应用化学2011，Vol.28Issue(10)：1148-1154,7.DOI:10.3724/SP.J.1095.2011.00620
离子液体中单电子转移活性自由基聚合法制备星形聚丙烯酰胺
Synthesis of Star Polyacrylamide by Single Electron Transfer Living Radical Polymerization in Ionic Liquid System
摘要
Abstract
A single electron transfer living radical polymerization (SET-LRP) is able to rapidly achieve high molecular mass, with excellent control of molecular mass distribution, represents a robust and versatile method for the rapid synthesis of macromolecules with defined architecture. The SET-LRP of acryl amide( AM) was investigated at 40℃ in 1-butyl, 3-methyl tetrafluoroborate ([ Bmim] BF4 ) ionic liquid, using Cu0 power/ tris(2-dimethylamin ethyl) amine( Me6-TREN) as catalyst, 2,2-dibromomethyl-l ,3-dibromopropane( PEBr4) as initiator. The polymerization showed some "living" features; the conversion and In ([M]0/[M]) increased linearly with- time as well as the number-average molecular mass increased linearly with conversion. The star polyacrylamide(sPAM) prepared via SET-LRP was characterized by GPC and 'H NMR to identify its polymerization mechanism, and the results showed that the polymer had the perfect functional chain ends and relatively low molecular mass distribution Mw/Mn ≈ 1. 26 (HnGPC = 14. 1 x 103 , conversion rate is 43. 4% ) , indicating a controlled polymerization. The effects of water, catalyst and initiator on polymerization were studied, and the dynamic experiments were carried out. A small amount of water added could accerlerate the polymerization, the apparent rate constants of propagation (kPapp) were 0.04248 h-1 and 0. 14869 h-1 for adding free water and 0. 5 mL H2 0 respectively; the control of polymerization could be improved with the presence of catalyst and increasing the concentration of initiator. The polymerization rate of SET-LRP increased with the amount of catalyst and initiator. In addition, Mn increased with the amount of catalyst or decreasing the amount of initiator and was closed to the theoretical molecular mass. The molecular mass distribution showed a decreasing trend, the minimum was about 1.26. The [Bmim]BF4 ionic liquid was a good solvent to PEBr4 and acryl amide, and the polymers were easily separated from the catalyst.关键词
单电子转移活性自由基聚合/离子液体/星形聚合物/丙烯酰胺Key words
single electron transfer living radical polymerization,ionic liquid,star polymer,acrylamide分类
化学化工引用本文复制引用
丁伟,孙颖,吕崇福,景慧,于涛,曲广淼..离子液体中单电子转移活性自由基聚合法制备星形聚丙烯酰胺[J].应用化学,2011,28(10):1148-1154,7.基金项目
国家科技重大专项(2008ZX05011),黑龙江省自然科学基金重点项目(ZJ0507),黑龙江省自然科学基金青年基金(QC08C33)资助项目,黑龙江省研究生创新科研基金(YJSCX2008-)44HIJ)资助项目 （2008ZX05011）
