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CN101045737A - Bridging metallocene dinuclear catalyst and its preparation method and application - Google Patents

  • ️Wed Oct 03 2007
Bridging metallocene dinuclear catalyst and its preparation method and application Download PDF

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Publication number
CN101045737A
CN101045737A CN 200710013764 CN200710013764A CN101045737A CN 101045737 A CN101045737 A CN 101045737A CN 200710013764 CN200710013764 CN 200710013764 CN 200710013764 A CN200710013764 A CN 200710013764A CN 101045737 A CN101045737 A CN 101045737A Authority
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China
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mol ratio
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2007-03-08
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Chinese (zh)
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CN100546994C (en
Inventor
班青
李鹏
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Qilu University of Technology
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Qilu University of Technology
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2007-03-08
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2007-10-03
2007-03-08 Application filed by Qilu University of Technology filed Critical Qilu University of Technology
2007-03-08 Priority to CNB2007100137644A priority Critical patent/CN100546994C/en
2007-10-03 Publication of CN101045737A publication Critical patent/CN101045737A/en
2009-10-07 Application granted granted Critical
2009-10-07 Publication of CN100546994C publication Critical patent/CN100546994C/en
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  • 239000003054 catalyst Substances 0.000 title claims description 23
  • 238000002360 preparation method Methods 0.000 title description 5
  • 150000001875 compounds Chemical class 0.000 claims abstract description 29
  • 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
  • 239000010936 titanium Substances 0.000 claims abstract description 10
  • RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
  • QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
  • 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
  • 229910052726 zirconium Chemical group 0.000 claims abstract description 9
  • 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
  • 125000003118 aryl group Chemical group 0.000 claims abstract description 5
  • YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
  • YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 38
  • MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 36
  • 239000007788 liquid Substances 0.000 claims description 31
  • 239000007787 solid Substances 0.000 claims description 31
  • 229910003002 lithium salt Inorganic materials 0.000 claims description 27
  • 159000000002 lithium salts Chemical class 0.000 claims description 27
  • VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
  • 238000000605 extraction Methods 0.000 claims description 25
  • OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 24
  • 238000006243 chemical reaction Methods 0.000 claims description 24
  • RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 23
  • LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 17
  • 239000002904 solvent Substances 0.000 claims description 16
  • OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 14
  • VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
  • 238000005119 centrifugation Methods 0.000 claims description 12
  • 239000007795 chemical reaction product Substances 0.000 claims description 12
  • 238000003756 stirring Methods 0.000 claims description 12
  • 229910052751 metal Inorganic materials 0.000 claims description 10
  • 239000002184 metal Substances 0.000 claims description 9
  • 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 8
  • ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
  • 239000000047 product Substances 0.000 claims description 8
  • XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 7
  • VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
  • PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
  • 238000001035 drying Methods 0.000 claims description 7
  • 230000007062 hydrolysis Effects 0.000 claims description 7
  • 238000006460 hydrolysis reaction Methods 0.000 claims description 7
  • 239000012044 organic layer Substances 0.000 claims description 7
  • 239000003960 organic solvent Substances 0.000 claims description 7
  • 229910002027 silica gel Inorganic materials 0.000 claims description 7
  • 239000000741 silica gel Substances 0.000 claims description 7
  • 229960001866 silicon dioxide Drugs 0.000 claims description 7
  • 238000000034 method Methods 0.000 claims description 6
  • 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 5
  • 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
  • 230000000379 polymerizing effect Effects 0.000 claims description 5
  • 238000010189 synthetic method Methods 0.000 claims description 4
  • 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
  • 229920002554 vinyl polymer Polymers 0.000 claims description 4
  • 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 3
  • 125000006038 hexenyl group Chemical group 0.000 claims description 3
  • CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 3
  • 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 claims description 3
  • 239000000376 reactant Substances 0.000 claims description 3
  • LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 2
  • 230000037048 polymerization activity Effects 0.000 abstract description 6
  • 150000001336 alkenes Chemical class 0.000 abstract description 5
  • 125000003710 aryl alkyl group Chemical group 0.000 abstract description 5
  • 125000000217 alkyl group Chemical group 0.000 abstract description 4
  • 125000000753 cycloalkyl group Chemical group 0.000 abstract description 3
  • JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
  • 125000006374 C2-C10 alkenyl group Chemical group 0.000 abstract 1
  • 238000001308 synthesis method Methods 0.000 abstract 1
  • 239000012968 metallocene catalyst Substances 0.000 description 26
  • 238000005160 1H NMR spectroscopy Methods 0.000 description 14
  • 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
  • 239000013078 crystal Substances 0.000 description 10
  • 230000003595 spectral effect Effects 0.000 description 10
  • 150000002469 indenes Chemical class 0.000 description 8
  • 239000003921 oil Substances 0.000 description 8
  • 238000010792 warming Methods 0.000 description 8
  • 229920000642 polymer Polymers 0.000 description 7
  • 239000005977 Ethylene Substances 0.000 description 6
  • 230000000694 effects Effects 0.000 description 6
  • 238000001953 recrystallisation Methods 0.000 description 6
  • BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
  • 239000000203 mixture Substances 0.000 description 5
  • -1 polyethylene Polymers 0.000 description 5
  • 239000000843 powder Substances 0.000 description 5
  • 229910052709 silver Inorganic materials 0.000 description 5
  • 239000004332 silver Substances 0.000 description 5
  • 239000000126 substance Substances 0.000 description 5
  • XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
  • XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
  • LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
  • WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
  • 125000002769 thiazolinyl group Chemical group 0.000 description 4
  • UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
  • OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
  • TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
  • 239000004698 Polyethylene Substances 0.000 description 3
  • 230000003197 catalytic effect Effects 0.000 description 3
  • 238000006555 catalytic reaction Methods 0.000 description 3
  • 239000000706 filtrate Substances 0.000 description 3
  • 239000007789 gas Substances 0.000 description 3
  • 229920000573 polyethylene Polymers 0.000 description 3
  • 229920000098 polyolefin Polymers 0.000 description 3
  • 238000001291 vacuum drying Methods 0.000 description 3
  • NBHBNYRLTADHQY-UHFFFAOYSA-N 1-benzyl-1h-indene Chemical class C1=CC2=CC=CC=C2C1CC1=CC=CC=C1 NBHBNYRLTADHQY-UHFFFAOYSA-N 0.000 description 2
  • PYSHWNQKDHBAAI-UHFFFAOYSA-N 1-but-3-enyl-1h-indene Chemical class C1=CC=C2C(CCC=C)C=CC2=C1 PYSHWNQKDHBAAI-UHFFFAOYSA-N 0.000 description 2
  • OWNWPBRJHNIUFC-UHFFFAOYSA-N 1-pent-4-enyl-1h-indene Chemical class C1=CC=C2C(CCCC=C)C=CC2=C1 OWNWPBRJHNIUFC-UHFFFAOYSA-N 0.000 description 2
  • 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
  • 125000006043 5-hexenyl group Chemical group 0.000 description 2
  • IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
  • VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
  • IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
  • 238000004458 analytical method Methods 0.000 description 2
  • 229910052786 argon Inorganic materials 0.000 description 2
  • 238000007334 copolymerization reaction Methods 0.000 description 2
  • 238000001914 filtration Methods 0.000 description 2
  • 230000004927 fusion Effects 0.000 description 2
  • 239000005457 ice water Substances 0.000 description 2
  • 238000001819 mass spectrum Methods 0.000 description 2
  • 150000003839 salts Chemical class 0.000 description 2
  • YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
  • 150000003755 zirconium compounds Chemical class 0.000 description 2
  • KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
  • HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
  • KKDBZWZRJNRBGA-UHFFFAOYSA-L Cl[Ti]Cl.[CH]1C=CC=C1 Chemical compound Cl[Ti]Cl.[CH]1C=CC=C1 KKDBZWZRJNRBGA-UHFFFAOYSA-L 0.000 description 1
  • XJONFIGVOQMBIP-UHFFFAOYSA-L Cl[Zr](Cl)C1C=CC=C1 Chemical compound Cl[Zr](Cl)C1C=CC=C1 XJONFIGVOQMBIP-UHFFFAOYSA-L 0.000 description 1
  • MFGOTAHWOBKNNU-XMHGGMMESA-N Isodigeranyl Chemical group CC(C)=CCC\C(C)=C\CC(C)(C=C)CCC=C(C)C MFGOTAHWOBKNNU-XMHGGMMESA-N 0.000 description 1
  • MFGOTAHWOBKNNU-FQEVSTJZSA-N Isodigeranyl Natural products CC(=CCCC(=CC[C@](C)(CCC=C(C)C)C=C)C)C MFGOTAHWOBKNNU-FQEVSTJZSA-N 0.000 description 1
  • 238000005481 NMR spectroscopy Methods 0.000 description 1
  • 229910007926 ZrCl Inorganic materials 0.000 description 1
  • 230000015572 biosynthetic process Effects 0.000 description 1
  • 238000012662 bulk polymerization Methods 0.000 description 1
  • 239000002131 composite material Substances 0.000 description 1
  • 238000010276 construction Methods 0.000 description 1
  • 230000002079 cooperative effect Effects 0.000 description 1
  • 230000000875 corresponding effect Effects 0.000 description 1
  • 230000001186 cumulative effect Effects 0.000 description 1
  • IDASTKMEQGPVRR-UHFFFAOYSA-N cyclopenta-1,3-diene;zirconium(2+) Chemical compound [Zr+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 IDASTKMEQGPVRR-UHFFFAOYSA-N 0.000 description 1
  • 229910003460 diamond Inorganic materials 0.000 description 1
  • 239000010432 diamond Substances 0.000 description 1
  • JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical group C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
  • 238000005516 engineering process Methods 0.000 description 1
  • 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
  • 238000004817 gas chromatography Methods 0.000 description 1
  • 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
  • 238000007429 general method Methods 0.000 description 1
  • 229910052735 hafnium Inorganic materials 0.000 description 1
  • VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
  • 238000007210 heterogeneous catalysis Methods 0.000 description 1
  • 229920001903 high density polyethylene Polymers 0.000 description 1
  • 230000003993 interaction Effects 0.000 description 1
  • 239000003446 ligand Substances 0.000 description 1
  • 229920001684 low density polyethylene Polymers 0.000 description 1
  • 238000012423 maintenance Methods 0.000 description 1
  • 238000005259 measurement Methods 0.000 description 1
  • 229910052757 nitrogen Inorganic materials 0.000 description 1
  • 239000003208 petroleum Substances 0.000 description 1
  • 238000012545 processing Methods 0.000 description 1
  • QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
  • 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
  • 230000009257 reactivity Effects 0.000 description 1
  • 238000011160 research Methods 0.000 description 1
  • 230000000087 stabilizing effect Effects 0.000 description 1
  • 239000000725 suspension Substances 0.000 description 1
  • 238000003786 synthesis reaction Methods 0.000 description 1
  • 230000029305 taxis Effects 0.000 description 1
  • 150000003609 titanium compounds Chemical class 0.000 description 1
  • 238000005303 weighing Methods 0.000 description 1
  • 239000004711 α-olefin Substances 0.000 description 1

