CN104271586B - Ansa-metallocene compounds and use the method that this compound prepares loaded catalyst - Google Patents
Ansa-metallocene compounds and use the method that this compound prepares loaded catalyst Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims description 59
- 230000000694 effects Effects 0.000 claims abstract description 30
- 229920000098 polyolefin Polymers 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims description 56
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 52
- 238000006116 polymerization reaction Methods 0.000 claims description 37
- -1 ethylene, propylene Chemical group 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000006555 catalytic reaction Methods 0.000 claims description 22
- 150000001336 alkenes Chemical class 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 101700002510 GCAT Proteins 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 7
- 239000000969 carrier Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-Hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical group CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-Methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N Decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L MgCl2 Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-Octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 38
- 238000010276 construction Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 45
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 34
- 239000000203 mixture Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 230000002194 synthesizing Effects 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 17
- 239000008079 hexane Substances 0.000 description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- LIKFHECYJZWXFJ-UHFFFAOYSA-N Dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 13
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 125000003710 aryl alkyl group Chemical group 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 125000002769 thiazolinyl group Chemical group 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 125000002877 alkyl aryl group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- UHOVQNZJYSORNB-MZWXYZOWSA-N Deuterated benzene Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 230000000737 periodic Effects 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 125000004429 atoms Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 150000002469 indenes Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 229910052768 actinide Inorganic materials 0.000 description 3
- 150000001255 actinides Chemical group 0.000 description 3
- 230000027455 binding Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 210000001699 lower leg Anatomy 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- ASGNRCDZSRNHOP-UHFFFAOYSA-N 2-methyl-4-phenyl-1H-indene Chemical class C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 ASGNRCDZSRNHOP-UHFFFAOYSA-N 0.000 description 2
- RNNYGJHJZKMOOZ-UHFFFAOYSA-N CC(C)C1=CC(C(C)C)=CC2=C1C=C(C)C2[SiH3] Chemical compound CC(C)C1=CC(C(C)C)=CC2=C1C=C(C)C2[SiH3] RNNYGJHJZKMOOZ-UHFFFAOYSA-N 0.000 description 2
- XEVRDFDBXJMZFG-UHFFFAOYSA-N Carbohydrazide Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N Methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LJWKFGGDMBPPAZ-UHFFFAOYSA-N ethoxyethane;toluene Chemical compound CCOCC.CC1=CC=CC=C1 LJWKFGGDMBPPAZ-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 238000011068 load Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- XFNIQDLAPZZUMH-UHFFFAOYSA-N 2-methyl-4,6-di(propan-2-yl)-1H-indene Chemical class CC(C)C1=CC(C(C)C)=CC2=C1C=C(C)C2 XFNIQDLAPZZUMH-UHFFFAOYSA-N 0.000 description 1
- UORKSJVSCNPZDH-UHFFFAOYSA-N CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[SiH](C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 Chemical compound CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[SiH](C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 UORKSJVSCNPZDH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N Methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- IIMIOEBMYPRQGU-UHFFFAOYSA-L Picoplatin Chemical compound N.[Cl-].[Cl-].[Pt+2].CC1=CC=CC=N1 IIMIOEBMYPRQGU-UHFFFAOYSA-L 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N Triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J Zirconium(IV) chloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- ODOOOEXDBNGOOF-UHFFFAOYSA-M [Cl-].CCCCCC[Mg+] Chemical compound [Cl-].CCCCCC[Mg+] ODOOOEXDBNGOOF-UHFFFAOYSA-M 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NTGONJLAOZZDJO-UHFFFAOYSA-M disodium;hydroxide Chemical compound [OH-].[Na+].[Na+] NTGONJLAOZZDJO-UHFFFAOYSA-M 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- HXHYTNUGRGBKIE-UHFFFAOYSA-N formazan Chemical group NN=CN=N.NN=CN=N HXHYTNUGRGBKIE-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N oxygen atom Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to a kind of ansa-metallocene compounds, the method preparing described ansa-metallocene compounds, and using described ansa-metallocene compounds to prepare polyolefinic method, described ansa-metallocene compounds has new construction, it is possible to provide various selectivitys and activity to polyolefin polymer.
Description
Technical field
The present invention relates to a kind of ansa-metallocene compounds and the method using this compound to prepare loaded catalyst.
Background technology
Ansa-metallocene is a kind of organo-metallic compound containing connected by abutment 2 parts.Described abutment prevents
Described part rotates and determines structure and the activity of metal center.
One potential application of ansa-metallocene is to be used in the polyreaction of olefin homo or copolymer.Especially,
Ansa-metallocene based on cyclopentadienyl-fluorenyl ligands is in having the polymerization of High molecular weight polyethylene of controllable microstructure
Become extremely important.Additionally, there is excellent activity containing the ansa-metallocene of indenyl ligands and can be used to production there is height
The polyolefin of stereoregularity.
Although as it has been described above, to there is high activity and can controlling the ansa-metallocene of olefin polymer micro structure
Compound carries out various research, but result is unsatisfactory.
Summary of the invention
Technical problem
The purpose of the present invention is for providing a kind of ansa-metallocene compounds, and it has new construction, and urges as support type
Agent has excellent activity and can successfully control the micro structure of olefin polymer simultaneously.
Another object of the present invention is for providing the preparation method of described ansa-metallocene compounds.
A further object of the present invention includes the olefinic polymerization supported catalyst of described ansa-metallocene compounds for providing
Agent.
Another object of the present invention uses described loaded catalyst to prepare polyolefinic method for providing.
Technical scheme
The present invention provides the ansa-metallocene compounds represented by formula 1 below.
[chemical formula 1]
Wherein, in chemical formula 1,
M1For the periodic table of elements the 3rd race, the 4th race or the transition metal of the 5th race, or it is actinides or lanthanide series；
X can be identical or different, respectively halogen；
A is the element of the periodic table of elements the 14th race, and plays the effect of the abutment connecting two indenyls；
R1For there is the alkyl of 1 to 20 carbon atoms, there is the thiazolinyl of 1 to 20 carbon atoms, there are 1 to 20 carbon atoms
Alkaryl, there is the aralkyl of 1 to 20 carbon atoms or there is the aryl of 1 to 20 carbon atoms；
R2The alkyl, the thiazolinyl with 1 to 20 carbon atoms that for hydrogen, there are 1 to 20 carbon atoms, there are 1 to 20 carbon
The alkaryl of atom, there is the aralkyl of 1 to 20 carbon atoms or there is the aryl of 1 to 20 carbon atoms；
R3、R3′、R4And R4′Can be identical or different, independently be and there is the alkyl of 1 to 20 carbon atoms, have 1 to 20
The thiazolinyl of individual carbon atom, there is the alkaryl of 1 to 20 carbon atoms, there is the aralkyl of 1 to 20 carbon atoms or have 1 to 20
The aryl of individual carbon atom；And
N is the integer of 1 to 20.
