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原位合成引发剂引发原子转移自由基及衰减链转移同步聚合
The atom transfer radical polymerization and degenerative transfer polymerization initiated by initiator formed in situ
【摘要】 在甲基丙烯酸甲酯(MMA)单体中,以偶氮二异丁腈(AIBN)与I2反应原位合成α-碘代异丁腈(IIBN),进一步作为原子转移自由基聚合引发剂分别与CuCl、FeCl2.4H2O等催化剂,MA5-DETA、PMDETA等络合剂相匹配引发MMA的ATRP,同时又作为衰减链转移聚合(DT)的可逆链转移剂同步进行DT聚合。实验结果表明:所得聚合物分子量可控,分子量分布(PDI)很窄(1.05~1.25),引发剂效率较高。动力学的研究结果显示:分子量随转化率而增长;由Ln[M]0/[M]t对时间作图,呈现良好的线形关系,表明聚合过程中增长自由基浓度是一个恒定值,证明由IIBN引发的聚合是典型的活性自由基聚合;这种方法克服了极不稳定的在α-位带有吸电子基团的碘化物的购运和储存的困难。不失是一种简单,快捷,方便的方法。
【Abstract】 A novel initiator α-iodoisobutyrontrile(IIBN),synthesized from the reaction of I2 with 2,2′-azobisisobutyronitrile(AIBN) in methyl methacrylate(MMA) is used as initiator for atom transfer radical polymerization(ATRP) and simultaneity as a transfer agent for degenerative transfer polymerization(DT) of MMA,using CuCl,FeCl2.4H2O etc.as catalysts and MA5-DETA,PMDETA etc.as ligands.Results exhibit: polymerization is well-controlled,results polymer with low polydispersities(PDI: 1.05 ~1.25) initiator efficiency of IIBN is rather high.The linearity of the semilogarithmic plot of Ln([M]0/[M]) vs.polymerization time indicates the polymerizations were first-order,concentration of the growing radicals remaine constant throughout reaction time.This method refrains from using expensive,toxic unstable iodides.Direct employment of IIBN as an initiator for ATRP and DT is a simple,effective and convenience method.
【Key words】 Atom transfer radical polymerization(ATRP); Degenerative transfer polymerization(DT); Initiator; α-iodoisobutyrontrile,;
- 【文献出处】 胶体与聚合物 ,Chinese Journal of Colloid & Polymer , 编辑部邮箱 ,2009年02期
- 【分类号】O631.5
- 【下载频次】121