the corresponding characteristic proton.All the results indicated a complete conversion of different substitute groups in the preparation process.Graft polymerization of butyl acrylate (BA) was carried out and gave out poly(styrene-g-butyl acrylate) successfully using PS-CH(CH 3)Br with low substitution degree as the ATRP macroinitiator in conjugation with CuBr and bipyridine at low monomer conversion.