新型水杨醛亚胺钛配合物的合成及催化乙烯聚合  

Synthesis of a Series Novel Titanium Complexes with Salicylaldimine Ligands and Their Catalytic Performance for Ethylene Polymerization

作　　者：程正载[1,2] 张卫星[1] 龚凯[1] 丛野[1] 陈红祥[1] 李文兵[1,2] 

机构地区：[1]武汉科技大学化学工程与技术学院,武汉430081 [2]煤转化与新型炭材料湖北省重点实验室,武汉430081

出　　处：《材料研究学报》2015年第6期453-462,共10页Chinese Journal of Materials Research

基　　金：国家自然科学基金20803054;湖北省自然科学基金2014CFB812;煤转化与新型炭材料湖北省重点实验室开放基金WKDM201302资助项目~~

摘　　要：以价廉的水杨醛和Ti Cl4为主要原料,合成了四种水杨醛亚胺配体(5-8)及含(双苯氧基亚胺)配体的钛配合物[O-C6H4-ortho-CH=N-2,6-(i-Pr)2-C6H3]2Ti Cl2(13),[O-(5-NO2)-C6H3-ortho-CH=N-2,6-(i-Pr)2-C6H3]2Ti Cl2(14),[O-(3,5-di-Br)-C6H2-orthoCH=N-2,6-(i-Pr)2-C6H3]2Ti Cl2(15)和[O-(3,5-di-C(CH3)3)-C6H2-ortho-CH=N-2,6-(i-Pr)2-C6H3]2Ti Cl2(16)。用MS、1H-NMR和元素分析等手段表征了配体5-8分子结构,用1H-NMR和元素分析表征了配合物13-16的分子结构。经MAO(甲基铝氧烷)活化后,钛配合物(13-16)在甲苯溶剂中能有效催化乙烯聚合。在60℃,2.0 MPa及助催化剂与主催化剂摩尔比n(MAO)/n(cat)=1500∶1条件下钛配合物(14-16)催化乙烯聚合活性为1022.73-1302.27 g·PE/(mmol·Ti·h·MPa)),远高于无取代水杨醛亚胺钛配合物(13)。所得聚乙烯粘均分子量(粘度法)为19266-44754,GPC测定分子量分布Mw/Mn为1.88-2.12。具有最高活性的催化剂15催化乙烯聚合得到的聚合物样品,经13C-NMR和DSC的表征,结果表明为线型结晶聚乙烯。Four salicylaldimine ligands(called after 5, 6, 7 and 8 respectively) and their titanium complexes containing bis(phenoxy-imine) ligands, namely [O-C6H4-ortho-CH=N-2, 6-(i-Pr)2-C6H3]2Ti Cl2(called after 13), [O-(5-NO2)-C6H3-ortho-CH= N-2, 6-(i-Pr)2-C6H3]2Ti Cl2(called after 14), [O-(3, 5-di-Br)-C6H2-ortho-CH=N- 2, 6-(i- Pr)2- C6H3]2Ti Cl2(called after 15) and [O-(3, 5- di- C(CH3)3)- C6H2- ortho- CH=N- 2, 6-(i- Pr)2- C6H3]2Ti Cl2(called after 16) have been synthesized with salicylaldehyde and Ti Cl4 as raw materials. The prepared ligands and complexes were characterized by means of1H-NMR and elemental analyses as well as mass spectra. After activated with methyaluminoxane(MAO), the complexes 13- 16 become efficient catalysts for ethylene polymerization in methylbenzene. Under the conditions of T= 60℃, P=2.0 MPa and n(MAO)/n(cat)=1500∶1, the catalytic activities for the activated complexes 14-16 reached 1022.73-1302.27 g·PE /(mmol·Ti·h·MPa), which were much higher than that for the activated complex 13. The prepared polyethylene possessed a viscosity-average molecular weight in a rang of 19266-44754 measured by viscometry and a molecular weight distribution Mw/Mnin a rang of 1.88-2.12 measured by Gel Permeation in Chromatography. Among others the activated complex 15 displays the highest activity for ethylene polymerization under the same conditions. The characterization by13C- NMR and DSC showed that the polymer synthesized with catalyst of the activated complex 15 was actually a kind of linear and crystalline polyethylene.

关 键 词：有机高分子材料 钛配合物 催化剂 乙烯聚合 苯氧基亚胺配体 活性 

分 类 号：O641.4[理学—物理化学]