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作 者:刘佳林[1] 丁文学[1] 张文传[1] 彭宇行[1]
机构地区:[1]中国科学院成都有机化学研究所
出 处:《化学研究与应用》1999年第3期259-263,共5页Chemical Research and Application
基 金:中国石油化工总公司资助
摘 要:本文研究了以甲苯为溶剂,AlCl3和BF3·OEt2为引发剂,1,3-戊二烯(PD)与苯乙烯(St)的阳离子共聚合反应,并用红外光谱测定聚合物的微观结构。由共聚单体PD和St加入顺序的不同可生成无规共聚物P(PD-co-St)和接枝共聚物P(PD-g-St)和P(St-g-PD)。无论是由AlCl3引发聚合反应,还是由BF3·OEt2引发聚合反应,St上的碳阳离子的活性都高于PD上碳阳离子的活性。由AlCl3首先引发PD进行聚合反应,结束后再引入St时,聚合体系不能引发St聚合反应;相反AlCl3首先引发St聚合后的体系能继续引发PD的聚合反应。BF3·OEt2无论先引发St或是PD,都能在聚合反应完成后接着引发另一单体而生成接枝共聚物P(PD-g-St)和P(St-g-PD)。二苯醚与烯丙基氯的加入,提高了碳阳离子的稳定性,增加了聚合物的分子量,但降低了碳阳离子的活性,使得聚合反应的产率降低。The cationic copolymerization of 1,3pentadiene (PD) with styrene (St) initiated by AlCl3 and BF3OEt2 was carried out in toluene.The microstructure of the copolymer was characterized by IR spectrometer.The random copolymer P(PDcoSt),graft copolymers P(PDgSt) and P(StgPD) result from three corresponding monomer addition procedure.The carbocation activity of PSt,whether initiated by AlCl3 or by BF3OEt2,is higher than that of PPD.After the polymerization of PD initiated by AlCl3 was completed,St can not be initiated by the polymerization system when St was introduced into the system.However,PD can be initiated by the polymerization system in which St has been first initiated by AlCl3,and the graft copolymer P(StgPD) has been produced.While BF3OEt2 is used as initiator,both polymerization systems of St and PD can initiate the polymerization of the other comonomer.Therefore,the graft copolymers P(PDgSt) and P(StgPD) could be produced through chain transfer processes.The introduction of diphenyl ether and
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