The present invention also provides for the preparation method of described ansa-metallocene compounds.
The present invention also provides for including the olefinic polymerization loaded catalyst of described ansa-metallocene compounds.
The present invention also provides the described loaded catalyst of use to prepare polyolefinic method.
Detailed description of the invention
Below, it will thus provide described ansa-metallocene compounds and the embodiment of its preparation method, comprise this compound
The embodiment of olefin polymerization catalysis and use described catalyst to prepare the embodiment of polyolefinic method.This is disclosed
The bright purpose of explanation that is preferred embodiment in order at, but it is not intended to limit the present invention.Therefore, the technology of this area
Personnel it will be appreciated that in the case of without departing from the scope and spirit of the present invention as disclosed in claims, various repair
It is possible for changing, increasing and substituting.
As used herein, term " comprises " or " containing " refers to include that a kind of composition (or component) does not limit,
But must not believe that eliminating increases other compositions (or component).
During repeatedly studying Metallocenic compound, inventor is prepared for a kind of ansa-metallocene compounds, and it contains
The indenyl 2 and 4 substituent groups introduced outside dehydrogenation is had as part and to have with the oxygen-confession playing lewis base effect
The abutment of the substituted linking ligand of body, and confirm, use this compound can hold as the loaded catalyst of catalyst precarsor
Preparation of changing places has the polyolefin of high activity and high molecular.
Therefore, according to an embodiment of the invention, it is provided that the ansa-metallocene represented by formula 1 below.
[chemical formula 1]
Wherein, in chemical formula 1,
M1For the periodic table of elements the 3rd race, the 4th race or the transition metal of the 5th race, or it is actinides or lanthanide series；
X can be identical or different, respectively halogen；
A is the element of the periodic table of elements the 14th race and the effect playing the abutment connecting two indenyls；
R1For there is the alkyl of 1 to 20 carbon atoms, there is the thiazolinyl of 1 to 20 carbon atoms, there are 1 to 20 carbon atoms
Alkaryl, there is the aralkyl of 1 to 20 carbon atoms or there is the aryl of 1 to 20 carbon atoms；
R2The alkyl, the thiazolinyl with 1 to 20 carbon atoms that for hydrogen, there are 1 to 20 carbon atoms, there are 1 to 20 carbon
The alkaryl of atom, there is the aralkyl of 1 to 20 carbon atoms or there is the aryl of 1 to 20 carbon atoms；
R3、R3′、R4And R4′Can be identical or different, independently be and there is the alkyl of 1 to 20 carbon atoms, have 1 to 20
The thiazolinyl of individual carbon atom, there is the alkaryl of 1 to 20 carbon atoms, there is the aralkyl of 1 to 20 carbon atoms or have 1 to 20
The aryl of individual carbon atom；And
N is the integer of 1 to 20.
Preferably, R1And R2Independently be the alkyl with 1 to 4 carbon atoms；R3And R3′Independently be and there are 1 to 20
The alkyl of carbon atom, there is the thiazolinyl of 1 to 20 carbon atoms or there is the aralkyl of 1 to 20 carbon atoms；R4And R4′Independently
For there is the aryl of 1 to 20 carbon atoms or there is the alkaryl of 1 to 20 carbon atoms；N is the integer of 1 to 6；And A is silicon
(Si)。
Because the ansa-metallocene of chemical formula 1 is connected by the substituted abutment of the oxygen donor playing lewis base effect containing useful
Two indenyls as part, so the catalysis activity of maximum can have been given play to.Therefore, if by the compound self of chemical formula 1
It is used as prepare polyolefinic catalyst or by chemical formula 1 compound loaded on carrier and as preparing polyolefinic catalysis
Agent, then can easily prepare the polyolefin with desired character.
Meanwhile, embodiment there is provided the side of the ansa-metallocene compounds that preparation is represented by chemical formula 1 according to another
Method.
The method of the ansa-metallocene compounds that described preparation is represented by chemical formula 1 comprises the steps that and makes by below formula a table
The compound shown and the compound represented by below formula b react prepares the compound represented by below formula c:
[chemical formula a]
[chemical formula b]
[chemical formula c]
Wherein, in chemical formula a, b and c,
A is the element of the periodic table of elements the 14th race；
M ' is lithium, sodium, potassium, MgCl, MgBr or MgI；
R1For there is the alkyl of 1 to 20 carbon atoms, there is the thiazolinyl of 1 to 20 carbon atoms, there are 1 to 20 carbon atoms
Alkaryl, there is the aralkyl of 1 to 20 carbon atoms or there is the aryl of 1 to 20 carbon atoms；
R2The alkyl, the thiazolinyl with 1 to 20 carbon atoms that for hydrogen, there are 1 to 20 carbon atoms, there are 1 to 20 carbon
The alkaryl of atom, there is the aralkyl of 1 to 20 carbon atoms or there is the aryl of 1 to 20 carbon atoms；
X can be identical or different, respectively halogen；And
N is the integer of 1 to 20；
Make the compound represented by above chemical formula c and represented by below formula d compound reaction prepare by with
The compound that lower chemical formula e represents:
[chemical formula d]
[chemical formula e]
Wherein, in chemical formula d and e,
A、R1、R2Identical with the definition in chemical formula c with n；
R3、R3′、R4And R4′Can be identical or different, independently be and there is the alkyl of 1 to 20 carbon atoms, have 1 to 20
The thiazolinyl of individual carbon atom, there is the alkaryl of 1 to 20 carbon atoms, there is the aralkyl of 1 to 20 carbon atoms or have 1 to 20
The aryl of individual carbon atom；And
The compound represented by above chemical formula e and the compound represented by below formula f is made to react:
[chemical formula f]
Wherein, in chemical formula f,
M1For the periodic table of elements the 3rd race, the 4th race or the transition metal of the 5th race, or it is actinides or lanthanide series；
And
X can be identical or different, respectively halogen.
