CN116410369A - Main catalyst of olefin polymerization catalyst, and preparation method and application thereof - Google Patents
Main catalyst of olefin polymerization catalyst, and preparation method and application thereof Download PDFInfo
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- CN116410369A CN116410369A CN202111672904.5A CN202111672904A CN116410369A CN 116410369 A CN116410369 A CN 116410369A CN 202111672904 A CN202111672904 A CN 202111672904A CN 116410369 A CN116410369 A CN 116410369A
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- compound
- catalyst
- olefin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 54
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002685 polymerization catalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- -1 C3-C20 cycloalkyl Chemical group 0.000 claims abstract description 39
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 150000003624 transition metals Chemical group 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 123
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 63
- 239000005977 Ethylene Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 238000007334 copolymerization reaction Methods 0.000 claims description 44
- 239000003446 ligand Substances 0.000 claims description 44
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 44
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 38
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 38
- 238000006116 polymerization reaction Methods 0.000 claims description 36
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 23
- 239000004711 α-olefin Substances 0.000 claims description 20
- 239000012968 metallocene catalyst Substances 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052735 hafnium Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007818 Grignard reagent Substances 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- NUUNDIOOYFEMQN-UHFFFAOYSA-N cyclopenta-1,3-diene;sodium Chemical compound [Na].C1C=CC=C1 NUUNDIOOYFEMQN-UHFFFAOYSA-N 0.000 claims description 4
- 150000004795 grignard reagents Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 150000003623 transition metal compounds Chemical class 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 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
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- SNTUCKQYWGHZPK-UHFFFAOYSA-N 4-ethenylbenzonitrile Chemical compound C=CC1=CC=C(C#N)C=C1 SNTUCKQYWGHZPK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 229940125904 compound 1 Drugs 0.000 claims description 2
- 229940125773 compound 10 Drugs 0.000 claims description 2
- 229940125782 compound 2 Drugs 0.000 claims description 2
- 229940126214 compound 3 Drugs 0.000 claims description 2
- 229940125898 compound 5 Drugs 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims description 2
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 claims description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 2
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 80
- 229910052757 nitrogen Inorganic materials 0.000 description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 40
- 229920000642 polymer Polymers 0.000 description 29
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 20
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 20
- 229910001220 stainless steel Inorganic materials 0.000 description 20
- 239000010935 stainless steel Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 10
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 10
- OHUVHDUNQKJDKW-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C=1C=C[CH-]C=1 OHUVHDUNQKJDKW-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 5
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 3
- YCITZMJNBYYMJO-UHFFFAOYSA-N chloro(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](Cl)C1=CC=CC=C1 YCITZMJNBYYMJO-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical class C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 description 1
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 1
- BJSVKBGQDHUBHZ-UHFFFAOYSA-N 2,4,6-trifluoroaniline Chemical compound NC1=C(F)C=C(F)C=C1F BJSVKBGQDHUBHZ-UHFFFAOYSA-N 0.000 description 1
- ODUZJBKKYBQIBX-UHFFFAOYSA-N 2,6-difluoroaniline Chemical compound NC1=C(F)C=CC=C1F ODUZJBKKYBQIBX-UHFFFAOYSA-N 0.000 description 1
- HTFNVAVTYILUCF-UHFFFAOYSA-N 2-[2-ethoxy-4-[4-(4-methylpiperazin-1-yl)piperidine-1-carbonyl]anilino]-5-methyl-11-methylsulfonylpyrimido[4,5-b][1,4]benzodiazepin-6-one Chemical compound CCOc1cc(ccc1Nc1ncc2N(C)C(=O)c3ccccc3N(c2n1)S(C)(=O)=O)C(=O)N1CCC(CC1)N1CCN(C)CC1 HTFNVAVTYILUCF-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- SOYVLBDERBHIME-UHFFFAOYSA-N chloro(diethyl)silicon Chemical compound CC[Si](Cl)CC SOYVLBDERBHIME-UHFFFAOYSA-N 0.000 description 1
- IGSUJBNDAWQLST-UHFFFAOYSA-N chloro-di(propan-2-yl)silicon Chemical compound CC(C)[Si](Cl)C(C)C IGSUJBNDAWQLST-UHFFFAOYSA-N 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a main catalyst of an olefin polymerization catalyst, which is a compound shown in a general formula (I),
in the general formula (1), R 1 、R 2 Each independently selected from one of C1-C20 linear alkyl, C3-C20 cycloalkyl, C6-C20 aryl; x is selected from F, cl, br, I or C1-C20 alkaneA base; m represents a transition metal atom selected from one of group IVB elements. The invention also provides a preparation method of the main catalyst of the olefin polymerization catalyst and the olefin polymerization catalyst containing the main catalyst.