Landscapes

  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

本发明提供如下结构式表示的双核茂金属化合物，式中M选自钛或锆，R选自H或C1～C10的烷基、C2～C10的烯基、C7～C10的芳烷基、C6～C10的环烷基或芳基。该化合物与助催化剂烷基铝氧烷配合用于烯烃聚合，具有高的聚合反应活性，并能得到高分子量和宽分子量分布的烯烃聚合产品。本发明还提供所述双核茂金属化合物的合成方法。

Figure 200710013764

The present invention provides a binuclear metallocene compound represented by the following structural formula, wherein M is selected from titanium or zirconium, R is selected from H or C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 7 -C 10 Aralkyl, C 6 -C 10 cycloalkyl or aryl. The compound is used for olefin polymerization in combination with cocatalyst alkyl aluminoxane, has high polymerization activity, and can obtain olefin polymerization products with high molecular weight and wide molecular weight distribution. The invention also provides a synthesis method of the binuclear metallocene compound.

Figure 200710013764

Description

Bridged metallocene double-core catalyst and preparation method thereof and application

Technical field

The invention belongs to polyolefin field, relate to the catalyzer of olefinic polymerization, relate in particular to the isospecific metallocene dinuclear catalyst and preparation method thereof and application of ethene and propylene polymerization.

Background technology

Metallocene catalyst is single because of its active centre, the taxis of activity of such catalysts, polymkeric substance, molecular weight and molecular weight distribution can be by changing ligand structure the controlled extensive concern that is subjected to, but because the polyolefin molecular weight narrowly distributing that obtains, processing difficulties and limited its process of industrialization.People attempt with composite catalyzing (Kaminsky W, Steiger R.Polymerization of olefins with homogeneous zirconocene/alumoxane catalysts, Polyhedron, 1988,7 (22-23): 2375-2381) or double-core multinuclear catalyzer (Feng Zuofeng, Xie Jun, Chen Bin etc., organic chemistry, 2001,21 (1), 33-40) improve the molecular weight distribution of polymkeric substance, from J ü ngling (J ü ngling S in 1993, M ü lhaupt R, Cooperative effects in binuclear zirconecenes:their synthesis and use as catalyst in propenepolymerization, J.Organomet.Chem., 1993,460:191-195) since the reported first benzene bridged binuclear metallocene catalyzed ethylene polymerization, this respect has become the focus of research.

Green has found general method (G.M.Diamond, A.N.Cherega, P.Mountford, the M.L.H.Green of synthetic carbon bound, J.Chem.Soc., Dalton Trans, 1996,921), and synthesize a series of carbon bridging dis-cyclopentadiene compoundses, be used for ethene, third rare polyreaction.Find that the double-core zirconium compounds is than monokaryon zirconium compounds and its hafnium homologue catalytic activity height.This is because [M (η-C 5H 5) 2] in the rotation of metal-metal key can M=Hf be 306KJ/mol, M=Zr is 284KJ/mol.The activity of isodigeranyl nuclear compound and close with binuclear compound, and be higher than its Hf analogue.Find that simultaneously the ethylene polymerization activity of binuclear compound depends primarily on C 5H 4The metal of the metal of one side rather than indenes one side.

Noh synthesized the carbon bridging of a series of different lengthss dicyclopentadiene two titanium compounds (S.K.Noh, J.Kim, J.Jung, C.S.Ra, D.Lee, H.B.Lee, S.W.Lee, W.S.Huh, J.Organomet.Chem., 1999,580,90-97).Be used for the catalyzed ethylene polymerization reaction.Discovery is along with (CH 2) nThe growth of bridge, polymericular weight reduces, and polymerization activity increases, and all than monokaryon compound activity height.This is because thereby long bridge can transmit higher electric density stabilizing active center, improves polymerization activity.Noh thinks that the interaction of atoms metal not only depends on the relative distance of metal center in the binuclear metallocene, and is also relevant with bridge construction.

