双核茂金属催化剂的合成、表征与应用
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摘要
使用桥连配体锂盐与MCl_4络合,合成了4个不同结构的双核茂金属化合物[μ,μ-(CH_2)_3]{[C(H)·(η~5-C_5H_4)(η~5-C_(13)H_8)](MCl_2)}_2[M=Zr or Ti](4,5)和[μ,μ-(CH_2)_3]{[C(H)(η~5-C_5H_4)(η~5-C_9H_6)]·(MCl_2)}_2[M=Zr or Ti](6,7),配体和化合物都经过核磁氢谱(~1H NMR)、碳谱(~(13)C NMR)、红外光谱(IR)及元素分析等表征,确认了化学结构.以甲基铝氧烷(MAO)为助催化剂,化合物4～7为催化剂催化丙烯聚合,考察了聚合温度、乙烯压力、铝钛或铝锆比对催化剂活性及聚合物分子量的影响.结果表明,多亚甲基桥连双核茂金属是高活性乙烯和丙烯聚合催化剂,乙烯聚合活性最高达到7.5×10~6g PE/(mol Zr·h)(化合物6),丙烯聚合活性达10×10~5g s PP/(mol Zr·h)(化合物4).所得间规聚丙烯(s PP)的间规度指数(SI,r)达到90%.在同样条件下,双核化合物的催化活性、聚合物分子量M_w(>100000)以及分子量分布(MWD>2.5)均比相应的单核化合物高(M_w<70000,MWD≤2),表明该体系中存在较强的核效应.
In order to investigate the differences between binuclear metallocene catalysts and mononuclear catalysts for propylene syndiotactic polymerization,binuclear metallocene complexes [μ,μ-(CH_2)_3]·{[C(H)(η~5-C_5H_4)(η~5-C_(13)H_8)](MCl_2)}_2[M = Zr or Ti ](4, 5), and [μ,μ-(CH_2)_3]·{ [C(H)(η~5-C_5H_4) ·(η~5-C_9H_6) ](MCl-2)}_2[M = Zr or Ti](6,7) were synthesized and characterized by ~1H NMR,~(13)C NMR,mass spectra and elemental analysis. When combined with methylaluminoxane(MAO),these metallocene complexes shown high catalytic activity for the polymerization of ethylene and propylene,the activity of polyethylene(PE) reaches up to 7. 5 × 10~6 g PE/(mol Zr·h)(complex 6) and 10 × 10~5 g sP P/(mol Zr·h)(complex 4) for polypropylene(PP). The syndiotacticity index(SI) of polypropylene(sP P) by complex 4 was more than 90%. It is found that,under the same conditions,binuclear complexes' catalytic activity,M_w(>100000) and molecular weight distribution(MWD>2. 5) are higher than that of corresponding mononuclear metallocene complexes(M_w<70000,MWD≤2),which suggests that there are cooperation effect in binuclear system.
In order to investigate the differences between binuclear metallocene catalysts and mononuclear catalysts for propylene syndiotactic polymerization,binuclear metallocene complexes [μ,μ-(CH_2)_3]·{[C(H)(η~5-C_5H_4)(η~5-C_(13)H_8)](MCl_2)}_2[M = Zr or Ti ](4, 5), and [μ,μ-(CH_2)_3]·{ [C(H)(η~5-C_5H_4) ·(η~5-C_9H_6) ](MCl-2)}_2[M = Zr or Ti](6,7) were synthesized and characterized by ~1H NMR,~(13)C NMR,mass spectra and elemental analysis. When combined with methylaluminoxane(MAO),these metallocene complexes shown high catalytic activity for the polymerization of ethylene and propylene,the activity of polyethylene(PE) reaches up to 7. 5 × 10~6 g PE/(mol Zr·h)(complex 6) and 10 × 10~5 g sP P/(mol Zr·h)(complex 4) for polypropylene(PP). The syndiotacticity index(SI) of polypropylene(sP P) by complex 4 was more than 90%. It is found that,under the same conditions,binuclear complexes' catalytic activity,M_w(>100000) and molecular weight distribution(MWD>2. 5) are higher than that of corresponding mononuclear metallocene complexes(M_w<70000,MWD≤2),which suggests that there are cooperation effect in binuclear system.
