光敏感三元共聚物的合成及溶液自组装  

SYNTHESIS AND SELF-ASSEMBLING OF A NEW PHOTO-SENSITIVE TERPOLYMER

作　　者：江金强 冯艳 王红梅[2] 朱叶 张胜文 陈明清 刘晓亚 

机构地区：[1]江南大学化学与材料工程学院,无锡214122 [2]北京药物化学研究所,北京102205

出　　处：《高分子学报》2009年第1期53-60,共8页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号20704017,20374025,50673038);复旦大学聚合物分子工程教育部重点实验室开放基金;江苏省高等学校优秀科技创新团队计划(《纳米颗粒材料的制备技术》,苏教科[2007]5号)资助项目

摘　　要：以一端为肉桂酸酯光交联基元、中间为聚己内酯长柔性链的甲基丙烯酸酯类大单体FM5C为第三单体,与马来酸酐(MAH)及苯乙烯(St)单体以AIBN引发共聚合,制备了光敏感三元共聚物P(FM5C-co-MAH-co-St).该三元共聚物可在选择性溶剂中形成纳米胶体粒子,并可先利用肉桂酸酯基元的光照交联作用使胶体粒子内聚合物交联,进而利用羧酸酐基元与2-氨基吡啶的室温氨解反应改变胶体粒子形态.用FTIR、GPC、1H-NMR等对该聚合物及其氨解产物进行了结构表征.用动态激光光散射(DLS)、透射电镜(TEM)、芘探针等技术研究了该聚合物胶体粒子微观形态、粒径与微环境在光照交联后及氨解后的变化.实验结果表明,P(FM5C-co-MAH-co-St)在选择性溶剂中可自组装成球形胶体粒子,肉桂酸酯光照交联作用使胶体粒子中的聚合物团聚得更加紧密,从而使其粒径更小、疏水区域更加集中;而进一步的室温氨解反应则使聚合物胶体粒子更松散、粒径变大.A new photo-sensitive polymaleic anhydride terpolymer （P（FM5C-co-MAH-co-St）） was synthesized using radical terpolymerization of maleic anhydride （MAH）, styrene （St） and the macromonomer （FM5 C, a methacrylate derivate） with a photo-crosslinkable cinnamate pendent. The terpolymer was characterized by GPC, FTIR and ^1H-NMR. The self-assembling of the terpolymer was carried out in aqueous solutions. The basic strategy is to form photo-crosslinked colloid panicles （PCCPs） by the photo-dimerization of the cinnamate groups under UV irradiation （ 〉 300 nm）, and then to regulate the morphology of PCCPs by the functional aminolysis reaction between maleic anhydride unit and 2-aminopyridine.h was found that the terpotymic colloid particles （TCPs） would gain a much closer morphology and a more hydrophobic local environment after the photo-crosslinking reaction, and the hydrophilic environment and the average size of PCCPs would increase after the aminolysis regulation. DLS analysis and TEM images showed that TCPs and PCCPs formed well defined solid nano-spheres in aqueous solutions with the average size of 100 nm, hut after aminolysis reaction, the average size for PCCPs dramatically increased to about 150 nm. The pyrene probe technique showed that TCPs would gain a much closer morphology and a more hydrophobic local environment after photo-crosslinking with a low 11/13 （1.40） against the high 11/13 （1.75） before photocrosslinking reaction, but after aminolysis reaction, the PCCPs expanded and the ratio increased to 1.67.

关 键 词：三元共聚物 肉桂酸酯 光交联 氨解 芘探针 

分 类 号：O631.3[理学—高分子化学]