活性阳离子聚合与原子转移自由基聚合转换合成聚beta-蒎烯接枝共聚物
首发时间:2005-12-14
摘要:通过活性阳离子聚合与原子转移自由基聚合(ATRP)转换合成了beta-蒎烯与甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、苯乙烯(St)的新型接枝共聚物。首先以alfa-氯代乙苯/TiCl4/Ti(OiP)4/nBu4NCl体系引发beta-蒎烯活性阳离子聚合,合成预定分子量大小和窄分子量分布的聚beta-蒎烯,然后经N-溴代琥珀酰亚胺(NBS)定量溴化,得到溴化聚beta-蒎烯大分子引发剂(Br/beta-蒎烯链节摩尔比为0.5)。然后将该大分子引发剂与溴化亚铜(CuBr)/2,2’-联二吡啶(bpy)复合,引发MMA、BA、St进行ATRP接枝聚合。接枝反应显示一级动力学特征,且产物的分子量及分子量分布可控,表明上述ATRP接枝聚合反应具有可控聚合特征。接枝产物的结构经1H NMR分析得到进一步证实。
关键词: beta-蒎烯接枝共聚物 活性阳离子聚合 ATRP
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Synthesis of New Copolymers of beta-Pinene by the Combination of Living Cationic Polymerization and ATRP
Abstract:New graft copolymers of beta-pinene with methyl methacrylate (MMA), butyl acrylate (BA) or styrene (St) were synthesized by the combination of living cationic polymerization and atom transfer radical polymerization (ATRP). beta-Pinene polymers with predetermined molecular weights and narrow molecular weight distributions (MWDs) were prepared by living cationic polymerization with the 1-phenylethyl chloride /TiCl4/Ti(OiPr)4/nBu4NCl initiating system, and the obtained polymers were brominated quantitatively by N-bromosuccinamide in the presence of AIBN, yielding poly(beta-pinene) macroinitiators with 50% of bromine contents (Br/beta-pinene unit molar ratio = 0.5). The macroinitiator, in conjunction with CuBr and 2,2’-bipyridine, was used to initiate ATRP grafting of BA, MMA and St. All of the grafting polymerizations induced linear first-order kinetic plots and gave graft copolymers with controlled molecular weights and MWDs, suggesting that these polymerizations are controlled. The structures of the obtained graft copolymers of beta-pinene with (methyl)methacrylate or styrene were confirmed by 1H NMR spectra.
Keywords: beta-pinene based graft copolymer, Living cationic polymerization, ATRP
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