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    郑浩, 王原, 刘婷婷, 叶晓峰, 罗勇. 水杨醛亚胺锆络合物的合成及其催化乙烯聚合[J]. 功能高分子学报, 2018, 31(4): 322-329. doi: 10.14133/j.cnki.1008-9357.20171212001
    引用本文: 郑浩, 王原, 刘婷婷, 叶晓峰, 罗勇. 水杨醛亚胺锆络合物的合成及其催化乙烯聚合[J]. 功能高分子学报, 2018, 31(4): 322-329. doi: 10.14133/j.cnki.1008-9357.20171212001
    ZHENG Hao, WANG Yuan, LIU Ting-ting, YE Xiao-feng, LUO Yong. Synthesis of Salicylaldiminato Zirconium Complexes and Its Catalysis Application for Ethylene Polymerization[J]. Journal of Functional Polymers, 2018, 31(4): 322-329. doi: 10.14133/j.cnki.1008-9357.20171212001
    Citation: ZHENG Hao, WANG Yuan, LIU Ting-ting, YE Xiao-feng, LUO Yong. Synthesis of Salicylaldiminato Zirconium Complexes and Its Catalysis Application for Ethylene Polymerization[J]. Journal of Functional Polymers, 2018, 31(4): 322-329. doi: 10.14133/j.cnki.1008-9357.20171212001

    水杨醛亚胺锆络合物的合成及其催化乙烯聚合

    Synthesis of Salicylaldiminato Zirconium Complexes and Its Catalysis Application for Ethylene Polymerization

    • 摘要: 以3-叔丁基-5-甲氧基水杨醛和邻取代苯胺为原料,合成了两个水杨醛亚胺配体( 1,2 )及相应的锆络合物( 3,4 )。用质谱(MS)、核磁共振氢谱(1H-NMR)和核磁共振碳谱(13C-NMR)等方法表征了配体及络合物的结构,采用流变仪、差示扫描量热仪(DSC)对聚合物进行了分析。研究了乙烯压力、聚合温度、时间、溶剂、铝锆物质的量之比(nAlnZr)等对络合物催化性能和聚乙烯分子量的影响。结果表明,在甲基铝氧烷(MAO)的助催化下,锆络合物在甲苯中对乙烯聚合具有较好的催化活性,所得聚合物为超高分子量聚乙烯。在30℃、0.9 MPa下,络合物 4 在正己烷中的催化活性达到60.2 kg/(mmol·h),聚乙烯的黏均分子量最高可达6.6×106,分子量分布为2.4,聚合过程具有良好的可控性。

       

      Abstract: Salicylaldehyde imine ligands ( 1, 2 ) and corresponding salicylaldiminato zirconium complexes ( 3, 4 ) were prepared via the condensation reaction by using 3-tert-butyl-5-methoxy salicylaldehyde and ortho-substituted anilines as the materials. Both ligands and complexes were characterized by mass spectrum, 1H-NMR and 13C-NMR spectroscopy. In the presence of methylaluminoxane (MAO) as a co-catalyst, both zirconium complexes exhibited good catalytic activity for ethylene polymerization in toluene, producing ultra high molecular weight polyethylene (UHMWPE). Complex 3 was found to exhibit the activity of 50.2 kg/(mmol·h) at 50℃ and 0.9 MPa pressure in toluene, resulting in UHMWPE with a viscosity average molecular weight value of 1.5×106. In case of complex 4 , the activity increased from 45.5 kg/(mmol·h) at 17℃ to 55.6 kg/(mmol·h) at 50℃. An obvious decrease of activity could be observed when the temperature was above 50℃. This decrease was probably due to the decomposition of active species at high temperature. High nAl:nZr ratio led to an enhancement in activity and a decrease in molecular weight, which could be ascribed to the more active species and higher chain transfer rate in the catalytic system. In addition, complex 4 showed higher ethylene polymerization activity of 60.2 kg/(mmol·h) at 30℃ and 0.9 MPa when n-hexane was employed as the solvent, affording the polyethylene with a viscosity average molecular weight value up to 6.6×106. The rheometer analysis of polymer generated from complex 4 revealed a narrow molecular weight distribution 2.4, indicating a well-controlled manner during the polymerization process. Characteristic absorption appearing at 1 471 cm-1 and 719 cm-1 from infrared spectrum proved that the microstructure of UHMWPE sample was linear. The high melting points of obtained polymers measured by Differential Scanning Calorimetry (DSC), ranging from 138℃ to 140℃, were typical for linear polyethylene.

       

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