Lang synthesized the luxuriant binuclear compound of two silyl-bridgeds (H.Lang, S.Blaw, A.Much, K.Wiess, U.Neugebauer, J.Organomet.Chem., 1995,490, c32-c36), catalyzed ethylene polymerization, active in 7.9 * 10 5GPE/mol Ti h, molecular weight reaches 1.2 * 10 6

CN1428355 discloses a kind of dinuclear metallocene compounds and preparation and the application in olefinic polymerization, discloses the binuclear compound of dimethyl-silicon bridging, and has been used for vinyl polymerization, and high reactivity can reach 10 6GPE/mol Cat.

Summary of the invention

The purpose of this invention is to provide class bridged metallocene double-core catalyst and preparation method thereof, this compound is used for olefin polymerization catalysis, can obtain the polyethylene of high molecular and wide molecular weight distribution.

Another object of the present invention is above-mentioned bridged metallocene double-core catalyst is used for olefinic polymerization as catalyzer a method.

Under identical catalytic condition, the catalytic activity of bridged metallocene double-core catalyst and monokaryon metallocene compound such as cyclopentadienyl titanium dichloride Cp 2TiCl 2Or cyclopentadienyl zirconium dichloride Cp 2ZrCl 2Catalytic activity belong to the same order of magnitude, but the binuclear metallocene catalyzer can make the molecular weight of polymkeric substance obviously increase, and molecular weight distribution is broadened.

The invention provides a kind of bridged metallocene double-core catalyst, have following structural formula:

Figure A20071001376400051

M is selected from titanium or zirconium in the formula; R is selected from H or C 1～C 10Alkyl, the thiazolinyl of C2～C10, the aralkyl of C7～C10, cycloalkyl or the aryl of C6～C10.

Preferably, R is selected from the alkyl of H or C1～C4, the thiazolinyl of C2～C8, the aralkyl of C7～C9.Preferred, R is selected from H, sec.-propyl, allyl group, butenyl, pentenyl, hexenyl or benzyl.

The present invention also provides the synthetic method of described dinuclear metallocene compounds, comprises the following steps:

1) C 9H 6R is dissolved in the organic solvent, is cooled to-90 ℃～-60 ℃; C 9H 6The concentration of R in organic solvent is 0.1～0.2mol/L;

2) at-90 ℃～-60 ℃, the organic solution of n-Butyl Lithium slowly adds in the reactant of step 1), adds HPT hexamethyl phosphoric triamine then; N-Butyl Lithium and C 9H 6The ratio of R is 1～1.2: 1; The add-on of HPT hexamethyl phosphoric triamine is C 9H 60.1～10% of R, mol ratio; Stirred 2～8 hours at 0～40 ℃;

3) solution step 2) is cooled to-90 ℃～-60 ℃, and 1-bromo-2-(9-fluorenes) ethane is added drop-wise to step 2) solution in, dropwise at 0-40 ℃ and stirred 24-70 hour; 1-bromo-2-(9-fluorenes) ethane and C 9H 6The mol ratio of R is 1: 1～1.2;

4) the product hydrolysis of step 3), organic layer anhydrous sodium sulfate drying, solvent removed in vacuo; Resistates is dissolved in pentane and purifies with silicagel column, gets part C 13H 8-CH 2CH 2-C 9H 5R;

5) part that step 4) is obtained is dissolved in the normal hexane, drips n-Butyl Lithium, and dropping temperature is-30～20 ℃, preferred-10～0 ℃.The mol ratio of part and n-Butyl Lithium is 1: 2.0～2.5, and progressively increasing finishes, and rises to room temperature naturally, reacts 8～15 hours.Remove by filter solvent, vacuum is drained solvent, obtains the part lithium salts.

6) add toluene in the part lithium salts that step 5) obtains, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, 0～40 ℃ adds CpZrCl down 3DME or CpTiCl 3, wherein DME is a glycol dimethyl ether, Cp is a cyclopentadienyl.CpZrCl 3DME or CpTiCl 3With the mol ratio of part lithium salts be 2～2.5: 1, temperature of reaction is 0～50 ℃, stirring reaction 10～20 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, and is concentrated into solid to occur, place for-25 ℃～-15 ℃ and promptly got Compound C Bridge 2 connection metallocene dinuclear catalyst in 20～30 hours, structure is shown below:

Figure A20071001376400061

M=titanium or zirconium; Cp is a cyclopentadienyl.

Step 2) needs in to add HPT hexamethyl phosphoric triamine (HMPT), to avoid generating 4,5,6,7-hexichol spiral shell [2,4] heptane.

Organic solvent in the reaction is selected from: a kind of in ether, sherwood oil, methyl ether, hexane, pentane, toluene, methylene dichloride, tetrahydrofuran (THF) or the normal hexane;

Preferably, the organic solvent in the step 1) is selected from ether, sherwood oil or methyl ether; Step 2) organic solution in is hexane solution or pentane solution;

R is selected from H or C 1～C 10Alkyl, the thiazolinyl of C2～C10, the aralkyl of C7～C10, cycloalkyl or the aryl of C6～C10.Preferably, R is selected from the alkyl of H or C1～C4, the thiazolinyl of C2～C8, the aralkyl of C7～C9.Preferred, R is selected from H, sec.-propyl, allyl group, butenyl, pentenyl, hexenyl or benzyl.

The present invention also provides a kind of ethene polymerization method, comprise that compound of the present invention is Primary Catalysts, is promotor with the alkylaluminoxane, under polymerizing condition, make vinyl polymerization, wherein in the promotor in Al and the Primary Catalysts mol ratio of metal be 250～1500: 1.Preferably, promotor is a methylaluminoxane, during polyreaction, in the promotor in Al and the Primary Catalysts mol ratio of metal be 250～1000: 1.Polymerizing condition is 50～80 ℃, 0.1～0.8MPa.

Embodiment

If no special instructions, each reaction of the present invention all needs to carry out under inert atmosphere, and rare gas element is argon gas or nitrogen.

Compound provided by the invention is as C 2～C 10The alpha-olefin homopolymerization or the Primary Catalysts of copolymerization.Also need add alkylaluminoxane during polymerization is promotor.Preferred promotor is a methylaluminoxane, during polyreaction, in the promotor in Al and the Primary Catalysts mol ratio of metal be 250～1500: 1, preferred 250～1000: 1.Polymerizing condition is 50～80 ℃, 0.1～0.8MPa.Be used for homopolymerization or copolymerization and get alkene optimal ethylene, propylene, butylene, hexene or octene.Polymerization process can adopt mass polymerization or solution polymerization.

Analytical procedure: NMR:Jeol JNM-EX 270E, Bruker ARX 250 and Bruker DRX 500 nmr determinations; Sample dissolves in 25 ℃ CDCl under argon shield 3Mass spectrum: Varian MAT CH7 mass spectrograph (70eV); GC/MS uses Varian 3700 gas-chromatographies and Varian MAT 312 mass spectrum logotypes.

Polymkeric substance is described: dsc (DSC): Perkin-Elmer DSC-7 calorimeter is used for the thermal properties of characterize polymers, before the measurement, and the vacuum-drying of polymkeric substance elder generation.

Following examples are to further specify of the present invention, but the present invention is not limited thereto.

