蓖麻油基活性聚合用引发剂的合成及其聚合特性研究  

Synthesis and Characterization of Castor Oil Based Initiator Used for Living Polymerization

作　　者：刘玉鹏[1,2] 俞娟[1] 黄海洲[3] 王春鹏[1,2] 季永新[3] 刘美红[1] 王基夫[1,2] 储富祥[1,2] 

机构地区：[1]中国林业科学研究院林产化学工业研究所,生物质化学利用国家工程实验室,国家林业局林产化学工程重点开放性实验室,江苏省生物质能源与材料重点实验室,江苏南京210042 [2]中国林业科学研究院林业新技术研究所,北京100091 [3]南京林业大学化学工程学院,江苏南京210037

出　　处：《林产化学与工业》2014年第6期1-7,共7页Chemistry and Industry of Forest Products

基　　金：中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFINT2010K04);江苏省自然科学基金面上项目资助(BK20131070)

摘　　要：将2-溴代异丁酰溴和蓖麻油的羟基按物质的量比1∶1进行酯化反应,一步法合成蓖麻油基的活性聚合用原子转移自由基聚合(ATRP)引发剂,采用FT-IR、1H NMR和13C NMR对其结构进行表征。红外谱图中3500 cm-1处的羟基的伸缩振动峰减弱,1740 cm-1处的酯基峰增强,表明蓖麻油中的羟基官能团基转变为酯基,溴代异丁酰基官能团成功接枝到蓖麻油分子上,1H NMR和13C NMR谱图的分析结果进一步证明蓖麻油基ATRP引发剂的合成和结构的正确性。采用单体/引发剂/溴化亚铜/配体物质的量之比100∶1∶0.5∶1,反应温度60℃(苯乙烯80℃)的聚合反应体系,GPC、1H NMR和13C NMR谱图结果显示,蓖麻油基ATRP引发剂可以高效的引发甲基丙烯酸甲酯,以及苯乙烯的ATRP聚合反应,整个过程高效和可控制。Castor oil based atom transfer radical polymerization （ ATRP ） initiator was synthesized by one-pot reaction of 2-bromoisobutyryl bromide with hydroxyl group in castor oil under hydroxyl-to-bromide molar ratio of 1∶1 and characterized by means of FT-IR, ^1H NMR and ^13C NMR . The results showed that the esterification for the synthesis of castor oil based ATRP initiator is prompt and highly efficient. In FT-IR spectrum, the conversion of hydroxyl group to ester group resulted in the decrease in the intensity of peak at 3500 cm^-1 corresponding to hydroxyl group and increase of peak at 1740 cm^-1 corresponding to ester group. This indicated that 2-bromoisobutyryl group was grafted on castor oil successfully. Subsequently, the castor oil based ATRP initiator was used to trigger the ATRP of methyl methacrylate （ MMA） and styrene （ St） under the condition of feeding molar ratio （monomer/initiator/CuBr/ligand） of 100∶1∶0. 5∶1 and reaction temperature 60 ℃ for MMA and 80 ℃ for St, respectively. GPC curves and spectra of ^1H NMR and ^13C NMR showed that polymerization process of MMA, as well as St, was highly efficient and well controlled.

关 键 词：蓖麻油 原子转移自由基聚合(ATRP)引发剂 活性聚合 

分 类 号：TQ35[化学工程]