According to an embodiment of the invention, the step of the described compound preparing chemical formula c comprises the steps that containing chemistry
The organic solvent of the organic solvent of the compound of formula a and the compound containing chemical formula b at a temperature of-200 DEG C to 0 DEG C, preferably-
Mix at a temperature of 150 DEG C to 0 DEG C and react.After isolating organic layer in mixed solution, vacuum can be carried out further and do
Dry separated organic layer and the step of removing excess reactant.
Additionally, the step of the described compound preparing chemical formula e comprises the steps that addition alkyl in the compound of chemical formula d
The solution of lithium etc., and at 10 DEG C to 50 DEG C, stir at preferably 20 DEG C to 40 DEG C.Then, be added dropwise in mixed solution above
The compound of chemical formula c of preparation, and make they temperature at-150 DEG C to 0 DEG C, anti-at a temperature of preferably-100 DEG C to 0 DEG C
Should, thus prepare the compound of chemical formula e.
Then in the organic solution of the compound containing chemical formula e, add the solution of lithium alkylide etc., make them at-150 DEG C
To the temperature of 0 DEG C, react at a temperature of preferably-100 DEG C to 0 DEG C, and in product, add the compound of chemical formula f also
Reaction.
Additionally, in addition to above-mentioned steps, may further include before or after each step the most any generally
The step carried out, and the preparation method of the present invention is not limited to above-mentioned steps.
Meanwhile, according to another implementation of the invention, it is provided that comprise the alkene of described ansa-metallocene compounds
Polymerization catalyst.
Ansa-metallocene compounds according to the present invention self can serve as olefin polymerization catalysis, or can be as urging
Agent precursor is used as olefin polymerization catalysis together with promoter.
Described olefin polymerization catalysis can be the catalyst at supported on carriers.
As described carrier, it is possible to use those carriers the most normally used and be not particularly limited, and
Preferably, it is possible to use at least one in silicon dioxide, silica-alumina, silica-magnesia.When inciting somebody to action
When described catalyst loads on silica supports, because described silica supports and described ansa-metallocene compounds
Functional group combines with chemical action, so there is no at catalyst described in olefin polymetiation process and separating from surface, and
Therefore, when preparing polyolefin by slurry or gas-phase polymerization, it is not result in polymer particles or the dirty on reactor wall surface.
Further, in the presence of the catalyst containing silica supports, the polyolefin of preparation has the apparent close of excellence
Degree and polymer particles shape, and therefore can compatibly be used in conventional slurry or gas-phase polymerization process.
Therefore, it can the load that be at high temperature dried and from the teeth outwards have high response siloxane group is preferably used
Body.Specifically, it is possible to use the silicon dioxide being at high temperature dried, silica-alumina etc., and they generally comprise oxygen
Compound, carbonate, sulfate, nitrate, such as Na2O、K2CO3、BaSO4、Mg(NO3)2Deng.
Described olefin polymerization catalysis can farther include the promoter being made up of alkylaluminoxane.If using described
Promoter, can use alkyl, such as, have the alkyl of 1 to 20 carbon atoms, replace and be attached to described Metallocenic compound
Metallic atom (M1Halogen group (X) on).
As described promoter, it is possible to use those promoters the most normally used and there is no special limit
System, and preferably, it is possible to use at least one in silicon dioxide, silica-alumina and organo-aluminum compound
Promoter.
The ansa-metallocene compounds catalyst of the present invention is a kind of polyolefin substantially can prepared and have high molecular
Catalyst, and if add hydrogen, the most i.e. use a small amount of hydrogen can also effectively prepare the polyolefin with low-molecular-weight, from
And widen the molecular weight ranges of final polymeric articles.
Meanwhile, according to another implementation of the invention, it is provided that one prepares polyolefinic method, it is included in institute
At least one olefinic monomer it is polymerized in the presence of stating olefin polymerization catalysis.
It is pungent that described olefinic monomer is selected from ethylene, propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-
Alkene, 1-decene, 1-laurylene, 1-tetradecylene, 1-hexadecylene, 1-octadecylene, 1-icosa alkene and combinations thereof.
Described olefinic polymerization can be 1 to 100kgf/cm at a temperature of 25 DEG C to 500 DEG C2Pressure under carry out 1 to 24
Hour.The reaction temperature of polymerization is preferably in the scope of 25 to 200 DEG C (degrees Celsius), and more preferably from 50 DEG C to 100 DEG C
In the range of.Further, polymerization pressure is preferably from 1 to 70kgf/cm2, and more preferably from 5 to 40kgf/cm2.During polymerization
Between be preferably from 1 to 5 hours.
On the other hand, according to whether there is hydrogen to design described polymerization technique to adjust the molecule of final polymeric articles
Amount.Especially, under conditions of hydrogen-free, high molecular polyolefine can be prepared.On the other hand, even if in the existence of a small amount of hydrogen
Under, it is also possible to obtain low-molecular-weight polyolefin.In this respect, the content of the hydrogen used in polymerization is at the reactor of 1 atmospheric pressure
Can be in the range of from 0.07L to 4L under pressure, or can be with 1 bar to 40 bar pressures or right with 168ppm to 8000ppm
The mol ratio of olefinic monomer provides hydrogen.
The polyolefin using the ansa-metallocene compounds catalyst of the present invention to prepare can have ratio and use conventional metals cyclopentadienyl
The molecular weight that polyolefin prepared by catalyst is high.Especially, at described ansa-metallocene compounds catalyst under hydrogen-free condition
In the presence of the polyolefin of preparation can have 200,000 or bigger, or from 200,000 to 600,000, preferably 250,000 or bigger,
The weight average molecular weight (Mw) of more preferably 300,000 or bigger.On the other hand, when having hydrogen condition (such as, when at 1 atmospheric pressure
Under reactor pressure add 0.37L hydrogen time) under use the ansa-metallocene compounds catalyst of the present invention to carry out polymerization technique
Time, polyolefin can have 90,000 or less, or from 55,000 to 90,000, preferably 85,000 or less, and more preferably 80,
The weight average molecular weight (Mw) of 000 or less.
As it has been described above, according to the content of hydrogen, can select in the presence of the ansa-metallocene compounds catalyst of the present invention
Prepare to selecting property the polyolefin of low-molecular-weight or high molecular.
The polyolefin prepared by described method can have 3.3 or less, or 1 to 3.3, and preferably 1.5 to 3.2, and more excellent
Select the distribution (Mw/Mn) of the weight-average molecular weight/number-average molecular weight of 2 to 3.
