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以(C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2和[Ph3C][B(C6F5)4]组成的单茂钪催化体系催化非共轭双烯均聚合及与乙烯共聚合,考察了聚合条件及非共轭双烯结构对聚合活性、产物分子量和微结构的影响.单茂钪催化体系中,单体浓度、聚合温度、聚合溶剂以及烷基铝试剂对1,5-己二烯的聚合活性和选择性以及聚合产物的分子量和分子量分布均有较大影响.室温甲苯溶剂中,单茂钪可以催化1,5-己二烯,1,6-庚二烯,1,7-辛二烯,1,9-癸二烯四种非共轭双烯聚合获得相应的聚合物;除1,9-癸二烯聚合获得不溶的交联聚合物外,其它非共轭双烯聚合均获得可溶的环烯烃聚合物.1,5-己二烯聚合形成亚甲基-1,3-环戊基(MCPN)五元环和四元环开环形成的3-乙烯基四亚甲基(VTM)结构单元.1,6-庚二烯聚合完全环化形成亚甲基-1,3-环己基(MCHX)六元环和乙烯基-1,2-环戊基(ECPN)五元环结构单元,1,7-辛二烯聚合形成亚甲基-1,3-环庚基(MCHP)七元环结构单元和未环化的悬挂己烯(HEB)结构单元.室温1.01×105Pa乙烯压力下,单茂钪催化体系还可以快速催化非共轭双烯1,5-己二烯,1,6-庚二烯,1,7-辛二烯,1,9-癸二烯与乙烯共聚合,获得含有环状结构单元、悬挂双键结构单元和聚乙烯嵌段的无规共聚物.在单茂钪催化非共轭双烯均聚合及与乙烯共聚合中,非共轭双烯的链长直接影响了其聚合活性和选择性.
The copolymerization of non-conjugated diene and copolymerization with ethylene was catalyzed by monofluorescein scandium catalyzed by (C5Me4SiMe3) Sc (CH2C6H4NMe2-o) 2 and [Ph3C] [B (C6F5) 4] Effect of the structure of the conjugated diene on the polymerization activity, product molecular weight and microstructure The polymerization activity and selectivity of 1,5-hexadiene in the monolayer scandium catalyst system with monomer concentration, polymerization temperature, polymerization solvent and aluminum alkyl reagent As well as the molecular weight and molecular weight distribution of the polymerization products have a greater impact.At room temperature in toluene, the monomer Mao scandium can catalyze 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1 , 9-decadiene four kinds of non-conjugated diene polymerization to obtain the corresponding polymer; 1,9-decadiene addition to obtain an insoluble cross-linked polymer, the other non-conjugated diene polymerization are soluble Cycloalkene polymers. The polymerization of 1,5-hexadiene to form 3-vinyltetramethylene (VTM) rings formed by the ring opening of methylene-1,3-cyclopentyl (MCPN) Structural unit .1,6-heptadiene polymerization completely cyclized to form methylene-1,3-cyclohexyl (MCHX) six-membered ring and vinyl-1,2-cyclopentyl (ECPN) , 1,7-octadiene polymerizes to form methylene-1,3 -cycloheptyl (MCHP) 7-membered ring structure unit and uncyclic hexene (HEB) structural unit.Under the pressure of 1.01 × 105Pa at room temperature, the monocene scandium catalyst system can also rapidly catalyze the non-conjugated diene 1, 5-hexadiene, 1,6-heptadiene, 1,7-octadiene and 1,9-decadiene are copolymerized with ethylene to obtain a copolymer containing a cyclic structural unit, a dangling double bond structural unit and a polyethylene In the copolymerization of mono-Mao scandium and non-conjugated dienes, the chain length of non-conjugated dienes directly affects their polymerization activity and selectivity.