氧桥联双核钛、镍配合物的合成及催化制备双峰聚乙烯
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摘要
从2种氧原子桥联双膦化合物双(2-二苯基膦苯基)醚(1a)和4,5-双(二苯基膦)-9,9-二甲基氧杂蒽(1b)出发,合成氧原子桥联双膦亚胺钛、镍配合物.在甲苯中回流条件下首先将化合物1a和1b与叠氮三甲基硅烷发生Staudinger反应,分别生成单和双膦亚胺前驱体2a和2b.然后再与环戊二烯基三氯化钛反应,脱去三甲基氯硅烷后得到相应膦亚胺过渡金属钛配合物3a和3b.单钛中心配合物3b进一步与乙二醇二甲醚溴化镍反应生成钛-镍异核双中心配合物4b.通过1H NMR,13C NMR,31P NMR,FTIR及元素分析对产物进行了表征,并利用X射线单晶衍射分析确定了配合物3a和3b的分子结构.在助催化剂甲基铝氧烷(MAO)作用下,配合物3a和4b对乙烯聚合均表现出较高的催化活性,其中双钛中心配合物3a催化得到较宽分子量的聚乙烯产物,而异核双中心配合物4b催化得到呈双峰分布的聚乙烯产物.
To explore the potential of oxygen-bridged bisphosphinimine titanium and nickel complexes possessing bimetallic centers as catalysts for olefin polymerization, two oxygen-bridged diphosphorus compounds,named bis-(2-diphenylphosphino) phenylether(1 a) and 9,9-dimethyl-4,6-bis(diphenylphosphino) xanthene(1 b),were synthesized. After Staudinger reaction with Me3 SiN3 in toluene under reflux,compound 1 a with a flexible diphenyl ether bridge was converted into the bisphosphinimine precusor,while compound 1 b with a rigid xanthene bridge was transformed into the monophosphinimine one. Subsequently,the dehalosilylation with CpTiCl3 afforded the corresponding phosphinimine titanium complexes 3 a and 3 b,respectively. Single titanium center complex 3 b further reacts with Ni Br2(DME) to translate into titaniumnickel heteronuclear bimetallic complex 4 b. The structures of the complexes were characterized by1 H,13 C,31 P NMR and elemental analyses. And the molecular structures of complexes 3 a and 4 b were further determined by single-crystal X-ray diffraction analysis. When activated by the methylaluminoxane(MAO),complexes 3 a and 4 b displayed high catalytic activity for ethylene polymerization. The bimetallic titanium complex 3 a produced a wide molecular weight distribution polyethylene product,while the titanium-nickel heteronuclear bimetallic complex 4 b gave rise to the bimodal polyethylene product.
To explore the potential of oxygen-bridged bisphosphinimine titanium and nickel complexes possessing bimetallic centers as catalysts for olefin polymerization, two oxygen-bridged diphosphorus compounds,named bis-(2-diphenylphosphino) phenylether(1 a) and 9,9-dimethyl-4,6-bis(diphenylphosphino) xanthene(1 b),were synthesized. After Staudinger reaction with Me3 SiN3 in toluene under reflux,compound 1 a with a flexible diphenyl ether bridge was converted into the bisphosphinimine precusor,while compound 1 b with a rigid xanthene bridge was transformed into the monophosphinimine one. Subsequently,the dehalosilylation with CpTiCl3 afforded the corresponding phosphinimine titanium complexes 3 a and 3 b,respectively. Single titanium center complex 3 b further reacts with Ni Br2(DME) to translate into titaniumnickel heteronuclear bimetallic complex 4 b. The structures of the complexes were characterized by1 H,13 C,31 P NMR and elemental analyses. And the molecular structures of complexes 3 a and 4 b were further determined by single-crystal X-ray diffraction analysis. When activated by the methylaluminoxane(MAO),complexes 3 a and 4 b displayed high catalytic activity for ethylene polymerization. The bimetallic titanium complex 3 a produced a wide molecular weight distribution polyethylene product,while the titanium-nickel heteronuclear bimetallic complex 4 b gave rise to the bimodal polyethylene product.
引文
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[3]Ban Q.,Sun J.Q.,Chem.J.Chinese Universities,2003,24(12),2304-2307(班青,孙俊全.高等学校化学学报,2003,24(12),2304-2307)
[4]Jin Y.L.,Zhao N.,Cheng R.H.,Liu B.P.,CIESC Journal,2017,68(2),485-495(金玉龙,赵柠,程瑞华,刘柏平.化工学报,2017,68(2),485-495)
[5]Cheng R.H.,Xue X.,Liu W.W.,Zhao N.,He X.L.,Liu Z.,Liu B.P.,Macromol.React.Eng.,2015,9(5),462-472
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[11]Li M.Y.,Shu X.,Cai Z.G.,Eisen M.S.,Organometallics,2018,37(7),1172-1180
[12]Delferro M.,Marks T.J.,Chem.Rev.,2011,111,2450-2485
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[17]Xu S.,Huang J.L.,J.Appl.Polym.Sci.,2013,130,2891-2900
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