乙烯与1-己烯共聚及其共聚物的微观结构  

Copolymerization of Ethylene and 1-Hexene and the Microstructure of 1-Hexene Copolymers

作　　者：吕春胜[1] 杨阳[1] 李东凯[1] 王俊[1] 母瀛[2] 周晓光[3] 

机构地区：[1]东北石油大学化学化工学院石油与天然气化工省重点实验室,黑龙江大庆163318 [2]吉林大学化学学院超分子结构与材料教育部重点实验室,吉林长春130012 [3]大庆油田有限责任公司海拉尔石油勘探开发指挥部开发技术中心,内蒙古海拉尔021000

出　　处：《石油学报（石油加工）》2015年第1期153-159,共7页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：黑龙江省科技攻关项目(GZ08A404)基金资助

摘　　要：采用限制几何构型催化剂2-四甲基环戊二烯基-4,6-二叔丁基苯氧基二氯化钛/助剂Al（i-Bu）3-[Ph3C]＋[B（C6F5）4]-催化体系催化乙烯与1-己烯共聚,采用13 C NMR、GPC和DSC表征了共聚物的结构和性质,探讨了反应温度（40~80℃）和共聚单体初始浓度（0.1~0.4mol/L）对该体系催化活性和共聚物性质及其微观结构的影响,并采用一级Markovian模型和Bernoullion模型对共聚物序列分布进行概率统计分析。结果表明,在实验条件下,得到的共聚物是无规结构的聚合物,具有较低的相对分子质量（（0.87~6.73）×10^4）、适中的共聚单体质量分数（8.8%~28.8%）和熔点（107.5~121.0℃）。该共聚物的链增长符合一级Markovian模型的链增长机理,1-己烯共聚单体配位或插入到{共聚物链-1-己烯-1-己烯-催化剂}序列（[HH]）要比配位或插入到{共聚物链-乙烯-1-己烯-催化剂}序列（[EH]）更容易（概率参数PHH〉PEH）,乙烯共聚单体配位或插入到{共聚物链-乙烯-乙烯-催化剂}序列（[EE]）要比配位或插入到{共聚物链-1-己烯-乙烯-催化剂}序列（[HE]）更容易（概率参数PEE〉PHE）。PEH〈0.5和PHE〉0.5表现出了随机分布的乙烯基共聚物的特征。Copolymerization of ethylene and 1-hexene was performed by using a constrained geometry catalyst of 2-（tetramethyl cyclopentadienyl）-4,6-di-tert-butylphenoxy-titanium dichloride with Al（i-Bu）3-[Ph3C]＋[B（C6F5）4]-.The copolymers were characterized by 13 C NMR,DSC and GPC methods.The effects of reaction temperature（40-80℃）and the concentration of 1-hexene comonomer（0.1-0.4 mol/L）on the copolymerization activity and properties of the copolymers were investigated.The probability analysis of the monomer triad sequence distribution was carried out based on the first-order Markovian model and Bernoullion model. The effect of the concentration of 1-hexene and reaction temperature on monomer sequence distribution was discussed.The results showed that the copolymers possessed a atactic structure,with the relative molecular mass of（0.87-6.73）×10^4,the co-monomer mass fraction of 8.8%-28.8% and the melting point of 107.5-121.0℃.The propagation mechanism of the copolymerization process was corresponded to the first-order Markovian model.It is more probable that a 1-hexene monomer unit is added to the sequence {polymer-1-hexene-1-hexene-catalyst}（[HH]）than to the sequence {polymerethylene-1-hexene-catalyst}（[EH]）（PHHPEH）,meanwhile,anethylene monomer unit is added to the sequence {polymer-ethylene-ethylene-catalyst}（[EE]）more easily than to the sequence {polymer-1-hexene-ethylene-catalyst}（[HE]）（PEE PHE）.The value of probability parameters（PEH 0.5and PHE0.5）showed a feature of vinyl copolymer possessing a random distribution.

关 键 词：限制几何构型催化剂 乙烯-己烯共聚 序列分布 概率统计 微观结构 

分 类 号：TE626[石油与天然气工程—油气加工工程]