Calculate with the ratio of the weight (kg) of polymer produced by the catalyst that the every mmol of time per unit (hr) uses, bag
The olefin polymerization catalysis of the ansa-metallocene compounds containing the present invention can have 20kg/mmol hr or higher, or 20 arrive
160kg/mmol hr, preferably 50kg/mmol hr or higher, more preferably 70kg/mmol hr or higher catalysis activity.This
Outward, with every weight portion (g) catalyst of time per unit (hr) produced polymer weight (kg) calculate, catalyst can show
Illustrating 1.0kg/gCat hr or higher, 1.0 arrive 10kg/gCat hr, preferably 2.0kg/gCat hr or higher, and more excellent
Select 3.0kg/gCat hr or higher catalysis activity.
Described polyolefin can have 90% or higher, preferably 92% or higher, and more preferably 95% or higher vertical structure
Regularity (XI).In this respect, described stereoregularity (XI) calculates according to equation 1 below.
[formula 1]
Stereoregularity (XI)=100-Xs
Wherein, in equation 1,
Xs=polymer solubilized mark (wt%) in o-Dimethylbenzene,
The initial volume (mL) of Vb0=o-Dimethylbenzene,
The volume (mL) of the sample that Vb1=extracts from the polymer being dissolved in o-Dimethylbenzene,
The volume (mL) of the o-Dimethylbenzene sample that Vb2=uses in blank experiment,
After the evaporation of W2=o-Dimethylbenzene, on aluminum dish, remaining polymer moral weight adds aluminum dish own wt (g),
The weight (g) of W1=aluminum dish,
The initial weight (g) of W0=polymer, and
B=average weight (g) of residue on aluminum dish in blank experiment.
Fusing point (Tm) and stereoregularity (XI) is can obviously improve by polyolefin prepared by polymerisation in bulk according to the present invention.
Polyolefinic fusing point can be 140 DEG C or higher, or 140 DEG C to 180 DEG C, preferably 143 DEG C or higher, and more preferably 145 DEG C or
Higher.
In the present invention, if desired, details in addition to the above can be adjusted, and it is not specifically limited.
Beneficial effect
Ansa-metallocene compounds according to the present invention has the catalysis activity of excellence, and if using this shank type metal
Cyclopentadinyl compound prepares polyolefin as catalyst or catalyst precarsor, then can easily control the micro structure of polymer, therefore
Easily preparation has the polyolefin of desired character.
Embodiment
The present invention be may be better understood by following example, but enumerating the following example is to illustrate this
Invention, and it is not intended that limit the present invention.
Embodiment 1
Under conditions of described in table 1 below, prepare the ansa-metallocene compounds of chemical formula 2 and include this ansa-metallocene
The olefinic polymerization loaded catalyst of compound.
[chemical formula 2]
The synthesis of metallocene
Step 1:(6-tert-butoxy hexyl) synthesis of dimethyl dichlorosilane (DMCS)
In the methyl trichlorosilane solution (about 0.21mol, hexane) of 100mL, it is slowly dropped into 100mL at-100 DEG C
Tertiary fourth oxygenBaseHexyl magnesium chloride solution (about 0.14mol, ether) 3 hours, is then stirred at room temperature 3 hours.
After transparent organic layer is separated from solution mixture, the transparent organic layer in vacuo so formed is dried, and
Remove the methyl trichlorosilane of excess, obtain (6-tert-butoxy hexyl) dimethyl dichlorosilane (DMCS), for transparency liquid (productivity 84%).
1H NMR(500MHz,CDCl3, 7.24ppm): 0.76 (3H, s), 1.11 (2H, t), 1.18 (9H, s), 1.32～
1.55(8H,m),3.33(2H,t)
Step 2:(6-tert-butoxy hexyl) synthesis of (methyl)-bis-(2-methyl 4-phenyl indenyl) silane
At 0 DEG C in the solution (34.9mmol) of the toluene/THF=10/1 of the 2-methyl 4-phenyl indenes of 70mL slowly
The n-butyllithium solution (2.5M, hexane) of dropping 15.4mL, then stirs reactant mixture 1 hour, then in room at 80 DEG C
It is stirred overnight under temperature.Hereafter, at-78 DEG C, in this reactant mixture, it is slowly added dropwise (the 6-tertiary fourth oxygen that 5g is prepared in step 1
Base hexyl) dimethyl dichlorosilane (DMCS), and gained mixture is stirred 10 minutes, then stir 1 hour at 80 DEG C.Washing with water
After washing, the organic layer so formed is passed through silica gel column chromatography purification, and is vacuum dried to obtain titled reference compound, for Huang
Color grease, productivity 78% (raceme: meso=1:1).
1H NMR(500MHz,CDCl3, 7.24ppm): 0.10 (3H, s), 0.98 (2H, t), 1.25 (9H, s), 1.36～
1.50(8H,m),1.62(8H,m),2.26(6H,s),3.34(2H,t),3.81(2H,s),6.87(2H,s),7.25(2H,t),
7.35(2H,t),7.45(4H,d),7.53(4H,t),7.61(4H,d)
Step 3:[(6-tert-butoxy hexyl methyl silane-diyl)-bis-(2-methyl 4-phenyl indenyls)] zirconium dichloride
Synthesis
To (6-tert-butoxy hexyl) (methyl) double (2-methyl 4-phenyl) indenes of the above-mentioned preparation of 50mL at-78 DEG C
Ether/hexane=1/1 (3.37mmol) solution of base silane is added dropwise over 3.0mL n-BuLi (2.5M in hexane), connects
And be stirred at room temperature about 2 hours, be then vacuum dried.Subsequently, the salt of gained hexane washs, and filters, and is vacuum dried,
Obtain faint yellow solid.By part salt and double (N, N'-diphenyl-1,3-the third diaminourea) dichloro of described preparation in glove box
Change zirconium-bis-(oxolane) [Zr (C5H6NCH2CH2CH2NC5H6)Cl2(C4H8O)2] weigh and join in Shu Lunke flask,
Then at-78 DEG C, it is slowly added dropwise ether wherein, then is stirred at room temperature one day.Subsequently, redness reaction solution was passed through
Filter separates, and is then slowly added dropwise the ethereal HCI solution (1M) of 4 equivalents at-78 DEG C, is then stirred at room temperature 3 hours.Cross
Then filter is vacuum dried, and obtains ansa-metallocene compounds, for orange solids, productivity 85% (raceme: meso=10:1).
