| 晁丽,王建伟,米普科.以硼化物为活化剂制备负载茂金属催化剂催化乙烯/α-烯烃共聚合[J].分子催化,2015,(3):197-206 |
| 以硼化物为活化剂制备负载茂金属催化剂催化乙烯/α-烯烃共聚合 |
| Ethylene/α-olefin copolymerization catalyzed by supported metallocene catalysts with boron activators |
| 投稿时间：2015-04-17 修订日期：2015-05-05 |
| DOI： |
| 中文关键词: 负载茂金属催化剂，硼，乙烯，α-烯烃，共聚 |
| 英文关键词:supported metallocene catalyst, boron, ethylene, α-olefin, copolymerization |
| 基金项目:国家自然科学基金项目（面上项目，重点项目，重大项目） |
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| 摘要点击次数: 2692 |
| 全文下载次数: 1912 |
| 中文摘要: |
| 本研究以硅胶为载体，以Cp2ZrCl2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?0-4mol/g SiO2，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/(molZr?h)，是相同条件下以MAO为活化剂时活性的511~1090倍，同样达到107g/(molZr?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2.97mol%；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0.91~0.92g/cm3之间，属于mLLDPE范畴。 |
| 英文摘要: |
| In this paper, the supported metallocene catalysts were prepared, in which SiO2 was used as the carrier, Cp2ZrCl2 was used as the main catalyst and MAO, B(C6F5)3, [HNMe2Ph][B(C6F5)4], [Ph3C][B(C6F5)4], B(C6F5)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 boron was 5.1?0-4 mol/g SiO2, the molar ratio of B:Zr was between 14.10~19.04, the activity of the supported metallocene catalysts reached up to 107 g/(molZr?h) which was 511~1090 times higher than that of MAO under the same conditions. 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(C6F5)3 as activator, the catalytic activity of supported metallocene catalyst with [HNMe2Ph][B(C6F5)4] or [Ph3C][B(C6F5)4] as activator was higher. It was also found that [Ph3C][B(C6F5)4] system had the most narrow molecular weight distribution(MWD) and maximum 1-hexene content(2.97 mol%). 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. |
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