基于复合配体的ATRP法合成PtBA的研究  

Study on the synthesis of poly tert-butylacrylate by ATRP using complex ligands

作　　者：李光华[1] 赵治巨[1] 杨苹苹[1] 李玉香[1] 何丽秋[1] 

机构地区：[1]广西大学化学化工学院,广西南宁530004

出　　处：《广西大学学报（自然科学版）》2010年第2期227-232,共6页Journal of Guangxi University（Natural Science Edition）

基　　金：广西大学科研基金(X071018);教育部留学回国人员科研启动基金(教外司留[2008]890号);广西区研究生创新项目(T32191)

摘　　要：以2,2′-联吡啶(bpy)和N,N,N′,N″,N″-五甲基二乙烯三胺(PMDETA)为复合配体,丙烯酸叔丁酯(tBA)为单体,EtBr-iB为引发剂,CuBr为催化剂,利用原子转移自由基聚合(ATRP)法合成了聚丙烯酸叔丁酯大分子引发剂(PtBA-Br)。同时,考察了在两种不同溶剂和温度下的聚合反应行为,并与bpy和PMDETA单一配体时的聚合进行了比较。利用FT-IR、1H-NMR和GPC对聚合物进行了表征。结果表明:在60℃下,以甲苯为溶剂,bpy+PMDETA为复合配体时,聚合反应动力学曲线呈很好的线性关系;聚合速率比bpy为配体时慢,而比PMDETA为配体时略快;其表观聚合速率常数k′p为2.1×10-5s-1,分子量分布小于1.3;溶剂为甲苯时聚合速率比THF为溶剂时快;温度60℃时分子量分布比90℃时窄。In this paper, poly （tert-butylacrylate） macroinitiator （PtBA-Br）was synthesized from tert-butylacrylate （tBA）, using atom transfer radical polymerization （ATRP） with ethyl 2-bromo- isobutylate （ EtBr-iB ） as an initiator and CuBr/2,2＇-bipyridine （bpy） ＋ N, N, N＇, N＂, N＂-pentamethyl diethylenetriamine （PMDETA） as a catalytic system. The polymerization reaction behaviors were investigated under two different solvents and temperature conditions, and compared with a single lig- and bpy or PMDETA. The resulting PtBA-Br was characterized by FT-IR, ^1 H-NMR and GPC. These results showed that the kinetic plots of the polymerization shows good linear relationship in toluene with bpy 4- PMDETA as a complex ligands at 60 ℃; the rate of polymerization is slower than with bpy, while faster than with PMDETA; the apparent rate constant k＇p is 2. 1 ×10^-5s^-1, and the molecular weight distributions are less than 1.3 ; the rate of polymerization in toluene is faster than in THF; the molecular weight distribution at 60℃ is narrower than at 90 ℃.

关 键 词：丙烯酸叔丁酯 大分子引发剂 复合配体 原子转移自由基聚合 动力学 

分 类 号：O631.5[理学—高分子化学]