引文
[1]Hao P.,Zhang S.,Yi J.J.,Sun W.H.,J.Mol.Catal.A:Chem.,2009,302,1-6
[2]Delferro M.,Marks T.J.,Chem.Rev.,2011,111,2450-2485
[3]Motta A.,Fragal2 I.L.,Marks T.J.,J.Am.Chem.Soc.,2009,131,3974-3984
[4]Suo H.Y.,Solan G.A.,Ma Y.P.,Sun W.H.,Coord.Chem.Rev.,2018,372,101-116
[5]Ewen J.A.,J.Am.Chem.Soc.,1984,106(21),6355-6364
[6]Zhang Y.T.,Ning Y.L.,Caporaso L.,Cavallo L.,Chen E.Y.X.,J.Am.Chem.Soc.,2010,132,2695-2709
[7]Lin W.F.,Tsai J.C.,J.Polym.Sci.,Part A:Polym.Chem.,2008,46(6),2167-2176
[8]Lin W.F.,Hsiao T.J.,Tsai J.C.,Chung T.M.,Ho R.M.,J.Polym.Sci.,Part A:Polym.Chem.,2008,46(14),4843-4856
[9]Kaminsky W.,Strübel C.,Lechert H.,Genske D.,Woo S.I.,Macromol.Rapid Commun.,2000,21,909-912
[10]Herzog T.A.,Zubris D.L.,Bercaw J.E.,J.Am.Chem.Soc.,1996,118,11988-11989
[11]Saito J.J.,Mitan M.,Onda M.,Mohri J.I.,Ishii S.I.,Yoshida Y.,Nakano T.,Tanaka H.,Matsugi T.,Kojoh S.I.,Kashiwa N.,Fujita T.,Macromol.Rapid Commun.,2001,22,1072-1075
[12]Miyake G.M.,Chen E.Y.X.,Polym.Chem.,2011,2,2462-2480
[13]Stephan J.,Rolf M.,Herbert P.,J.Organomet.Chem.,1993,460(2),191-195
[14]Green M.L.H.,Ishihara N.,J.Chem.Soc.Dalton Trans.,1994,5(5),657-665
[15]Diamond G.M.,Chernega A.N.,Mountford P.,Green M.L.H.,J.Chem.Soc.,Dalton Trans.,1996,921-938
[16]Yan X.F.,Chernega A.,Green M.L.H.,Sanders J.,Souter J.,Ushioda T.,J.Mol.Catal.A:Chem.,1998,128,119-141
[17]Wu Q.L.,Su Q.,Ye L.,Li G.H.,Mu Y.,Dalton Trans.,2010,39,2525-2535
[18]Sun T.X.,Yi J.J.,Wang Y.G.,Zhang M.G.,Yuan Y.,Mao J.,Binuclear Heterocyclic Catalyst and Application Thereof in Propylene Homopolymerization and Copolymerization,CN106543302A,2015-09-18(孙天旭,义建军,王永刚,张明革,袁苑,毛静.双核杂环催化剂及其在丙烯均聚和共聚中的应用,CN106543302A,2015-09-18)
[19]Xu S.,Huang J.L.,J.Appl.Polym.Sci.,2013,130(4),2891-2900
[20]Khalil C.,Henrik O.,Cheminform,2004,45,6741-6744
[21]Erickson M.S.,Cronan J.M.,Garcia J.G.,J.Org.Chem.,1992,57(8),2504-2508
[22]Razavi A.,Atwood J.L.,J.Organomet.Chem.,1996,520(s1/2),115-120
[23]Wang B.Q.,Mu B.,Deng X.B.,Cui H.L.,Xu S.S.,Zhou X.Z.,Zou F.L.,Li Y.,Yang L.,Yi Y.F.,Ha Y.L.,Chem.A:Eur.J.,2004,11(2),669-679
[24]Li T.C.,Lan Z.,Xie G.Y.,Luo D.R.,Li L.,Xiong S.F.,Zhang L.,Ou Y.,Li P.,Zhang A.Q.,Catal.Lett.,2017,147(4),996-1005
[25]Li W.W.,Mu H.L.,Liu J.Y.,Li Y.S.,J.Organomet.Chem.,2017,836/837,34-43
[26]Chen Z.T.,Yao E.D.,Wang J.C.,Gong X.Y.,Ma Y.G.,Macromolecules,2016,49,8848-8854
[27]Chen Z.T.,Zhao X.X.,Gong X.Y.,Xu D.,Ma Y.G.,Macromolecules,2017,50,6561-6568
[28]Xu D.,Zhao X.X.,Chen Z.T.,Ma Y.G.,Chinese J.Polym.Sci.,2018,36(2),244-251
[29]Xing Q.F.,Song K.F.,Liang T.L.,Liu Q.B.,Sun W.H.,Redshaw C.,Dalton Trans.,2014,43,7830-7837
[30]Luo G.,Luo Y.,Hou Z.M.,Qu J.P.,Organometallics,2016,35,778-784
[31]Ye J.D.,Ye Z.B.,Polymers,2017,9(282),1-21
[32]Brintzinger H.H.,Fischer D.,Mülhaupt R.,Angew.Chem.Int.Ed.,1995,34(11),1143-1170