Embodiment 1: metallocene catalyst A's is synthetic

Step 1: part synthetic

10mmol 1-allyl group indenes is dissolved in the 60ml sherwood oil, be cooled to-78 ℃, 6.25ml n-Butyl Lithium (1.6M hexane solution) slowly adds in the 60ml petroleum ether solution of 10mmol 1-allyl group indenes, adds 6ml HMPT again, slowly rise to 20 ℃, stir 5h down at 20 ℃.

Slowly be cooled to-78 ℃, 2.73g (10mmol) 1-bromo-2-(9-fluorenes) ethane is added drop-wise in the above-mentioned solution, and compound of reaction stirred 30 hours at 20 ℃.Mixture 50ml water hydrolysis, organic layer anhydrous sodium sulfate drying, solvent removed in vacuo.Resistates is dissolved in pentane and purifies with silicagel column, and the oil reservoir that removes after desolvating can be directly used in synthetic compound.Productive rate 79%.Product is 1-(9-fluorenes)-2-[1-(3-allyl group) indenes] ethane; GC 2820s; MS:m/e 348 (M +);

1H NMR(CDCl3，25℃)：7.74(d，J＝7.6Hz，2H)，7.48-7.15(10H)，6.14(d，J＝2.0Hz，1H，CH ind)，6.10(m，1H，＝CH)，5.15(m，1H，CH 2)，5.15(m，1H，＝CH 2)，3.96(t，J＝5.5Hz，1H，CH)，3.29-3.26(m，3H，CH，CH 2)，2.12(m，1H，CH 2)，1.95(m，1H，CH 2)，1.70(m，1H，CH 2)，1.38(m，1H，CH 2)，

13C NMR(CDCl3，25℃)：148.0，147.0，146.9，141.5，141.2(Cq)，135.5(＝CH)，133.7，126.9，126.8，126.2，124.7，124.2，122.7，119.7，119.7，119.1(CH)，116.2(＝CH 2)，48.8，47.3(CH)，32.2，29.6，26.7(CH 2)；

Step 2: the two lithium salts of part synthetic:

0.0266mol part is dissolved in the 80ml normal hexane, ice-water bath drips the n-Butyl Lithium of 0.0592mol down, dropwises the water-bath of recession deicing, rises to room temperature naturally, reacts 12 hours.Remove by filter solvent, vacuum is drained, and gets the white powder solid.Be the part lithium salts.

Step 3: metallocene catalyst A's is synthetic:

Add toluene in the part lithium salts that step 2 obtains, obtain white opacity liquid, 0 ℃ adds CpZrCl down 3DME, wherein DME is a glycol dimethyl ether, Cp is a cyclopentadienyl.CpZrCl 3The mol ratio of DME and part lithium salts is 2: 1, temperature of reaction is 0 ℃, stirring reaction 15 hours, reaction product are through centrifugation, and residual solid is used dichloromethane extraction again, all extraction liquids and the centrifugal liquid that obtains are merged, be concentrated into and solid occurs, placed 20 hours for-25 ℃, the silver color crystal, be metallocene catalyst A, productive rate 49.5%.Structure is shown below:

Figure A20071001376400081

The R=allyl group

Relevant spectral data is as follows:

1H NMR(CDCl3，25℃)：7.95(d，J＝8.5Hz，1H)，7.85(d，J＝8.5Hz，1H)，7.75-7.65(2H)，7.48-7.22(6H)，7.01-6.99(2H)，6.56(t，2H，C 5H 5，a，J H-H＝2.63Hz)，6.47(d，8H，C 5H 5，a，J H-H＝5.04Hz)，5.98(s，1H，CH ind)，5.71(m，1H，＝CH)，4.89(m，1H，＝CH 2)，4.30(m，1H，CH 2)，4.16-3.99(2H，CH 2)，3.89(m，1H，CH 2)，3.34(2H)；

13C NMR(CDCl3，25℃)：136.3(＝CH)，128.6，128.5(CH)，127.4，127.3(Cq)，126.2，125.9(CH)，125.6，125.5(Cq)，125.4，125.3，125.0，124.6，123.9(CH)，123.4，122.7(Cq)，122.6，122.4(CH)，121.7(Cq)，120.8(CH)，120.1(Cq)，115.9(＝CH 2)，115.8，115.6，115.5，115.4，115.3，115.0，114.9，114.7，114.6，114.5，113.7(CH ind)，103.7(Cq ind)，32.6，29.7，29.3(CH 2)；

Embodiment 2: metallocene catalyst B's is synthetic

Other are with embodiment 1, and difference is: in the step 3 with CpTiCl 3Replaced C pZrCl 3DME, reaction product is through centrifugation, and residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, placed 20 hours, and got red crystals for 1/3 ,-25 ℃ that are concentrated into original volume, be metallocene catalyst B, structure is shown below, productive rate 46.5%.

The R=allyl group

Relevant spectral data is as follows:

1H NMR(CDCl3，25℃)：7.96(d，J＝8.5Hz，1H)，7.83(d，J＝8.5Hz，1H)，7.74-7.68(2H)，7.48-7.25(6H)，7.01-6.99(2H)，6.57(t，2H，C 5H 5，a，J H-H＝2.63Hz)，6.48(d，8H，C 5H 5，a，J H-H＝5.04Hz)，5.99(s，1H，CH ind)，5.74(m，1H，＝CH)，4.88(m，1H，＝CH 2)，4.32(m，1H，CH 2)，4.17-3.98(2H，CH 2)，3.87(m，1H，CH 2)，3.32(2H)；

13C NMR(CDCl3，25℃)：136.4(＝CH)，128.7，128.5(CH)，127.3，127.3(Cq)，126.2，125.9(CH)，125.6，125.5(Cq)，125.4，125.3，125.0，124.6，123.9(CH)，123.3，122.7(Cq)，122.7，122.4(CH)，121.7(Cq)，120.8(CH)，120.0(Cq)，115.9(＝CH 2)，115.8，115.7，115.5，115.4，115.3，115.0，114.9，114.7，114.6，114.5，113.8(CH ind)，103.7(Cq ind)，32.7，29.7，29.5(CH 2)；

Embodiment 3: metallocene catalyst C's is synthetic

Step 1: part synthetic:

10mmol 1-(3-butenyl) indenes is dissolved in the 60ml ether, be cooled to-60 ℃, 6.30ml n-Butyl Lithium (1.6M hexane solution) slowly adds in the 60ml diethyl ether solution of 10mmol 1-(3-butenyl) indenes, adds 6ml HMPT then, compound is warming up to 0 ℃, and stirs 3h.

