新型双苯并环己酮芳亚胺镍(Ⅱ)催化降冰片烯与甲基丙烯酸丁酯共聚合

Copolymerization of Norbornene and n-Butyl Methacrylate Catalyzed by Novel Ni(Ⅱ)( benzocyclohexan-ketoarylimino)_2

采用自制的新型双苯并环己酮芳亚胺镍催化剂双苯并环己酮-2,6-二甲基苯亚胺镍(Ⅱ)(Ni{C10H8(O)C[2,6-C6H3(CH3)2N]CH3}2,C1)和双苯并环己酮-2,6-二氯苯亚胺镍(Ⅱ)(Ni{C10H8(O)C[2,6-C6H3Cl2N]CH3}2,C2)与三五氟苯硼[B(C6F5)3]结合,在一定的反应条件下可高效催化降冰片烯(NB)与甲基丙烯酸正丁酯(n-BMA)的乙烯基加成共聚合.提出了催化聚合时存在的可能失活机理;研究了不同单体投料比对催化活性、产率及产物性能的影响.根据Kelen-Tüds方法分别估算出2种单体在不同催化体系下的竞聚率,即当催化体系为C1/B(C6F5)3时,竞聚率rn-BMA=0.02,rNB=16.28,rNB·rn-BMA=0.32;当催化体系为C2/B(C6F5)3时,rn-BMA=0.01,rNB=64.83,rNB·rn-BMA=0.65.结果表明,2种单体在2种体系催化下均为无规共聚合.

Vinyl-addition copolymerization of norbomene （NB） and polar monomer n-butyl methacrylate （n-BMA） were carried out via two novel high activity catalysts, Ni（Ⅱ） （benzocyclohexan-ketoarylimino）2 （Ni{C10Hs（O）C[2,6-C6H3（CH3）2N]CH3}2, C1） and Ni{C10H8（O）C[2,6-C6H3Cl2N] CH3}2, C2）, in combination with tris（pentafluorophenyl） -borance V B （ C6F5 ） 3 1＂ A possible catalytic deactivation mechanism of polymerization was presented. Influence of monomer feed ratio on catalytic activity, conversion rate and properties of outcomes were investigated. Reactivity ratios of co-monomers were estimated by Kelen-Tudos method, they are rn-BMA = 0. 02, NB = 16. 28, rnB ~ rn.BMA = O. 32 for C1/B （ C6F5 ）3 catalytic system, and rn-BMA =0.01, r=MB =64. 83, rNB · rn-BMA =0. 65 for C2/B（ C6F5 ）3 catalytic system. These indicate the random copolymerization of NB/n-BMA occurs with both C1/B（ C6F5 ）3 and C2/B（C6F5）3.