[2]Delferro M.,Marks T.J.,Chem.Rev.,2011,111,2450-2485
[3]Motta A.,Fragal2 I.L.,Marks T.J.,J.Am.Chem.Soc.,2009,131,3974-3984
[4]Suo H.Y.,Solan G.A.,Ma Y.P.,Sun W.H.,Coord.Chem.Rev.,2018,372,101-116
[5]Ewen J.A.,J.Am.Chem.Soc.,1984,106(21),6355-6364
[6]Zhang Y.T.,Ning Y.L.,Caporaso L.,Cavallo L.,Chen E.Y.X.,J.Am.Chem.Soc.,2010,132,2695-2709
[7]Lin W.F.,Tsai J.C.,J.Polym.Sci.,Part A:Polym.Chem.,2008,46(6),2167-2176
[8]Lin W.F.,Hsiao T.J.,Tsai J.C.,Chung T.M.,Ho R.M.,J.Polym.Sci.,Part A:Polym.Chem.,2008,46(14),4843-4856
[9]Kaminsky W.,Strübel C.,Lechert H.,Genske D.,Woo S.I.,Macromol.Rapid Commun.,2000,21,909-912
[10]Herzog T.A.,Zubris D.L.,Bercaw J.E.,J.Am.Chem.Soc.,1996,118,11988-11989
[11]Saito J.J.,Mitan M.,Onda M.,Mohri J.I.,Ishii S.I.,Yoshida Y.,Nakano T.,Tanaka H.,Matsugi T.,Kojoh S.I.,Kashiwa N.,Fujita T.,Macromol.Rapid Commun.,2001,22,1072-1075
[12]Miyake G.M.,Chen E.Y.X.,Polym.Chem.,2011,2,2462-2480
[13]Stephan J.,Rolf M.,Herbert P.,J.Organomet.Chem.,1993,460(2),191-195
[14]Green M.L.H.,Ishihara N.,J.Chem.Soc.Dalton Trans.,1994,5(5),657-665
[15]Diamond G.M.,Chernega A.N.,Mountford P.,Green M.L.H.,J.Chem.Soc.,Dalton Trans.,1996,921-938
[16]Yan X.F.,Chernega A.,Green M.L.H.,Sanders J.,Souter J.,Ushioda T.,J.Mol.Catal.A:Chem.,1998,128,119-141
[17]Wu Q.L.,Su Q.,Ye L.,Li G.H.,Mu Y.,Dalton Trans.,2010,39,2525-2535
[18]Sun T.X.,Yi J.J.,Wang Y.G.,Zhang M.G.,Yuan Y.,Mao J.,Binuclear Heterocyclic Catalyst and Application Thereof in Propylene Homopolymerization and Copolymerization,CN106543302A,2015-09-18(孙天旭,义建军,王永刚,张明革,袁苑,毛静.双核杂环催化剂及其在丙烯均聚和共聚中的应用,CN106543302A,2015-09-18)
[19]Xu S.,Huang J.L.,J.Appl.Polym.Sci.,2013,130(4),2891-2900
[20]Khalil C.,Henrik O.,Cheminform,2004,45,6741-6744
[21]Erickson M.S.,Cronan J.M.,Garcia J.G.,J.Org.Chem.,1992,57(8),2504-2508
[22]Razavi A.,Atwood J.L.,J.Organomet.Chem.,1996,520(s1/2),115-120
[23]Wang B.Q.,Mu B.,Deng X.B.,Cui H.L.,Xu S.S.,Zhou X.Z.,Zou F.L.,Li Y.,Yang L.,Yi Y.F.,Ha Y.L.,Chem.A:Eur.J.,2004,11(2),669-679
[24]Li T.C.,Lan Z.,Xie G.Y.,Luo D.R.,Li L.,Xiong S.F.,Zhang L.,Ou Y.,Li P.,Zhang A.Q.,Catal.Lett.,2017,147(4),996-1005
[25]Li W.W.,Mu H.L.,Liu J.Y.,Li Y.S.,J.Organomet.Chem.,2017,836/837,34-43
[26]Chen Z.T.,Yao E.D.,Wang J.C.,Gong X.Y.,Ma Y.G.,Macromolecules,2016,49,8848-8854
[27]Chen Z.T.,Zhao X.X.,Gong X.Y.,Xu D.,Ma Y.G.,Macromolecules,2017,50,6561-6568
[28]Xu D.,Zhao X.X.,Chen Z.T.,Ma Y.G.,Chinese J.Polym.Sci.,2018,36(2),244-251
[29]Xing Q.F.,Song K.F.,Liang T.L.,Liu Q.B.,Sun W.H.,Redshaw C.,Dalton Trans.,2014,43,7830-7837
[30]Luo G.,Luo Y.,Hou Z.M.,Qu J.P.,Organometallics,2016,35,778-784
[31]Ye J.D.,Ye Z.B.,Polymers,2017,9(282),1-21
[32]Brintzinger H.H.,Fischer D.,Mülhaupt R.,Angew.Chem.Int.Ed.,1995,34(11),1143-1170