摘要
以α-氯代丙酸乙酯(ECP)为引发剂,N,N,N’,N",N”-五甲基二亚乙基三胺(PMDE—TA)为配体,在N,N'-二甲基甲酰胺(DMF)溶液中引发甲基丙烯酸叔丁酯(tBMA)进行原子转移自由基聚合(ATRP),调节聚合反应时间得到了端基为氯原子,数均分子量为1.8×10^2~6.4×10^2的聚甲基丙烯酸叔丁酯(PtBMA—CD大分子引发剂。采用合成的5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环化合物(Me5[14]aneN4)为配体,使PtBMA-Cl引发4-乙烯吡啶(4VP)进行ATRP反应,得到了PtBMA—b-P4VP两嵌段共聚物,可使P4VP的收率达到60%。通过对PtBMA—b—P4VP的不同链段进行季铵化和水解反应,得到了聚甲基丙烯酸-b-季铵化聚4-乙烯吡啶(PMAA—b—QPVPB)亲水性嵌段共聚物。傅里叶变换红外光谱(FT—IR)、核磁共振(^1 H—NMR)和凝胶渗透色谱(GPC)分析表明:所得嵌段共聚物的结构明确,可将PtBMA与P4VP的链段长度之比调整在1:0.5~1:1的范围内。
Atom transfer radical polymerization (ATRP) of tert-butylmethacrylate (tBMA) was studied using ethyl-2-chloropropionate (ECP) as initiator in DMF. The number-average molecular weight of the PtBMA-C1 with a chlorine end group (PtBMA-C1) can be controlled from 1. 8 × 10^3 to 6. 4 × 10^2 by adjusting the polymerization time. Poly (tert-butylmethacrylate)-b-poly (4-vinylpyridine) (PtBMA-b- P4VP) was prepared by ATRP using PtBMA-C1 as macroinitiator, CuC1 and 5, 5, 7, 12, 12, 14-hexamethyl-1,4,8, 11-tetraazamacrocyclotetradecane (Me6 [-14-]aneN4) as catalyst and ligand. In this case, the yield of P4VP can be up to 60%. Structure and number-average molecular weight of PtBMA-C1 and PtBMA-b-P4VP were characterized by means of Fourier transform infrared(FT-IR) spectroscopy, nu- clear magnetic resonance (1 H-NMR) and gel permeation chromatography (GPC). Furthermore, the quat- ernization of the synthesized diblock copolymer were finished at first. The quaternizated diblock copolymer was then hydrolyzed under room temperature to form hydrophilic PMAA-b-QPVPB diblock copolymer. The results show that the chain lenth ratio of PtBMA with P4VP can be adjusted in rage of 1 : 0.5--1 : 1 in ATRP process. The structure of black copolymers was clear based on the analysis of ^1 H-NMR and FT-IR.
出处
《功能高分子学报》
CAS
CSCD
北大核心
2009年第1期23-29,共7页
Journal of Functional Polymers
基金
国家自然科学基金(2067104320876070)