聚2-丙烯酰氧乙基二茂铁甲酸酯的合成及性能  

Synthesis and Properties of Poly(2-acryloyloxyethyl ferrocenecarboxylate)

作　　者：李科[1] 张教强[1] 康拴艳 石绘敏 周宏玉[1] 

机构地区：[1]西北工业大学理学院应用化学系,西安710129

出　　处：《高分子学报》2015年第2期236-244,共9页Acta Polymerica Sinica

基　　金：陕西省自然科学基金(基金号2014KA110035)资助项目

摘　　要：以二茂铁甲酸（FCA）和2-羟乙基丙烯酸酯（HEA）为反应物、以二环己基碳二亚胺（DCC）为脱水剂、以对二甲氨基吡啶（DMAP）为催化剂通过酯化反应合成并表征了2-丙烯酰氧乙基二茂铁甲酸酯（AEFC）.然后以AEFC为单体、3种不同溴代烷为引发剂、溴化亚铜（Cu Br）和2,2-联吡啶（bpy）为催化体系、甲苯为溶剂在100℃下通过ATRP方法合成并表征了聚2-丙烯酰氧乙基二茂铁甲酸酯（PAEFC）.这3种引发剂分别为：溴代乙酸乙酯（EBr A）、2-溴丙酸甲酯（2-MBP）和2-溴异丁酸乙酯（EBi B）,同时还比较了3种引发剂对聚合物动力学的影响,结果表明EBr A为引发剂时AEFC的聚合过程不是以一个＂活性＂/可控的方式进行的,而2-MBP和EBi B为引发剂时聚合过程是以一个＂活性＂/可控的方式进行的,但是2-MBP的可控性较EBi B差.另外还研究了EBi B为引发剂时,EBi B的用量对聚合过程的影响,结果表明[AEFC]∶[EBi B]=100∶1时聚合过程的可控性较高.催化剂的用量对聚合过程的影响研究表明当[AEFC]∶[Cu Br]=100∶2时聚合过程的可控性较高.聚合物的热力学性能表明其有较低熔点160.6℃,热分解焓变为9541 J/g,较高的分解温度200~460℃.To obtain side-chain ferrocene-containing muhifunctional polymers 2-acryloyloxyethyl ferrocenecarboxylate（ AEFC ） was synthesized and characterized via esterification reaction in this work. Ferrocenecarboxylic acid （ FCA）, 2-hydroxyethylacrylate （ HEA ）, N, N＇-dicyclohexylcarbodiimide （ DCC ） and 4-di （methylamino） -pyridine （DMAP） were used as reagent, dehydrating agent and catalyst, respectively. Then poly（2-acryloyloxyethyl ferrocenecarboxylate） （PAEFC） was synthesized and characterized by ATRP in toluene at 100 ℃, wherein, AEFC, copper（I） bromide （CuBr） ,2,2＇-bipyridine （bpy） and three kinds of bromoalkane were used as monomer, catalyst, ligand, and initiator, respectively. Three kinds of different initiators are ethyl bromoacetate （EBrA） , methyl 2-bromopropionate （2-MBP）＂ and ethyl 2-bromoisobutyrate （EBiB） respectively. Meanwhile,the influences of these different initiators on the polymerization kinetics were compared. These studies indicated that the procedure of polymerization of monomers doesn＇ t follow a ＂living＂/ controlled manner with EBrA as initiator, while, the procedure of polymerization follows a ＂ living＂/controlled manner with 2-MBP and EBiB as initiator,respectively, and the controlability of EBiB is better than that of 2- MBP. In addition,the effects of EBiB and CuBr dosages on the process of polymerization were studied, and the suggested molar ratios AEFC/EBiB and AEFC/CuBr were 100/1 and 100/2,respectively. Thermal properties of the polymer demonstrated that it has lower melting point 158.2 ℃ ,thermal decomposition enthalpy of 9541 J/g and higher decomposition temperature of 200 -460℃.

关 键 词：原子转移自由基聚合 二茂铁 均聚物 引发剂 含二茂铁基的聚合物 

分 类 号：O634[理学—高分子化学]