乙烯与降冰片烯的共聚及产物表征  

Synthesis and Characterization of Copolymers from Ethylene with Norbornene

作　　者：吕春胜[1] 许云飞[1] 颜子龙[1] 陈怡[1] 王丹丹[2] 

机构地区：[1]东北石油大学化学化工学院,黑龙江大庆163318 [2]大庆油田有限责任公司第九采油厂,黑龙江大庆163318

出　　处：《高分子材料科学与工程》2013年第2期31-34,共4页Polymer Materials Science & Engineering

基　　金：黑龙江省科技攻关项目(GZ08A404)

摘　　要：用限制几何构型茂金属催化体系[2-Me4Cp-4,6-tBu2-PhO]TiCl2/Al(iBu)3/Ph3C+B(C6F5)4-(CGC)研究了乙烯/降冰片烯的共聚。考察了降冰片烯单体浓度对聚合反应活性和聚合物性能、结构的影响。用核磁共振(13C-NMR)、扫描电镜(SEM)、差热分析(DSC)和X射线衍射(X-ray)方法对共聚物进行了表征。结果表明,所得产物(降冰片烯含量(2.5～9.4)NB%)的形貌是交联网状的,主要是含有等规和间规交替序列的无规共聚物;在0.4 mol/L浓度下可得到有双熔点(92℃,112℃)分布的共聚物。Copolymerization of ethylene with norbornene was studied using metallocene with constrained geometry catalyst [ 2-Me4Cp-4,6-tBu2-PhO ] TICl2/Al （iBu）3/Ph3C＋ B （ C6Fs ）4- as catalyst. Effects of norbornene monomer concentration on the copolymerization activity and copolymer structure of ethylene-norbornene were investigated. The ethylene-norbornene copolymers were characterized by 13 C-NMR, SEM, DSC and X-ray. Under experiment conditions（temperature = 70 ℃, copolymerization time = 30 rain, p （ethylene） = 5.07 × 10^5 Pa, Al/Ti = 120, B/Ti = 1.2, solvent = toluene, catalyst = 1 mg）, the results show that polymerization activity is （3217 -- 5186） kg· polymer / （mol Ti＂ h ） and norbornene insertion rate on the copolymer straight chain is 2.5% -9.4%. Copolymer microstructures indicate that the product is mainly alternating stereoirregular copolymer, which contains the isotactic and syndiotactic sequence. Copolymers are displayed two melting temperatures（92 ℃, 112 ℃ ） under 0.4mol/L concentration, and the SEM photographs show that the morphologies of the copolymers are cross-linked.

关 键 词：限制几何构型茂金属催化剂 乙烯 降冰片烯 共聚反应 微观结构 

分 类 号：TQ316.342[化学工程—高聚物工业]