摘要：以偶氮双异丁腈(AIBN)作引发剂,研究3,3,3-三氟丙烯(TFP)的本体均聚及其在超临界二氧化碳(sc-CO₂)中与烯类单体如醋酸乙烯酯(VAc)、丙烯酸甲酯(MA)、苯乙烯(St)、异丁基乙烯基醚(IBVE)、丙烯酸(AA)5种单体的溶液共聚合反应,测定总单体转化率和TFP转化率随时间的变化及最终产物的平均分子量;对TFP与VAc在sc-CO₂中的溶液共聚合除测定上述聚合参数外,采用红外光谱和¹⁹F-核磁共振谱表征共聚物的结构,应用核磁共振和电位分析法对比表征共聚物中TFP的结合量、共聚物数均分子量及其分布指数随TFP与VAc的物质的量比、TFP转化率的变化。结果表明:无论是本体聚合还是在sc-CO₂中的溶液聚合,TFP都很难发生自由基均聚,但在sc-CO₂中TFP却可与上述5种单体发生自由基共聚合,相同条件下50 h TFP的转化率顺序是:Y(TFP-VAc)>Y(TFP-IBVE)>Y(TFP-MA)≈Y(TFP-St)>Y(TFP-AA)。对于TFP-VAc在sc-CO₂中的共聚,发现有明显的交替共聚倾向,当n(TFP)∶n(VAc)>0.5时,可获得n(TFP):n(VAc)接近1:1的交替共聚物。 还原

关键词： 超临界二氧化碳；三氟丙烯；均聚；共聚

Abstract：The homopolymerization of 3，3，3-trifluorpropene （TFP） and copolymerization of TFP with 5 vinyl monomers including vinyl acetate （VAc）， isobutyl viny ether （IBVE）， methyl acrylate （MA）， stylene（St） and acrylic acid （AA） in supercrical carbon dioxide （sc-CO₂） by using azobisisobutryonitrile （AIBN） as initiator were studied. The structure of as-prepared copolymer and its properties were characterized by FTIR，¹⁹F-NMR. The results showed that TFP was very difficult to homopolymerize in bulk or in sc-CO₂ by using AIBN as initiator， but it was easy to copolymerize with vinyl monomers under same polymerization condition. Among the vinyl monomers， in the same condition，TFP conversion rate order was Y（TFP-VAc）＞Y（TFP-TBVE） ＞Y（TFP-M）≈ Y（TFP-ST）＞Y（TFP-AA）.Only the copolymerization of TFP-IBVE and TFP-VAc got the alternating copolymer in which the mol ratio of TFP and comonomers approached 1∶1. 

Keywords: supercritical carbon dioxide； trifluorpropene； homopolymerization； copolymerization