1H NMR(500MHz,C6D6, 7.24ppm): 1.19 (9H, s), 1.32 (3H, s), 1.48～1.86 (10H, m),
2.25(6H,s),3.37(2H,t),6.95(2H,s),7.13(2H,t),7.36(2H,d),7.43(6H,t),7.62(4H,d),
7.67(2H,d)
The preparation of loaded catalyst
It is added thereto to the Shu Lunke flask of 3g silicon dioxide adds the MAO (MAO) of 52mmol, then
React 24 hours at 90 DEG C.After precipitation, remove supernatant and the precipitation toluene so formed is washed 2 times.By 240 μ
The ansa-metallocene compounds of the above-mentioned synthesis of mol is dissolved in toluene, then reacts 5 hours at 40 DEG C.Reacting and heavy
After shallow lake completes, remove supernatant and the precipitation toluene so formed is washed twice, then washing twice with hexane, then
Vacuum drying, obtains the silicon dioxide carried metalloscene catalyst of 5g solid particulate form.
[comparative example 1]
Prepare the ansa-metallocene compounds of chemical formula 3 under conditions of describing in table 1 below and include this ansa-metallocene
The olefin polymerization catalysis of compound.
[chemical formula 3]
The preparation of Metallocenic compound
Step 1:(6-tert-butoxy hexyl) synthesis of dimethyl dichlorosilane (DMCS)
(6-tert-butoxy hexyl) dimethyl dichlorosilane (DMCS) is prepared by method same as in Example 1.
The synthesis of step 2:6-tert-butoxy hexyl-bis-indenyl methyl-monosilanes
The n-BuLi being slowly added dropwise 27.9mL at 0 DEG C in the indenes solution (77.55mmol in ether) of 50mL is molten
Liquid (2.5M in hexane), is then stirred at room temperature reactant mixture about 2 hours.Hereafter, mix to this reaction at-78 DEG C
Compound is slowly added dropwise in the step 1 of 9.96g (6-tert-butoxy hexyl) dimethyl dichlorosilane (DMCS) of preparation, and gained is mixed
Thing stirs 10 minutes, is then stirred at room temperature about 3 hours.Subsequently, filter and be vacuum dried product, obtaining the tertiary fourth of 6-
Epoxide hexyl-bis-indenyl methyl-monosilanes, for sticky oil thing (productivity 75%).
1H NMR(500MHz,CDCl3, 7.26ppm): 1.35 (2H, m), 1.55 (2H, m), 1.62 (12H, m), 1.90～
1.67(6H,m),3.76(3H,m),4.04(2H,m),6.82(1H,t),7.04(1H,d),7.34(1H,d),7.38(1H,t),
7.63(2H,m),7.70(2H,m),7.83(1H,d),7.93(3H,m)
Step 3:[(6-tert-butoxy hexyl monosilane-diyl)-bis-(indenyls)] synthesis of zirconium dichloride
To (6-tert-butoxy hexyl)-bis-(indenyl) the methyl-monosilane solution of the above-mentioned preparation of 50mL at-78 DEG C
(29mmol, ether) is slowly added dropwise the n-butyllithium solution (2.5M in hexane) of 26mL, is then stirred at room temperature, then
It is vacuum dried again.Subsequently, gained salt hexane washs, and filters, and is vacuum dried, obtains white solid.To this white solid
Add toluene and glycol dimethyl ether and dissolve, at-78 DEG C, adding ZrCl4Toluene slip, and it is stirred at room temperature mixing
Thing about 3 hours.Subsequently, product it is vacuum dried and adds hexane, filtering the most at low temperatures, obtain [(6-tertiary fourth oxygen
Base hexyl methyl silane-diyl)-bis-(indenyls)] zirconium dichloride, for orange solids.
1H NMR(500MHz,C6D6, 7.26ppm): 1.17 (12H, m), 1.70～1.20 (10H, m), 3.32 (2H, m),
5.86(2H,dd),6.89(1H,m),7.01(2H,m),7.17(2H,m),7.29(2H,d),7.32(2H,m),7.40(2H,d)
The preparation of loaded catalyst
Except ansa-metallocene compounds [(the 6-tert-butoxy hexyl methyl silane-diyl)-bis-(indenes using above-mentioned synthesis
Base)] beyond zirconium dichloride, prepare silicon dioxide carried catalyst by method same as in Example 1.
[comparative example 2]
Prepare the ansa-metallocene compounds of chemical formula 4 under conditions of describing in table 1 below and include this ansa-metallocene
The olefin polymerization catalysis of compound.
[chemical formula 4]
The preparation of Metallocenic compound
Step 1: the synthesis of double (the 2-methyl 4-phenyl indenyl) silane of dimethyl
At 0 DEG C in the solution (49.5mmol) of the toluene/THF=10/1 of the 2-methyl 4-phenyl indenes of 77mL slowly
The n-butyllithium solution (2.5M, hexane solvent) of dropping 21.8mL, then stirs 1 hour at 80 DEG C, the most at room temperature stirs
Mix one day.Hereafter, at a temperature of equal to or less than 0 DEG C, it is slowly added dropwise the dimethyl dichlorosilane (DMCS) of 2.98mL, and stirs reaction
Mixture about 10 minutes, then stirring 1 hour, is warmed up to 80 DEG C simultaneously.Subsequently, add water and isolate organic layer, then
Silica column purification and being vacuum dried, obtains thick yellow oil, yield 61% (raceme: meso=1:1).
1H NMR(500MHz,CDCl3,7.24ppm):0.02(6H,s),2.37(6H,s),4.00(2H,s),6.87(2H,
t),7.38(2H,t),7.45(2H,t),7.57(4H,d),7.65(4H,t),7.75(4H,d)
Step 2:[dimethylsilane diyl double (2-methyl 4-phenyl indenyl)] synthesis of zirconium dichloride
To ether/hexane=1/1 of double (the 2-methyl 4-phenyl indenyl) silane of the dimethyl of 240mL at-78 DEG C
(12.4mmol) solution is slowly added dropwise the n-butyllithium solution (2.5M in hexane) of 10.9mL.Hereafter, it is stirred at room temperature
Reactant mixture one day, then filters and is vacuum dried, it is thus achieved that light yellow solid.By in glove box synthesis part salt and
Double (N, N'-diphenyl-1,3-the third diaminourea) zirconium dichloride double (oxolane) is weighed, then ,-78 in Shu Lunke flask
It is slowly added dropwise ether at DEG C, and stirs reactant mixture one day.Gained red solution is isolated by filtration, vacuum drying, and
And the solution of addition toluene/ether=1/2, obtain limpid red solution.1.5～2 equivalents it are slowly added dropwise at-78 DEG C
Ethereal HCI solution (1M), is then stirred at room temperature 3 hours.Subsequently, filter and be vacuum dried reaction solution, obtaining orange
Solid catalyst, productivity 70% (only raceme).
