文献类型：期刊文献

中文题名：以硼化物为活化剂制备负载茂金属催化剂催化乙烯均聚和乙烯/α-烯烃共聚合(英文)

英文题名：Ethylene Homopolymerization and Ethylene/α- olefin Copolymerization Catalyzed by Supported Metallocene Catalysts with Boron Activators

作者：晁丽[1];王建伟[1];米普科[1];许胜[1];陈谦[2];王斯晗[2]

机构：[1]华东理工大学材料科学与工程学院上海市先进聚合物材料重点实验室超细材料制备与应用教育部重点实验室,上海200237;[2]中国石油天然气股份有限公司石油化工研究院大庆化工研究中心,黑龙江大庆163714

年份：2015

卷号：29

期号：3

起止页码：197

中文期刊名：分子催化

外文期刊名：Journal of Molecular Catalysis(China)

收录：CSTPCD;;EI(收录号：20153101095234);Scopus;北大核心:【北大核心2014】；CSCD:【CSCD2015_2016】；

基金：supported by the National Natural Science Foundation of China(No.U1162111 and U1362111)

语种：中文

中文关键词：负载茂金属催化剂;硼;乙烯;α-烯烃;共聚

外文关键词：supported metallocene catalyst;;boron;;ethylene;;α-olefin;;copolymerization

摘要：以硅胶为载体,以Cp2ZrC l2为主催化剂,分别以甲基铝氧烷(MAO)、三五氟苯基硼(B(C6F5)3)、N,N-二甲基苯铵四(五氟苯基)硼酸盐([HNMe2Ph][B(C6F5)4])、三苯碳鎓四(五氟苯基)硼酸盐([Ph3C][B(C6F5)4])、三五氟苯基硼/三甲基铝(B(C6F5)3/TMA)为活化剂制备了负载茂金属催化剂,考察了它们对乙烯均聚、乙烯/α-烯烃共聚合的影响.实验结果表明,当硼化物用量为5.1×10-4mol/g SiO 2,B/Zr在14.10~19.04之间时,负载茂金属催化剂催化烯烃聚合活性达107g/(molZ r·h),是相同条件下以MAO为活化剂时活性的511~1 090倍,同样达到107g/(molZ r·h)的催化活性,硼化物用量仅仅为MAO用量1/16;和B(C6F5)3相比,以[HNMe2Ph][B(C6F5)4]和[Ph3C][B(C6F5)4]为活化剂制备的负载茂金属催化剂活性较高,并且以[Ph3C][B(C6F5)4]为活化剂制备的负载茂金属催化剂所得共聚物分子量分布最窄,乙烯/1-己烯共聚物中共单体含量最高,为2.97%;采用硼化物为活化剂制备的负载茂金属催化剂催化乙烯/1-己烯、乙烯/1-辛烯共聚合所得共聚产物分子量分布较窄,密度在0.91~0.92 g/cm3之间,属于mL LDPE范畴.
In this paper,the supported metallocene catalysts were prepared,in which SiO2 was used as the carrier,Cp2 ZrCl2 was used as the main catalyst and MAO,B(C6 F5 )3 ,[HNMe2 Ph][B(C6 F5 )4 ],[Ph3 C][B(C6 F5 )4 ],B(C6 F5 )3 /TMA were used as the activators respectively.The effect of the activators on the catalytic properties in ethylene homopolymerization and ethylene /α-olefins copolymerization was investigated.From the results,it was found that when the added amount of bo-ron was 5.1×10-4 mol/g SiO2 ,the molar ratio of B ∶Zr was between 14.10 ~19.04,the activity of the supported metallo-cene catalysts reached up to 107 g/(molZr·h)which was 511 ~1 090 times higher than that of MAO under the same condi-tions.The added amount of boron was only 1 /16 of MAO for the same catalytic activity of 107 g/(molZr·h).Compared with the supported catalyst with B (C6 F5 )3 as activator,the catalytic activity of supported metallocene catalyst with [HNMe2 Ph][B(C6 F5 )4 ]or [Ph3 C][B(C6 F5 )4 ]as activator was higher.It was also found that [Ph3 C][B(C6 F5 )4 ] system had the most narrow molecular weight distribution(MWD)and maximum 1-hexene content(2.97%).Copolymers prepared by the supported metallocene catalysts with boron activators had narrow MWD and density between 0.91 ~0.92 g/cm3 which belonged to the scope of mLLDPE.