纸质出版日期:2006-2-20
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通过活性正离子聚合与原子转移自由基聚合(ATRP)转换合成了β-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α-氯代乙苯/TiCl4/Ti(OiPr)4/nBu4NCl体系引发β-蒎烯活性正离子聚合,合成预定分子量大小和窄分子量分布的聚β-蒎烯,然后经N-溴代琥珀酰亚胺(NBS)定量溴化,得到溴化聚β-蒎烯大分子引发剂(Br/β-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.
Graft copolymers of βpinene 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).β-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(β—pinene)macroinitiators with 50% of bromine contents(Br/β-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 controllable.The structures of the obtained graft copolymers of β-pinene with(methyl)methacrylate or styrene were confirmed by 1H-NMR spectra.
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