Be cooled to-70 ℃, 2.73g (10mmol) 1-bromo-2-(9-fluorenes) ethane is added drop-wise in the above-mentioned solution, and compound of reaction is warming up to 10 ℃ and stirred 60 hours.Mixture 50ml water hydrolysis, organic layer anhydrous sodium sulfate drying, solvent removed in vacuo.Resistates is dissolved in pentane and purifies with silicagel column, and the oil reservoir that removes after desolvating can be directly used in synthetic compound.Productive rate 88%.Product is 1-(9-fluorenes)-2-[1-(3-fourth-3-thiazolinyl) indenes] ethane; GC 2976s; MS:m/e 362 (M +);

1H NMR(CDCl3，25℃)：7.90-7.82(，2H)，7.67(m，1H)，7.49-7.24(8H)，7.13(d，J＝6.6Hz，1H)，6.26(d，J＝1.6Hz)，6.22(d，J＝1.6Hz，1H，CH ind)，6.01(m，1H，＝CH)，5.15(m，1H，＝CH 2)，5.15(m，1H，＝CH 2)，4.21(t，J＝5.0Hz，1H，CH)，4.05(d，J＝5.4Hz，1H，CH)，3.42(m，1H，CH)，2.70(m，1H，CH 2)，2.57-2.40(3H，CH 2)，2.20(m，1H，CH 2)，2.15-1.94(m，1H，CH 2)，1.78(m，1H，CH 2)，1.62(m，2H，CH 2)；

13C NMR(CDCl3，25℃)：148.5，148.1，147.1，147.1，145.1，144.8，143.4，143.0，141.4，141.3，141.3(Cq)，138.7，138.4(＝CH)，132.9，132.7，127.1，127.0，126.9，126.3，126.3，126.0，124.8，124.4，124.3，122.9，122.8，120.0，120.0，119.9，119.8，119.8，119.0，118.9，118.6(CH)，114.9，114.8(＝CH 2)，48.8，48.4，47.4，47.3(CH)，32.1，31.8，31.3，31.0，29.6，26.8(CH 2)；

Step 2: the two lithium salts of part synthetic:

0.0266mol part is dissolved in the 80ml normal hexane ,-30 ℃ of cryosels are bathed the n-Butyl Lithium that drips 0.0532mol down, dropwise recession deicing salt bath, rise to room temperature naturally, react 12 hours.Remove by filter solvent, vacuum is drained, and gets the white powder solid.Be the part lithium salts.

Step 3: metallocene catalyst C's is synthetic:

Add toluene in the part lithium salts that step 2 obtains, obtain white opacity liquid, 340 ℃ add CpM down 1Cl 3DME, wherein DME is a glycol dimethyl ether, and Cp is a cyclopentadienyl, and M1 is titanium or zirconium.CpM 1Cl 3The mol ratio of DME and part lithium salts is 2.3: 1, temperature of reaction is 50 ℃, stirring reaction 10 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, and is concentrated into solid to occur, place for-25 ℃ and promptly got metallocene catalyst C in 20 hours, structure is shown below:

The R=3-butenyl

Solid gets the silver color crystal with 50ml toluene recrystallization.Productive rate 44.8%.Relevant spectral data is as follows:

1H NMR(CDCl3，25℃)：7.97(d，J＝8.4Hz，1H)，7.87(d，J＝7.3Hz，1H)，7.78-7.66(3H)，7.56(t，J＝6.9，1H)，7.43-7.32(2H)，7.29-7.20(2H)，7.15-7.01(2H)，6.56(t，2H，C 5H 5，a，J H-H＝2.63Hz)，6.47(d，8H，C 5H 5，a，J H-H＝5.04Hz)，5.96(s，1H，CH ind)，5.70(m，1H，＝CH)，4.91(m，1H，＝CH 2)，4.91(m，1H，＝CH 2)，4.30(m，1H，CH 2)，4.19-3.97(2H，CH 2)，3.86(m，1H，CH 2)，2.79(m，2H，CH 2)，2.18(m，2H，CH 2)，

13C NMR(CDCl3，25℃)：137.8(＝CH)，128.5，128.4(CH)，127.3，127.2(Cq)，126.1，125.7(CH)，125.6，125.3(Cq)，125.3，125.2，124.9，124.6，123.8(CH)，123.4，122.6(Cq)，122.5，122.3(CH)，122.2，121.4(Cq)，120.8(CH)，115.8，115.6，115.5，115.4，115.3，115.1(＝CH 2)，115.0，114.9，114.7，114.6，114.5，113.4(CH ind)，103.6(Cq ind)，34.1，29.7，29.2，27.6(CH 2)；

Embodiment 4: metallocene catalyst D's is synthetic

Other are with embodiment 3, and difference is: in the step 3 with CpTiCl 3Replaced C pZrCl 3DME, reaction product is through centrifugation, and residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, placed 20 hours for 1/3 ,-25 ℃ that are concentrated into original volume, i.e. metallocene catalyst D, structure is shown below.Solid gets red crystals, productive rate 56.9% with 50ml toluene recrystallization.

Figure A20071001376400102

The R=3-butenyl

Relevant spectral data is as follows:

1H NMR(CDCl3，25℃)：7.99(d，J＝8.4Hz，1H)，7.88(d，J＝7.3Hz，1H)，7.78-7.68(3H)，7.56(t，J＝6.9，1H)，7.43-7.32(2H)，7.29-7.20(2H)，7.15-7.04(2H)，6.56(t，2H，C 5H 5，a，J H-H＝2.63Hz)，6.47(d，8H，C 5H 5，a，J H-H＝5.04Hz)，5.96(s，1H，CH ind)，5.72(m，1H，＝CH)，4.91(m，1H，＝CH 2)，4.91(m，1H，＝CH 2)，4.30(m，1H，CH 2)，4.19-3.99(2H，CH 2)，3.84(m，1H，CH 2)，2.77(m，2H，CH 2)，2.14(m，2H，CH 2)，

13C NMR(CDCl3，25℃)：137.9(＝CH)，128.6，128.6(CH)，127.4，127.2(Cq)，126.1，125.7(CH)，125.6，125.3(Cq)，125.3，125.2，124.9，124.6，123.8(CH)，123.6，122.6(Cq)，122.5，122.3(CH)，122.2，121.6(Cq)，120.8(CH)，115.8，115.6，115.5，115.4，115.3，115.1(＝CH 2)，115.0，114.9，114.7，114.6，114.5，113.4(CH ind)，103.6(Cq ind)，34.3，29.7，29.4，27.6(CH 2)；

Embodiment 5: metallocene catalyst E's is synthetic

10mmol 1-(4-pentenyl) indenes is dissolved in the 70ml methyl ether, be cooled to-80 ℃, 6.20ml n-Butyl Lithium (1.6M hexane solution) slowly adds in the 50ml methyl ether solution of 10mmol 1-(4-pentenyl) indenes, adds 6ml HMPT then, is warming up to 30 ℃ and stir 8h at 30 ℃.

Be cooled to-80 ℃, 2.73g (10mmol) 1-bromo-2-(9-fluorenes) ethane is added drop-wise in the above-mentioned solution, is warming up to 30 ℃ and stirred 40 hours down at 30 ℃.Mixture 50ml water hydrolysis, organic layer anhydrous sodium sulfate drying, solvent removed in vacuo.Resistates is dissolved in pentane and purifies with silicagel column, and the oil reservoir that removes after desolvating can be directly used in synthetic compound.Productive rate 70%.Product is 1-(9-fluorenes)-2-[1-(3-penta-4-thiazolinyl) indenes] ethane; GC 3061s; MS:m/e 376 (M +);

1H NMR(CDCl3，25℃)：7.94-7.85(2H)，7.67(m，1H)，7.53-7.12(8H)，7.05(m，1H)，6.23(d，J＝1.9Hz)，6.17(d，J＝1.9Hz，CH ind)，5.89(m，1H，＝CH)，5.09(m，1H，＝CH 2)，5.09(m，1H，＝CH 2)，4.18(t，J＝5.5Hz)，4.01(t，J＝5.5Hz，1H)，3.37(m，1H，CH)，2.61-2.36(3H，CH 2)，2.23-2.11(m，3H，CH 2)，1.89-1.77(m，2H，CH 2)，1.57-1.34(2H，CH 2)；

13C NMR(CDCl3，25℃)：148.6，148.1，147.1，147.0，145.1，144.8，143.4，143.1，141.3，141.3，141.2(Cq)，138.8，138.7(＝CH)，133.0，132.8，132.7，127.0，126.9，126.2，124.6，124.3，122.8，119.8，119.8，119.8，118.9(CH)，114.8，114.6(＝CH 2)，48.9，48.7，47.5，47.3，47.2(CH)，34.1，33.6，31.3，27.2，27.0，26.9，23.3，18.3(CH 2)；

Step 2: the two lithium salts of part synthetic:

0.0266mol part is dissolved in the 80ml normal hexane ,-10 ℃ of cryosels are bathed the n-Butyl Lithium that drips 0.0556mol down, dropwise recession deicing salt bath, rise to room temperature naturally, react 8 hours.Remove by filter solvent, vacuum is drained, and gets the white powder solid.Be the part lithium salts.