1H NMR(500MHz,C6D6,7.24ppm):1.32(6H,s),2.24(6H,s),6.93(2H,s),7.10(2H,
t),7.32(2H,t),7.36(2H,d),7.43(4H,t),7.60(4H,d),7.64(2H,d)
The preparation of loaded catalyst
Use Metallocenic compound [dimethylsilane diyl is double (2-methyl 4-phenyl the indenyl)] dichloride of above-mentioned synthesis
Zirconium, prepares silicon dioxide carried metalloscene catalyst by method same as in Example 1.
[comparative example 3]
Under conditions of describing in table 1 below, prepare the ansa-metallocene compounds of chemical formula 5 as follows and include this shank type gold
Belong to the olefin polymerization catalysis of cyclopentadinyl compound.
[chemical formula 5]
The preparation of Metallocenic compound
Step 1: the synthesis of double (2-methyl-4,6-diisopropyl indenyl) silane of dimethyl
It is slowly added dropwise in 2-methyl-4,6-diisopropyl indenes solution (3.45mmol in ether) of 10mL at 0 DEG C
The n-butyllithium solution (2.5M in hexane) of 7.83mL, is then stirred at room temperature mixed solution about 3 hours.Then, exist
It is slowly added dropwise the dimethyl dichlorosilane (DMCS) of 0.2mL at a temperature of less than or equal to 0 DEG C, stirs about 10 minutes, be then warmed up to room
Temperature and stir mixed solution 3 hours.Subsequently, filter and be vacuum dried product, obtain dimethyl double (2-methyl-4,
6-diisopropyl indenyl) silane.
1H NMR(500MHz,CDCl3, 7.24ppm): 0.39 (6H, s), 1.30～1.23 (24H, m), 2.25 (6H, m),
2.91(2H,q),3.18(2H,q),3.53(2H,s),6.71(2H,s),6.95(2H,s),7.14(2H,s)
Step 2:[dimethylsilane diyl double (2-methyl-4,6-diisopropyl indenyl)] synthesis of zirconium dichloride
At 0 DEG C to double (2-methyl-4,6-diisopropyl indenyl) solution of silane of the dimethyl of 10mL (in ether
It is slowly added dropwise the n-butyllithium solution (2.5M in hexane) of 2.3mL in 2.55mmol), is then stirred at room temperature about 4 hours,
Then it is vacuum dried.Then gained salt wash with hexane, filters, and is vacuum dried, obtains white solid.To this white solid
Add toluene and glycol dimethyl ether and dissolve, at-78 DEG C, adding ZrCl4Toluene slip, and it is stirred at room temperature mixing
Thing about 3 hours.Subsequently, it is vacuum dried described mixture, adds hexane, the most at low temperatures filtering mixt, obtain [dimethyl
Silane diyl is double (2-methyl-4,6-diisopropyl indenyl)] zirconium dichloride (raceme: meso=1:1).
1H NMR(500MHz,C6D6, 7.24ppm): 1.19～1.34 (30H, m), 2.22 (6H, s), 2.84 (2H, q),
3.03(2H,q),6.79(2H,s),7.04(2H,q),7.27(2H,s)
The preparation of loaded catalyst
Except the ansa-metallocene compounds [double (2-methyl-4,6-diisopropyl of dimethylsilane diyl using above-mentioned synthesis
Indenyl)] beyond zirconium dichloride, prepare silicon dioxide carried metalloscene catalyst by method same as in Example 1.
[comparative example 4]
Under conditions of describing in table 1 below, prepare the ansa-metallocene compounds of chemical formula 6 as follows and include this shank type gold
Belong to the olefin polymerization catalysis of cyclopentadinyl compound.
[chemical formula 6]
The preparation of Metallocenic compound
The synthesis of (dimethylsilane diyl-bis-indenyls) zirconium dichloride
In the solution containing 44mL indenes and 150mL oxolane (THF), the lithium methide of 215mL it is slowly added dropwise at 0 DEG C
Solution (1.4M in THF), is then stirred at room temperature about 2 hours, is then vacuum dried.Subsequently, it is slowly added dropwise at 0 DEG C
The methyUithium solution (1.4M in THF) of 225mL, makes mixture reaction, is stirred at room temperature about 1 hour simultaneously.Meanwhile, exist
In the THF of-80 DEG C of 200cc, add 40g Zirconium tetrachloride., then heat to 25 DEG C.In this mixture, by above-mentioned mixing also
The indenes solution of reaction is slowly added in this zirconium halide solution, makes mixture reaction, stirs 1 hour at 25 DEG C simultaneously.By described
Mixture is dried 24 hours, obtains oily mater, filters this material, obtains (dimethylsilane diyl-bis-indenyls) zirconium dichloride,
For yellow solid.
1H NMR(500MHz,C6D6,7.26ppm):0.54(6H,s),5.774(2H,d),6.80(2H,d),6.86(2H,
t),7.14(2H,t),7.22(2H,d),7.33(2H,d)
The preparation of loaded catalyst
In addition to using ansa-metallocene compounds (dimethylsilane diyl-bis-indenyls) zirconium dichloride of above-mentioned synthesis,
Silicon dioxide carried metalloscene catalyst is prepared by method same as in Example 1.
[table 1]
Preparation embodiment 1～2 and contrast preparation embodiment 1～4
Use the metalloscene catalyst of preparation in embodiment 1 and comparative example 1～4 to prepare polypropylene as follows respectively to gather
Compound.
Propylene polymerization
First, the stainless steel reactor of 2L it is dried at 65 DEG C and cools down, under room temperature, being added thereto to 1.5mmol's
Triethyl aluminum, then order adds hydrogen and the propylene of 1.5L of 0.37L.Hereafter, stirring mixture 10 minutes, then at nitrogen gas
Atmosphere downhill reaction device adds every kind of metalloscene catalyst of preparation in the embodiment 1 of 0.019g and comparative example 1～3.This
Time, hydrogen is simultaneously introduced with described metalloscene catalyst.Subsequently, the temperature of reactor is slowly raised to 70 DEG C, in this temperature
Under carry out being polymerized 1 hour.After having reacted, discharge unreacted propylene monomer.
