摘要
研究了三氟甲基磺酸三甲基硅酯／三氯化锑（（ＣＨ３）３ＳｉＯＳＯ２ＣＦ３／ＳｂＣｌ３）复合引发体系对１，３戊二烯的聚合行为．在（ＣＨ３）３ＳｉＯＳＯ２ＣＦ３引发剂中加入ＳｂＣｌ３后，使聚合反应速率提高了２４倍，产率从（ＣＨ３）３ＳｉＯＳＯ２ＣＦ３引发的５５％提高到８０％以上，分子量提高１７倍．在聚合体系中加入酮类后，产率和分子量相对于（ＣＨ３）３ＳｉＯＳＯ２ＣＦ３／ＳｂＣｌ３配比为０２：１时引发所得聚合物均呈下降趋势；但对不同的酮来说，随着酮的位阻的增大，聚合物的产率和分子量均增大．聚合物的１ＨＮＭＲ图和红外谱图数据均证明该聚合反应是通过（ＣＨ３）３ＳｉＯＳＯ２ＣＦ３与体系中残存的水水解所形成的质子酸ＨＯＳＯ２ＣＦ３与ＳｂＣｌ３反应所形成的复合体系引发进行的．
Cationic polymerization of 1,3 pentadiene (PD) by trimethylsilyl trifluoromethanesulfonate ((CH 3) 3SiOSO 2CF 3) in combination with SbCl 3 were carried out in n hexance at 30℃. Addition of SbCl 3 into the (CH 3) 3SiOSO 2CF 3 induced PD polymerization. The polymer yield increases from 55% to 80%, the polymerization is accelerated 2 4 times and the molecular weight of polymer is 1 7 times. Various ketones were used to mediate the initiating system (CH 3) 3SiOSO 2CF 3/SbCl 3, the more bulky the ketone is, the higher yield and molecular weight are obtained. The 1H NMR and the IR show that the polymerization of PD was initiated by the SbCl 3 in complexation with trific acid (HOTf) resulting from hydrolysis of (CH 3) 3SiOSO 2CF 3 by adventitious water.
出处
《高分子学报》
SCIE
CAS
CSCD
北大核心
1999年第1期1-6,共6页
Acta Polymerica Sinica
基金
国家自然科学基金
关键词
戊二烯
阳离子聚合
引发剂
聚戊二烯
Trimethylsilyl, Trifluoromethanesulfonate 1,3 Pentadiene, Cationic polymerization