Step 3: metallocene catalyst E's is synthetic:

Add toluene in the part lithium salts that step 2 obtains, obtain white opacity liquid, 30 ℃ add CpM down 1Cl 3DME, wherein DME is a glycol dimethyl ether, and Cp is a cyclopentadienyl, and M1 is titanium or zirconium.CpM 1Cl 3The mol ratio of DME and part lithium salts is 2.1: 1, temperature of reaction is 30 ℃, stirring reaction 20 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, and is concentrated into solid to occur, place for-15 ℃ and promptly got metallocene catalyst E in 30 hours, structure is shown below:

Figure A20071001376400121

The R=4-pentenyl;

-20 ℃ left standstill 20 hours, got the silver color crystal.Productive rate 52.5%.Relevant spectral data is as follows:

1H NMR(CDCl3，25℃)：7.94(d，J＝8.4Hz，1H)，7.85(d，J＝8.2Hz，1H)，7.76-7.64(3H)，7.54(t，J＝6.9Hz，1H)，7.41-7.23(4H)，7.11-6.99(2H)，6.56(t，2H，C 5H 5，a，J H-H＝2.63Hz)，6.47(d，8H，C 5H 5，a，J H-H＝5.04Hz)，5.95(s，1H，CH ind)，5.73(m.1H，＝CH)，4.93(m，1H，CH 2)，4.93(m，1H，CH 2)，4.36(m，1H，CH 2)，4.19-3.97(2H，CH 2)，3.87(m，1H，CH 2)，2.60(m，2H，CH 2)，1.97(m，2H，CH 2)，1.50(m，2H，CH 2)；

13C NMR(CDCl3，25℃)：138.3(＝CH)，128.5，128.4(GH)，127.3，127.1(Cq)，126.0，125.6(CH)，125.5，125.3(Cq)，125.2，125.1，124.9，124.5，123.9(CH)，123.3，123.0，122.6(Cq)，122.5，122.3(CH)，121.4(Cq)，120.8(CH)，115.8，115.6，115.5，115.4，115.3，115.0，114.9，114.7，114.6，114.5，114.6(＝CH 2)，113.4(CH ind)，103.5(Cq ind)，33.4，29.7，29.4，29.2，27.5(CH 2)；

Embodiment 6: metallocene catalyst F's is synthetic:

Other are with embodiment 5, and difference is: in the step 3 with CpTiCl 3Replaced C pZrCl 3DME, reaction product is through centrifugation, and residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, placed 20 hours for 1/3 ,-25 ℃ that are concentrated into original volume, i.e. metallocene catalyst F, structure is shown below.Solid gets red crystals, productive rate 49.9% with 50ml toluene recrystallization.

The R=4-pentenyl;

Relevant spectral data is as follows:

1H NMR(CDCl3，25℃)：7.96(d，J＝8.4Hz，1H)，7.88(d，J＝8.2Hz，1H)，7.77-7.65(3H)，7.54(t，J＝6.9Hz，1H)，7.41-7.25(4H)，7.11-6.99(2H)，6.57(t，2H，C 5H 5，a，J H-H＝2.63Hz)，6.48(d，8H，C 5H 5，a，J H-H＝5.04Hz)，5.96(s，1H，CH ind)，5.73(m.1H，＝CH)，4.93(m，1H，CH 2)，4.95(m，1H，CH 2)，4.36(m，1H，CH 2)，4.19-3.97(2H，CH 2)，3.88(m，1H，CH 2)，2.62(m，2H，CH 2)，1.99(m，2H，CH 2)，1.50(m，2H，CH 2)；

13C NMR(CDCl3，25℃)：138.5(＝CH)，128.4，128.3(GH)，127.2，127.1(Cq)，126.0，125.6(CH)，125.5，125.3(Cq)，125.2，125.1，124.9，124.6，123.8(CH)，123.2，123.0，122.6(Cq)，122.5，122.3(CH)，121.4(Cq)，120.7(CH)，115.7，115.6，115.5，115.4，115.3，115.0，114.9，114.7，114.6，114.5，114.6(＝CH 2)，113.2(CH ind)，103.5(Cq ind)，33.2，29.7，29.2，29.1，27.4(CH 2)；

Embodiment 7: metallocene catalyst G's is synthetic:

10mmol1-(5-hexenyl) indenes is dissolved in the 50ml ether, be cooled to-78 ℃, 6.28ml n-Butyl Lithium (1.6M pentane solution) slowly adds in the 50ml diethyl ether solution of 10mmol1-(5-hexenyl) indenes, adds 6ml HMPT again, is warming up to 10 ℃ and stir down 2h at 10 ℃.

Be cooled to-78 ℃, 2.73g (10mmol) 1-bromo-2-(9-fluorenes) ethane is added drop-wise in the solution, and reactant is warming up to 0 ℃ and stirred 66 hours down at 0 ℃.Mixture 50ml water hydrolysis, organic layer anhydrous sodium sulfate drying, solvent removed in vacuo.Resistates is dissolved in pentane and purifies with silicagel column, and the oil reservoir that removes after desolvating can be directly used in synthetic compound.Productive rate 86%.Product is 1-(9-fluorenes)-2-[1-(3-oneself-5-thiazolinyl) indenes] ethane; GC 3300s; MS:m/e 390 (M +);

Step 2: the two lithium salts of part synthetic:

0.0266mol part is dissolved in the 80ml normal hexane ,-20 ℃ of cryosels are bathed the n-Butyl Lithium that drips 0.0556mol down, dropwise the recession deicing and bathe, and rise to room temperature naturally, react 10 hours.Remove by filter solvent, vacuum is drained, and gets the white powder solid.Be the part lithium salts.

Step 3: metallocene catalyst G's is synthetic:

Add toluene in the part lithium salts that step 2 obtains, obtain white opacity liquid, 20 ℃ add CpM down 1Cl 3DME, wherein DME is a glycol dimethyl ether, and Cp is a cyclopentadienyl, and M1 is titanium or zirconium.CpM 1Cl 3The mol ratio of DME and part lithium salts is 2: 1, temperature of reaction is 20 ℃, stirring reaction 15 hours, and reaction product is through centrifugation, residual solid is used dichloromethane extraction again, all extraction liquids and the centrifugal liquid that obtains are merged, be concentrated into and solid occurs, after the filtration filtrate is concentrated into 1/3 of original volume,-20 ℃ left standstill 20 hours, get the silver color crystal, be metallocene dinuclear catalyst G, structure is shown below:

Figure A20071001376400131

The R=5-hexenyl;

Productive rate 51.3%.Relevant spectral data is as follows:

1H NMR(CDCl3，25℃)：7.93(d，J＝8.4Hz，1H)，7.84(d，J＝8.4Hz，1H)，7.73(d，J＝8.5Hz，1H)，7.67-7.63(2H)，7.53-7.20(6H)，7.12-6.98(2H)，6.56(t，2H，C 5H 5，a，J H-H＝2.63Hz)，6.47(d，8H，C 5H 5，a，J H-H＝5.04Hz)，5.94(s，1H，CH ind)，5.71(m，1H，＝CH)，4.91(m，1H，＝CH 2)，4.33(m，1H，CH 2)，4.16-4.00(2H，CH 2)，3.87(m，1H，CH 2)，2.67(m，1H，CH 2)，2.56(m，1H，CH 2)，1.97(m，2H，CH 2)，1.44-1.22(4H，CH 2)，

13C NMR(CDCl3，25℃)：138.7(＝CH)，128.5，128.4(CH)，127.3，127.2(Cq)，126.1，125.7(CH)，125.5，125.4(Cq)，125.3，125.1，124.9，124.6，123.9(CH)，123.4，123.3，122.6(Cq)，122.5，122.4(CH)，121.4(Cq)，120.8(CH)，115.8，115.6，115.5，115.4，115.3，115.0，114.9，114.7，114.6，114.5，114.4(＝CH 2)，113.4(CH ind)，103.6(Cq ind)，33.5，28.7，29.3，28.7，28.0(CH 2)；

Embodiment 8: metallocene catalyst H's is synthetic:

Other are with embodiment 7, and difference is: in the step 3 with CpTiCl 3Replaced C pZrCl 3DME, reaction product is through centrifugation, and residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, placed 20 hours for 1/3 ,-25 ℃ that are concentrated into original volume, i.e. metallocene catalyst H, structure is shown below.Solid gets red crystals, productive rate 48.6% with 50ml toluene recrystallization.

The R=5-hexenyl;

Relevant spectral data is as follows:

1H NMR(CDCl3，25℃)：7.94(d，J＝8.4Hz，1H)，7.86(d，J＝8.4Hz，1H)，7.74(d，J＝8.5Hz，1H)，7.68-7.64(2H)，7.54-7.21(6H)，7.13-6.97(2H)，6.58(t，2H，C 5H 5，a，J H-H＝2.63Hz)，6.48(d，8H，C 5H 5，a，J H-H＝5.04Hz)，5.95(s，1H，CH ind)，5.71(m，1H，＝CH)，4.91(m，1H，＝CH 2)，4.34(m，1H，CH 2)，4.16-4.02(2H，CH 2)，3.87(m，1H，CH 2)，2.68(m，1H，CH 2)，2.57(m，1H，CH 2)，1.98(m，2H，CH 2)，1.44-1.22(4H，CH 2)，

13C NMR(CDCl3，25℃)：138.8(＝CH)，128.6，128.5(CH)，127.4，127.3(Cq)，126.2，125.7(CH)，125.5，125.4(Cq)，125.3，125.1，124.9，124.6，123.9(CH)，123.4，123.3，122.6(Cq)，122.5，122.4(CH)，121.3(Cq)，120.9(CH)，115.8，115.7，115.5，115.4，115.3，115.0，114.9，114.7，114.6，114.5，114.4(＝CH 2)，113.4(CH ind)，103.7(Cq ind)，33.6，28.8，29.4，28.6，28.2(CH 2)；

Embodiment 9: metallocene catalyst I's is synthetic:

10mmol 1-benzyl indenes is dissolved in the 60ml ether, is cooled to-70 ℃, and 6.30ml n-Butyl Lithium (1.6M pentane solution) slowly adds in the 70ml diethyl ether solution of 10mmol 1-benzyl indenes, adds 6ml HMPT then, is warming up to 0 ℃ and stir 4h.

Be cooled to-78 ℃, 2.73g (10mmol) 1-bromo-2-(9-fluorenes) ethane is added drop-wise in the solution, slowly rises to 10 ℃ and stirred 69 hours.Mixture 50ml water hydrolysis, organic layer anhydrous sodium sulfate drying, solvent removed in vacuo.Resistates is dissolved in pentane and purifies with silicagel column, and the oil reservoir that removes after desolvating can be directly used in synthetic compound.Productive rate 77%.

1-(9-fluorenes)-2-[1-(3-phenmethyl) indenes] ethane: GC 3341 s.MS:m/e 398 (M +).

1H NMR(CDCl3，25℃)：7.94-7.83(3H)，7.58-7.31(13H)，7.14(m，1H)，6.67(d，J＝5.5Hz，2H)，6.27(d，J＝5.5Hz，1H)，6.23(m)，6.18(m)，6.15(m，1H，CH ind)，4.03(m，2H)，3.97(s，1H，CH)，3.44(s，1H，CH)，2.44(2H，CH 2)，2.23(m，1H，CH 2)，2.05(m，1H，CH 2)；

Step 2: the two lithium salts of part synthetic:

0.0266mol part is dissolved in the 80ml normal hexane, ice-water bath drips the n-Butyl Lithium of 0.0532mol down, dropwises the recession deicing and bathes, and rises to room temperature naturally, reacts 15 hours.Remove by filter solvent, vacuum is drained, and gets the white powder solid.Be the part lithium salts.

Step 3: metallocene catalyst I's is synthetic:

Add toluene in the part lithium salts that step 2 obtains, obtain white opacity liquid, 10 ℃ add CpM down 1Cl 3DME, wherein DME is a glycol dimethyl ether, and Cp is a cyclopentadienyl, and M1 is titanium or zirconium.CpM 1Cl 3The mol ratio of DME and part lithium salts is 2: 1, temperature of reaction is 10 ℃, stirring reaction 15 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, and is concentrated into solid to occur, place for-25 ℃ and promptly got bridged metallocene double-core catalyst I in 20 hours, structure is shown below:

The R=benzyl;

80 ℃ of filtrations, resistates is incorporated filtrate into the extraction of 60ml toluene, filtrate is concentrated into 1/3 ,-20 ℃ of original volume left standstill 20 hours, red solid.Solid gets the silver color crystal with 50ml normal hexane recrystallization.Productive rate 39.9%.Relevant spectral data is as follows:

1H NMR(CDCl3，25℃)：7.92(d，J＝8.0Hz，1H)，7.81(J＝8.0Hz，1H)，7.68-7.61(3H)，7.53(m，1H)，7.50-6.98(11H)，6.56(t，2H，C 5H 5，a，J H-H＝2.63Hz)，6.47(d，8H，C 5H 5，a，J H-H＝5.04Hz)，5.94(d，J＝3.2Hz，1H)，4.31(m，1H，CH 2)，3.97(m，3H，，CH 2)，3.92(2H)；

Embodiment 10: metallocene catalyst J's is synthetic:

Other are with embodiment 9, and difference is: in the step 3 with CpTiCl 3Replaced C pZrCl 3DME, reaction product is through centrifugation, and residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, and places 25 hours for 1/2 ,-25 ℃ that are concentrated into original volume, promptly gets metallocene catalyst J, and structure is shown below.Solid gets red crystals, productive rate 48.3% with 50ml toluene recrystallization.

