沉淀聚合法制备单分散聚(4-乙烯基吡啶-co-二乙烯基苯/三羟甲基丙烷三甲基丙烯酸酯)聚合物微球  

Monodisperse Poly(4-vinylpyridine-co-divinyl benzene/trimethylolpropane trimethacrylate) Microspheres Prepared via Precipitation Polymerization

作　　者：卢春霞[1] 唐宗贵[1] 王静[1] 罗志根[1] 陈霞[1] 李红敏[1] 

机构地区：[1]新疆农垦科学院分析测试中心农业部食品质量监督检验测试中心(石河子),石河子832000

出　　处：《高分子学报》2016年第11期1538-1545,共8页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号31260412);兵团博士基金项目(基金号2014BB007)资助项目

摘　　要：以4-乙烯基吡啶（4-VP）为功能单体、二乙烯基苯（DVB）和三羟甲基丙烷三甲基丙烯酸酯（TRIM）为混合交联剂，偶氮二异丁腈（AIBN）为引发剂，乙腈为反应介质，采用沉淀聚合法制备单分散聚合物微球．考察了共聚单体、溶剂、引发剂等聚合条件对聚合物微球粒径、分散性以及产率的影响．并用扫描电镜（SEM）、激光粒度分析仪、热重分析仪和红外光谱对微球进行了表征．结果表明，聚合物微球的表面形貌和产率可通过改变溶剂体积、单体／交联剂摩尔比和引发剂浓度等因素进行控制．降低乙腈溶液体积、增加DVB摩尔比例及交联剂摩尔比、可增加聚合物粒径及粒度分布均匀性，而聚合物产率随溶剂体积和DVB摩尔比增大而减小，随交联剂摩尔比和引发剂浓度的增加而增加．在最优条件下，即DVB和TRIM两者摩尔比4：1，单体／交联剂摩尔比1：5，乙腈用量为5．6mL（单体和交联剂占介质体积的7％），引发剂浓度为2wt％～6wt％（占总反应单体的量）时，可获得形貌规则、产率较高的单分散poly（4-VP-CO-DVB／TRIM）微球，微球平均粒径约4．02μm，粒径分布指数（u）为1．013．此外，热重分析结果显示，聚合微球于350℃时开始分解，600℃时失重率达84．9％．Monodisperse poly-（4-vinylpyridine-co-divinyl benzene/trimethylolpropane trimethacrylate） （poly- （4-VP-co-DVB/TRIM） ） microspheres with smooth surface were successfully prepared by precipitation polymerization in acetonitrile with 4-vinylpyridine （4-VP） , divinyl benzene （ DVB ） and trimethylolpropane trimethacrylate （TRIM） as comonomers, 2,2-azobisisobutyronitrile （AIBN） as initiator. Effects of the polymerization conditions,such as comonomer ratio, solvents and initiator amount,on the morphology and yield of polymer microspheres were also investigated. The prepared polymers were characterized by scanning electron microscopy （SEM） , Fourier transform infrared （FTIR） , thermal gravimetric analysis （TGA） and particle size analysis. Results showed that polymerization parameters （including solvent type and amount, molar ratio of cross-linker to comonomer,ratio of the cross-linkers DVB to TRIM and initiator concentrations） had significant influence on the morphologies and yield of the resulting polymer microspheres. Particle size and uniformity of polymer increased with decreasing acetonitrile amount while increases in cross-linker and initiator loading caused larger particle sizes. The polymer yield increased gradually with the increases in the concentration of initiator and molar ratio of cross-linker,and decreased with the increase in the amount of the acetonitrile and molar ratio of cross-linker. When molar ratio of 4-VP： （DVB ＋ TRIM） was 1：5 and DVB： TRIM was 4： 1,with 2 wt% - 6 wt% of AIBN as initiator （based on all monomer weight） ,5.6 mL of acetonitrile as solvent, reaction temperature at 65 ℃ ,reaction time for 24 h,monodisperse poly-（4-VP-co-DVB/TRIM） microspheres with better spherical shape and high yields were obtained,and the average diameters and polydispersity index of the polymer microspheres were 4.02 μm and 1. 024, respectively. Moreover, thermal gravimetric analysis showed that the weight loss for polymer microspheres in the tempe

关 键 词：沉淀聚合 聚合物微球 4-乙烯基吡啶(4-VP) 二乙烯基苯(DVB) 三羟甲基丙烷三甲基丙烯酸酯(TRIM) 

分 类 号：TQ317[化学工程—高聚物工业]