对丙烯腈聚合有高活性的催化体系:二(叔丁基环戊二烯基)钕甲基配合物/季铵盐(苯酚钠、萘酚钠)

A High Active Catalyst System for Polymerization of Acrylonitrile:[(Bu^tCp)_2NdMe]_2/Quarternary Ammonium Salt(Sodium Phenolate、Sodium Naptholate) System

添加适量的对叔丁基苯酚钠、2 ,6-二叔丁基对甲基苯酚钠、2 -甲基萘酚钠或季铵盐可以显著提高二(叔丁基环戊二烯基 )钕甲基配合物催化丙烯腈聚合的活性 .考察了由 ( C4H9) 4NBr与 [( But Cp) 2 Nd Me]2 组成的催化体系中季铵盐用量、聚合温度、催化剂用量、单体浓度及溶剂对聚合活性的影响 .当 ( C4H9) 4NBr与[( But Cp) 2 Nd Me]2 的摩尔比等于 2 ,催化剂用量为每克单体 2 .0× 1 0 - 5 mol,4 0℃ ,聚合 2 h,转化率可达65.4 % .

The polymerization of acrylonitrile catalyzed by [(Bu t Cp) 2NdMe] 2/quarternary ammonium salt(sodium phenolate、sodium naptholate) was first studied. The catalytic activity of [(Bu t -Cp) 2NdMe] 2(Cat) was greatly increased by adding quarternary ammonium salt, sodium phenolate or sodium naptholate, such as CH 3(CH 2) 15 NBrMe 3, Me 4NBr, (C 4H 9) 4NBr, 2,6-di-Bu t 2-4-MeC 6H 2ONa, 4-Bu t C 6H 4ONa and (2-MeC 10 H 6ONa). The polymerization conditions were investigated, including the effects of the mole ratio of (C 4H 9) 4NBr to (Cat), the amount of (Cat), monomer concentration, polymerization temperature and solvent. The conversion of acrylonitrile was as high as 65.4% at the polymerization conditions: [(C 4H 9) 4NBr]/[Cat]=2, [Cat]=2.0×10 -5 mol/g, x (M)=50%, 40 ℃ , toluene, 2 h.