Figure A20071001376400161

The R=benzyl;

Relevant spectral data is as follows:

1H NMR(CDCl3，25℃)：7.95(d，J＝8.0Hz，1H)，7.82(J＝8.0Hz，1H)，7.69-7.62(3H)，7.53(m，1H)，7.50-6.99(11H)，6.57(t，2H，C 5H 5，a，J H-H＝2.63Hz)，6.48(d，8H，C 5H 5，a，J H-H＝5.04Hz)，5.95(d，J＝3.2Hz，1H)，4.32(m，1H，CH 2)，3.98(m，3H，，CH 2)，3.94(2H)；

Embodiment 11-20: vinyl polymerization

Catalyzer is made into toluene solution, adds 10% MAO toluene solution, catalyzer and toluene successively in the exsiccant reaction flask, the control cumulative volume is 25ml, is warming up to 60 ℃, feeds ethylene gas, and maintenance system is a normal pressure, reacts 0.5 hour.With dilute hydrochloric acid and ethanol stopped reaction, filter, product was 60 ℃ of vacuum-dryings 3 hours, and the catalyzer that adds in the reaction process and the amount of promotor, catalyst activity and polymer property see Table 1, and wherein weight-average molecular weight and molecular weight distribution mw/mn are recorded by GPC.

It should be noted that, the metallocene catalyst that has ω-alkenyl group can be used as comonomer and enters the polyolefin polymers chain, in this case, being equivalent to these metallocene catalysts is immobilized, polymer chain is as organic carrier, and the polymer chain that obtains later is that heterogeneous catalysis obtains.The catalysis data see Table 1.The polyethylene fusing point that obtains is at 131.7 to 140.0 ℃, and the fusion enthalpy difference is very big, and the polyethylene fusion enthalpy that the catalyzer of C2 bridging obtains is up to 16095J g -1, corresponding degree of crystallinity is 53 to 57%, (α=40-50%) and PE-HD are (between the α=60-80%) between PE-LD.

Embodiment 21-30: ethylene homo reaction

Carry out ethene party reaction by the method for the foregoing description, different is that ethene, with dilute hydrochloric acid and ethanol stopped reaction, is filtered after 1 hour 80 ℃ of polymerizations, and product was 60 ℃ of vacuum-dryings 3 hours, and weighing gets polymer weight, calculates polymerization activity.The catalysis data see Table 1.

Table 1 polymerization activity and polymer analysis

Embodiment number The catalyzer numbering Catalyzer add-on (mmol) MAO add-on (ml) Al/M Catalyst activity (10 5gPE/mol Cat h) Mw Mw/Mn Tm (℃)
11 A 0.01 6.4 500 1.87 211500 3.01 135.42
12 B 0.0069 8.8 1000 4.39 420530 2.93 131.68
13 C 0.006 3.9 500 1.89 807300 2.81 135.92
14 D 0.004 2.57 500 8.15 198000 2.58 135.05
15 E 0.0095 6.04 500 2.8 393000 2.04 134.27
16 F 0.006 3.9 500 2.44 289000 2.10 136.11
17 G 0.0066 4.2 500 1.03 375300 2.44 134.75
18 H 0.004 5.08 1000 1.04 398000 3.22 135.02
19 I 0.002 2.85 500 0.75 404000 1.95 139.9
20 J 0.0012 7.8 500 0.6 598000 2.21 137.37
21 A 0.012 7.8 500 1.44 314500 2.31 136.21
22 B 0.0069 8.8 1000 4.12 390000 2.63 132.64
23 C 0.006 3.9 500 1.75 754300 2.72 136.13
24 D 0.004 2.57 500 8.03 212000 2.49 134.82
25 E 0.011 7.7 500 2.46 364000 2.11 133.57
26 F 0.006 3.9 500 2.33 279000 2.02 137.19
27 G 0.008 4.9 500 1.01 365300 2.30 135.08
28 H 0.004 12.85 1500 1.03 358000 3.15 134.92
29 I 0.002 5.08 500 0.74 364000 1.89 139.46
30 J 0.002 5.08 250 0.59 488000 2.23 138.27

Claims (7)

1. dinuclear metallocene compounds has following structural formula:

Figure A2007100137640002C1

M is selected from titanium or zirconium in the formula; R is selected from H or C 1～C 10Alkyl, C 2～C 10Thiazolinyl, C 7～C 10Aralkyl, C 6～C 10Cycloalkyl or aryl.

2. dinuclear metallocene compounds as claimed in claim 1 is characterized in that R is selected from H, sec.-propyl, allyl group, butenyl, pentenyl, hexenyl or benzyl.

3. the synthetic method of dinuclear metallocene compounds as claimed in claim 1 or 2 comprises the following steps:

1) C 9H 6R is dissolved in the organic solvent, is cooled to-90 ℃～-60 ℃; C 9H 6The concentration of R in organic solvent is 0.1～0.2mol/L;

2) at-90 ℃～-60 ℃, the organic solution of n-Butyl Lithium slowly adds in the reactant of step 1), adds HPT hexamethyl phosphoric triamine then; N-Butyl Lithium and C 9H 6The ratio of R is 1～1.2: 1; The add-on of HPT hexamethyl phosphoric triamine is C 9H 60.1～10% of R, mol ratio; Stirred 2～8 hours at 0～40 ℃;

3) solution step 2) is cooled to-90 ℃～-60 ℃, and 1-bromo-2-(9-fluorenes) ethane is added drop-wise to step 2) solution in, dropwise at 0～40 ℃ and stirred 24-70 hour; 1-bromo-2-(9-fluorenes) ethane and C 9H 6The mol ratio of R is 1: 1～1.2;

4) the product hydrolysis of step 3), organic layer anhydrous sodium sulfate drying, solvent removed in vacuo; Resistates is dissolved in pentane and purifies with silicagel column, gets part C 13H 8-CH 2CH 2-C 9H 6R;

5) part that step 4) is obtained is dissolved in the normal hexane, drips n-Butyl Lithium, and dropping temperature is-30～20 ℃; The mol ratio of part and n-Butyl Lithium is 1: 2.0～2.5, and progressively increasing finishes, and rises to room temperature naturally, reacts 8～15 hours; Remove by filter solvent, vacuum is drained solvent, obtains the part lithium salts;

6) add toluene in the part lithium salts that step 5) obtains, obtain white opacity liquid, 0～40 ℃ adds CpZrCl down 3DME or CpZrCl 3, wherein DME is a glycol dimethyl ether, Cp is a cyclopentadienyl; CpZrCl 3DME or CpZrCl 3With the mol ratio of part lithium salts be 2～2.5: 1, temperature of reaction is 0～40 ℃, stirring reaction 10～20 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, and is concentrated into solid to occur, place for-25 ℃～-15 ℃ and promptly got Compound C Bridge 2 connection metallocene dinuclear catalyst in 20～30 hours, structure is shown below:

Figure A2007100137640003C1

M=titanium or zirconium, R are selected from H or C 1～C 10Alkyl, C 2～C 10Thiazolinyl, C 7～C 10Aralkyl, C 6～C 10Cycloalkyl or aryl.

4. the synthetic method of dinuclear metallocene compounds as claimed in claim 3 is characterized in that, dropping temperature is-10～0 ℃ in the step 5).

5. the synthetic method of dinuclear metallocene compounds as claimed in claim 3 is characterized in that, the organic solvent in the step 1) is selected from ether, sherwood oil or methyl ether; Step 2) organic solution in is hexane solution or pentane solution.

6. ethene polymerization method, comprise with the described compound of claim 1 and be Primary Catalysts, be promotor with the alkylaluminoxane, under polymerizing condition, make vinyl polymerization, wherein in the promotor in Al and the Primary Catalysts mol ratio of metal be 250～1500: 1; Polymerizing condition is 50～80 ℃, 0.1～0.8MPa.

7. ethene polymerization method as claimed in claim 6 is characterized in that promotor is a methylaluminoxane, during polyreaction, in the promotor in Al and the Primary Catalysts mol ratio of metal be 250～1000: 1.

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