Measure the content of catalyst and the character of polymer that is active and that produced, and data collect in table 2 below.
<method measuring polymer property>
(1) catalyst activity: the weight of every deal used catalyst (mmol and g) the produced polymer of time per unit (hr)
The ratio of amount (kg PP).
(2) fusing point (Tm) of polymer: use differential scanning calorimetry (DSC) (DSC2920, TA instrument) to measure the molten of polymer
Point.In short, polymer temperature is risen to 220 DEG C and keeps 5 minutes at this temperature, then drop to 20 DEG C, then
Heat up from this temperature again.In this respect, with constant heating rates sintering and the cooling of 10 DEG C/min.
(3) crystallization temperature (Tc) of polymer: use DSC to be reduced the phase by temperature under conditions of identical with measuring fusing point
Between draw curve determination Tc.
(4) stereoregularity (XI) of polymer: after polymer is dissolved 1 hour in the o-Dimethylbenzene of boiling, polymerization
The percentage by weight (%) of the soluble part of thing.
In short, by No. 4 filter paper filterings by 200mm of the 200mL o-Dimethylbenzene in flask.Individually, by aluminum dish
It is dried in an oven at 150 DEG C 30 minutes, cools down in exsiccator, and weigh.Then, by filtered for 100mL adjacent two
Toluene moves liquid in aluminum dish, then this aluminum dish is heated to 140～150 DEG C, evaporates o-Dimethylbenzene the most completely.Subsequently, exist
Under 13.3kPa pressure, described aluminum dish is vacuum dried 1 hour at 100 ± 5 DEG C.Then, described aluminum dish is cooled down in exsiccator.
This process twice is repeated to complete only with the blank experiment of o-Dimethylbenzene in the range of the weight error of 0.0002g.
Then, the polymer produced by aforesaid propylene polymerization technique is dried (70 DEG C, 13.3kPa, 60 minutes, very
Empty), and the sample of the 2 ± 0.0001g polymer cooled down in exsiccator is put in the flask of 500mL, then to flask
The o-Dimethylbenzene of middle addition 200mL.While continuing the supply of nitrogen and cooling water to described flask, by o-Dimethylbenzene at high temperature
Lower backflow 1 hour.Then, described flask is cooled down in atmosphere 5 minutes to less than 100 DEG C, shake, and put into water-bath (25
± 0.5 DEG C) in 30 minutes to precipitate soluble part.Gained is repeated by No. 4 extraction paper of 200mm with the solution of precipitation
Filter until solution turned clear.Filter liquor is dried 30 minutes at 150 DEG C, and cools down in exsiccator.Clear by 100mL
Clear filter liquor is placed in the aluminum dish measuring weight in advance.Adjacent diformazan is evaporated by heating aluminum dish at 145～150 DEG C
Benzene.After having evaporated, under the pressure of 13.3kPa by aluminum dish 70 ± 5 DEG C vacuum drying 1 hour and in exsiccator cold
But.This process twice is repeated to measure the weight of solubilized part in the range of the weight error of 0.0002g.
The percentage by weight (Xs) of polymer solubilized part in o-Dimethylbenzene calculates according to equation 1 below, and
The weight percent using it to obtain the soluble part of polymer is used for stereoregularity (XI).
[formula 1]
Stereoregularity (XI)=100-Xs
Wherein, in equation 1,
Xs=polymer solubilized mark (wt%) in o-Dimethylbenzene,
The initial volume (mL) of Vb0=o-Dimethylbenzene,
The volume (mL) of the sample that Vb1=extracts from the polymer being dissolved in o-Dimethylbenzene,
The volume (mL) of the o-Dimethylbenzene sample that Vb2=uses in blank experiment,
After W2=evaporation o-Dimethylbenzene, on aluminum dish, the weight of remaining polymer adds aluminum dish own wt (g),
The weight (g) of W1=aluminum dish,
The initial weight (g) of W0=polymer, and
B=average weight (g) of residue on aluminum dish in blank experiment.
(5) molecular weight distribution (PDI, polydispersity index) of polymer and weight average molecular weight (Mw): the weight average of polymer divides
Son amount (Mw) and number-average molecular weight (Mn) use gel permeation chromatography (GPC, Waters) to measure, and molecular weight distribution
(PDI) by calculating except weight average molecular weight by number-average molecular weight.To this, with polystyrene standardized at 160 DEG C in trichlorine
Benzene is measured molecular weight.
Use in embodiment 1 and comparative example 1～4 metalloscene catalyst of preparation in preparation embodiment 1～2 and contrast
Prepare the polymerization process condition in embodiment 1～4, and prepared polyacrylic character collects in table 2 below.
[table 2]
As shown in table 2, there is the Metallocenic compound of indenyl and the special substituent on abutment as load in use
In the preparation embodiment 1～2 of type catalyst, high activity and the effect of molecular weight increase can be obtained when preparing polyolefin.Special
, in preparation embodiment 1～2, it is not catalyzed superior activity, is 80.9～138.5kg/mmol hr and 3.05～5.21kg/
GCat hr, and the polymer produced has the stereoregularity (XI) that 98.18%～98.22% improvement is a lot.This
Outward, be there is the excellent molecular weight distribution (MWD:Mw/ of 2.19～2.57 by the polyacrylic polymer of preparation embodiment 1～2 preparation
Mn)。
Meanwhile, in preparation embodiment 1 and 2, further increase activity by addition hydrogen upon polymerization, though and logical
Cross and add a small amount of hydrogen and can also effectively prepare high fluidity polymer.Especially, in the case of preparation embodiment 1, it is being not added with
Enter in the case of hydrogen by carrying out the polypropylene that polymerization technique can have the high molecular of 381,000 with high activity preparation.This
Outward, in the case of preparation embodiment 2, can also have 76 with high activity preparation by adding a small amount of hydrogen in the course of the polymerization process,
The polypropylene of the low-molecular-weight of 500.Additionally, by preparation embodiment 1～2 produce polyacrylic polymer have 148.4 to
The fusing point (Tm) being obviously improved of 150.4 DEG C.
On the contrary, the Metallocenic compound the not having special substituent contrast as catalyst is being used to prepare embodiment 1～2
In, catalysis activity and produced polyolefinic stereoregularity etc. and be decreased obviously.Especially, in the feelings of contrast preparation embodiment 1
Under condition, when using the Metallocenic compound not containing special substituent on indenyl to carry out polymerization technique as catalyst, catalysis
Activity obviously drops to 6.05kg/mmol hr and 0.30kg/gCat hr, and the stereoregularity of produced polymer is not
Good, it is 89.8%.
