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教育部高分子合成与功能构造重点实验室 浙江大学高分子科学与工程学系,杭州,310027
纸质出版日期:2012-11-20,
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李欣, 倪旭峰, 沈之荃. Sc(P204)3/烷基铝体系催化降冰片烯聚合[J]. 高分子学报, 2012,(11):1270-1275.
Xin Li, Xu-feng Ni, Zhi-quan Shen. POLYMERIZATION OF NORBORNENE CATALYZED BY Sc(P204)3/ALKYL ALUMINIUM SYSTEM[J]. Acta Polymerica Sinica, 2012,(11):1270-1275.
李欣, 倪旭峰, 沈之荃. Sc(P204)3/烷基铝体系催化降冰片烯聚合[J]. 高分子学报, 2012,(11):1270-1275. DOI: 10.3724/SP.J.1105.2012.12042.
Xin Li, Xu-feng Ni, Zhi-quan Shen. POLYMERIZATION OF NORBORNENE CATALYZED BY Sc(P204)3/ALKYL ALUMINIUM SYSTEM[J]. Acta Polymerica Sinica, 2012,(11):1270-1275. DOI: 10.3724/SP.J.1105.2012.12042.
以钪的膦酸酯盐Sc(P204)3和烷基铝组成催化体系催化降冰片烯(NBE)聚合
考察了聚合反应条件对单体转化率、产物分子量以及微观结构的影响.当以三乙基铝为助催化剂时
[NBE]/[Sc]=50(摩尔比)
[Al]/[Sc]=30(摩尔比)
40℃陈化5 min
在甲苯中于60℃聚合7 h
单体转化率为98%
所得聚合物可部分溶于有机溶剂;NBE以开环聚合方式为主
开环产物含量为81%~88%
其中顺式双键含量为48%~58%
分子量2.4103~3.0103
分子量分布1.9~2.2.当以三异丁基铝为助催化剂时
[NBE]/[Sc]=50(摩尔比)
[Al]/[Sc]=5(摩尔比)
50℃陈化2 h
80℃下于甲苯中聚合4 h
单体转化率为39%
所得白色聚合产物很难溶于有机溶剂
以开环聚合方式为主
产物中反式双键含量90%.
Polymerization of norbornene (NBE) was carried out using scandium phosphonate (Sc(P204)3) combined with alkyl aluminium as catalysts.13C-NMR
1H-NMR and FTIR analyses indicate that the PNBE are mainly prepared by the ring-opened type polymerization
and also show ring-retention to varying degrees in this type of catalytic system.It was found that alkyl aluminium cocatalyst plays an important role in the polymerization.Catalyzed by Sc(P204)3/Al-iBu3 system under the optimal polymerization conditions:n(Al)/n(Sc)=5 aging at 50℃ for 2 h
n(NBE)/n(Sc)=50
polymerization at 80℃ for 4 h producing a insoluble and crosslink polymer with 39% yield was obtained.While AlEt3 was used as cocatalyst
the PNBE obtained are partly soluble in organic solvents with 98% yield under the optimal polymerization conditions:n(Al)/n(Sc)=30 aging at 40℃ for 5 min
n(NBE)/n(Sc)=50
polymerization at 60℃ for 7 h.Measured by GPC
the soluble fraction of PNBE exhibits low molecular weight Mn =2.4103~3.0103 with moderate molecular weight distributions (MWD=1.9~2.2).The soluble fraction of PNBE consists of 81%~88% ring-opened type polymer with 48%~58% cis- double carbon bond content.
膦酸酯钪降冰片烯开环易位聚合加成聚合
Scandium phosphonateNorborneneROMPVinyl addition
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