摘要
以丙烯酸2-(2-溴异丁酰氧基)乙酯(BIEA)为引发剂单体(inimer),丙烯酸甲酯(MA)为单体,Cu0/CuBr2和N,N,N',N″,N″-五甲基二亚乙基三胺(PMDETA)为催化体系,二甲亚砜(DMSO)为溶剂,在常温(25℃)下通过单电子转移活性自由基聚合(SET-LRP)合成支化聚丙烯酸甲酯.聚合反应过程中,采用气相色谱(GC)、核磁共振(1H-NMR)和三检测体积排除色谱(TD-SEC)等测试手段跟踪分析和表征支化聚合物的结构.研究结果表明,采用SET-LRP方法,铜粉作为催化剂,常温下聚合反应就能快速进行,130 min之内MA的转化率已达99%以上,制备出高分子量支化聚合物.随着反应的不断进行,聚合物支化程度不断提高,相比较同分子量下的线型聚合物其黏度不断下降,Mark-Houwink特征常数α最小可达0.290.此外,低分子量聚合物组分随着反应不断减少,在高单体转化率下,聚合体系中以高支化度的聚丙烯酸甲酯为主.
The branched poly （methyl acrylate） was prepared by using 2-（2-bromoisobutyryloxy） ethyl acrylate as inimer agent, methyl acrylate as monomer and Cu^0/CuBr2/PMDETA as catalyst system via single electron transfer living radical polymerization （SET-LRP） in DMSO polar solvent at room temperature. In the polymerization process, gas chromatography （GC） , nuclear magnetic resonance spectroscopy （^1H-NMR） and triple detection size exclusion chromatography （TD-SEC） were used to analyse and characterize the polymerization and the resulting polymers. The results showed that the polymerization rate was significantly fast at room temperature,when the polymerization time was 130 rain, the conversion of monomer methyl acrylate was over 99%. The degree of branching for the branched polymer increased gradually with monomer conversion, and the viscosity of branched polymer was low compared to that of the linear polymer at the same molecular weight. Therefore, the characteristic constant c~ of Mark-Houwink would be minimized to 0. 290. In addition, the primary chains with low molecular weight （component 1 ） in the branched polymers were decreasing during the whole reaction. In the late stages of the reaction, the high branched poly （methyl acrylate） component was mainly obtained.
出处
《高分子学报》
SCIE
CAS
CSCD
北大核心
2012年第4期398-403,共6页
Acta Polymerica Sinica
基金
国家自然科学基金(基金号20574032
21104006)
江苏省自然科学基金(基金号BK2007045)
常州大学科技项目(项目号ZMF1002118)
常州市高分子新材料重点实验室资助项目
关键词
单电子转移活性自由基聚合
丙烯酸甲酯
支化聚合物
Single electron transfer living radical polymerization, Methyl acrylate, Branched polymer