Additionally, do not contain special substituent and abutment on abutment with methyl substituted Metallocenic compound as urging using
In the case of embodiment 2 is prepared in the contrast of agent, catalysis activity is bad, for 14.6kg/mmol hr and 0.55kg/gCat
hr.Visible, in contrast preparation embodiment 2, owing to not including oxygen-donor functional group in abutment, so carrier efficiency reduces
And activity decrease.Additionally, at the Metallocenic compound of the different substituents using different substituents and the abutment with indenyl
In the case of preparing embodiment 3 as the contrast of catalyst, polymerization never occurs, thus, it could be seen that [dimethylsilane diyl
Double (2-methyl-4,6-diisopropyl indenyls)] catalyst precarsor of zirconium dichloride has low activity, and is formed without support type
Catalyst.
Additionally, do not contain special substituent and abutment on indenyl only with methyl substituted existing Metallocenic compound using
In the case of preparing embodiment 4 as the contrast of catalyst, catalysis activity is bad, for 14.3kg/mmol hr and 0.54kg/
gCat·hr.In addition, it is seen then that in the case of contrast preparation embodiment 4, although application is as prepared the same terms of embodiment 1,
Still show the lowest molecular weight, and the polyacrylic polymer of high molecular can not be produced.Especially, in contrast preparation embodiment
In the case of 4, catalyst component discharges from loaded catalyst upon polymerization, produces dirty the most in the reactor.
In addition, it is seen then that the polyacrylic polymer produced by contrast preparation embodiment 1 and 4 is respectively provided with 138.7 Hes
The fusing point (Tm) substantially reduced of 135.2 DEG C.
Claims (11)
1. the ansa-metallocene compounds represented by formula 1 below:
[chemical formula 1]
Wherein, in chemical formula 1,
M1For Zr；
X is identical or different, respectively halogen；
R1And R2Independently be the alkyl with 1 to 4 carbon atoms；R3And R3′Independently be the alkane with 1 to 20 carbon atoms
Base；R4And R4′Independently be the aryl with 6 to 20 carbon atoms；N is the integer of 1 to 6；And A is silicon.
2. the method preparing the ansa-metallocene compounds represented by chemical formula 1 of claim 1, comprises
The compound represented by below formula a and the compound reaction represented by below formula b is made to prepare following chemistry
The compound of formula c:
[chemical formula a]
[chemical formula b]
[chemical formula c]
Wherein, in chemical formula a, b and c,
A is silicon；
M ' is lithium, sodium, potassium, MgCl, MgBr or MgI；
R1And R2Independently be the alkyl with 1 to 4 carbon atoms；
X is identical or different, respectively halogen；And
N is the integer of 1 to 6；
The compound represented by above chemical formula c and the compound reaction represented by below formula d is made to prepare following chemistry
The compound of formula e:
[chemical formula d]
[chemical formula e]
Wherein, in chemical formula d and e,
A、R1、R2Identical with the definition in chemical formula c with n；
R3And R3′Independently be the alkyl with 1 to 20 carbon atoms；R4And R4′Independently be the virtue with 6 to 20 carbon atoms
Base；And
The compound represented by above chemical formula e and the compound represented by below formula f is made to react:
[chemical formula f]
Wherein, in chemical formula f,
M1For Zr；And
X is identical or different, respectively halogen.
3. an olefin polymerization catalysis, it comprises ansa-metallocene compounds as claimed in claim 1.
Olefin polymerization catalysis the most according to claim 3, wherein, described ansa-metallocene compounds is supported on selected from two
On the carrier of silicon oxide, silica-alumina, silica-magnesia and combinations thereof.
5. preparing a polyolefinic method, it is polymerized in the presence of being included in the catalyst as described in claim 3 or 4
At least one olefinic monomer.
Method the most according to claim 5, wherein, described in be aggregated at a temperature of 25 to 500 DEG C 1 to 100kgf/cm2
Pressure under carry out 1 to 24 hours.
Method the most according to claim 5, wherein, described olefinic monomer is selected from ethylene, propylene, 1-butylene, 1-amylene, 1-
Hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-laurylene, 1-tetradecylene, 1-hexadecylene, 1-octadecylene, 1-icosa alkene
And combinations thereof.
Method the most according to claim 5, wherein, the polymerization that the catalyst used with the every mmol of time per unit is produced
The ratio of the weight of thing calculates, and catalyst activity is 20kg/mmol hr or higher.
Method the most according to claim 5, wherein, it is poly-that the catalyst used with the every weight portion of time per unit is produced
The ratio of the weight of compound calculates, and catalyst activity is 1.0kg/gCat hr or higher.
Method the most according to claim 5, wherein, described polyolefin has 90% or higher stereoregularity.
11. methods according to claim 5, it is the polymerisation in bulk for acrylic polymers.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20120048850 | 2012-05-08 | ||
| KR10-2012-0048850 | 2012-05-08 | ||
| KR1020130049315A KR101549206B1 (en) | 2012-05-08 | 2013-05-02 | Ansa-metallocene catalyst and preparation method of supported catalyst by using the same |
| PCT/KR2013/003807 WO2013168928A1 (en) | 2012-05-08 | 2013-05-02 | Ansa-metallocene compound and method for preparing supported catalyst using same |
| KR10-2013-0049315 | 2013-05-02 |
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| CN104271586A CN104271586A (en) | 2015-01-07 |
| CN104271586B true CN104271586B (en) | 2016-11-30 |
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| US6350830B1 (en) * | 1998-02-19 | 2002-02-26 | Tagor Gmbh | Catalyst system, method for the production thereof and its use for the polymerization of olefins |
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| US6350830B1 (en) * | 1998-02-19 | 2002-02-26 | Tagor Gmbh | Catalyst system, method for the production thereof and its use for the polymerization of olefins |
| US20010053833A1 (en) * | 2000-05-23 | 2001-12-20 | Chisso Corporation | Metallocene compound, olefin polymerization catalyst containing the compound, and method for producing an olefin polymer by use of the catalyst |
| US7094857B2 (en) * | 2004-03-10 | 2006-08-22 | Chevron Phillips Chemical Company, L.P. | Ethylene polymers and copolymers with high optical opacity |
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