Description
Technical Field
The invention belongs to the field of olefin polymerization catalysts and olefin coordination polymerization, and in particular relates to a main catalyst of an olefin polymerization catalyst for ethylene or propylene homopolymerization, ethylene/alpha-olefin copolymerization or propylene/alpha-olefin copolymerization, ethylene/polar olefin monomer copolymerization and propylene/polar olefin monomer copolymerization, and a preparation method and application thereof.
Background
Metallocene catalysts have been receiving attention because of their single active center, and their activity, stereoregularity of polymers, molecular weight and molecular weight distribution can be controlled by changing ligand structures; and the superior properties of metallocene catalyst synthesized polymers have been consistently recognized.
Polyolefin products have many advantages such as easy processing, good thermal stability, good weatherability, good chemical resistance and long service life, etc., and are well received by the market. However, polyolefin (such as PE, PP, etc.) has poor low temperature resistance and high crystallinity, which results in limited application range. If a certain amount of higher alpha-olefin (such as 1-octene, etc.) is inserted into the molecular chain of polyolefin to prepare block copolymer, the structure and property of polyolefin will developThe obvious change is that: the density of the polymer can be lower than that of common polyolefin, and is 0.85-0.92 g/cm 3 Between them; the glass transition temperature is low, the low temperature resistance is good, and the dispersibility, the weather resistance, the flexibility and the processability are good. The performance of ethylene/1-octene copolymer is superior to that of ethylene/propylene copolymer and ethylene/1-butene copolymer, and the age of ethylene/1-octene copolymer to replace ethylene/propylene copolymer and ethylene/1-butene copolymer is coming.
Metallocene catalysts have appeared in the fifties of the twentieth century, and such catalysts have been easy to achieve olefin copolymerization, thereby synthesizing polyolefin materials excellent in performance. In addition, the design and synthesis of the ligand structure of the metallocene catalyst are greatly changeable. It develops rapidly from the first appearance and has been paid attention to.
Ma Lifu [ Ma L F, et al journal Polymer Science: part A: polymer Chemistry,2008,46:33; ma L F, et al journal Polymer Science: part A: polymer Chemistry,2010,48:417] prepare a series of [ N, N ] heterocyclic non-metallocene compounds, and after MAO activation, ethylene polymerization and ethylene/1-hexene copolymerization can be efficiently catalyzed to obtain broad/bimodal polyethylene.
Keim [ George J.P et al journal of Molecular Catalysis A:chemical 110 (1996): 77-87] synthesized palladium catalysts of the type [ N, O ], [ P, O ], [ O, O ], [ S, O ], catalyzed copolymerization of styrene with ethylene, studied the relationship between the structure and catalytic activity of the catalyst ligand.
Sun Wenhua A series of catalysts containing [ N, N ] aminoindoles [ Zhang W J, et al J of Organometallic chem 2006,691:4759-4767], [ N, N, O ] pyridylsalicyl catalysts [ Shaofeng Liu, et al journal of Polymer Science:part A: polymer Chemistry,2008,46:3411-3423], [ P, N, N ] and [ P, N, P ] types of catalysts [ Hou J X, et al organometallics,2006,25:236-244] are active for catalyzing ethylene polymerization.
Patent 200310108556 reports a composition containing [ O, N, N, O ]]Ligand complex as olefin polymerization catalyst with catalytic activity of 10 5 gPE/molTi.h. Patent CN102030843 discloses a catalyst containing [ N, N, O]Alkene of structural ligandHydrocarbon polymerization non-metallocene catalysts. When the olefin polymerization is catalyzed, the catalyst has better catalytic activity on ethylene homopolymerization, ethylene/alpha-olefin and ethylene/polar monomer copolymerization.
The main ring structures of the metallocene catalysts disclosed above all contain carbon atoms, heteroatoms and transition metal atoms.
Disclosure of Invention
The invention aims to provide a main catalyst of an olefin polymerization catalyst, wherein a main ring of the main catalyst is composed of hetero atoms (N, si) and transition metal atoms IVB besides carbon atoms. The heterocyclic metallocene catalyst can effectively catalyze ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar olefin monomer copolymerization or propylene and polar olefin monomer copolymerization, and has high catalyst activity; the heterocyclic metallocene catalyst can also be loaded on a carrier to prepare a supported catalyst, so that ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar olefin monomer copolymerization and propylene and polar olefin monomer copolymerization are effectively catalyzed, and the catalyst activity is high.
Another object of the present invention is to provide a method for preparing a main catalyst of an olefin polymerization catalyst and use of the main catalyst.
The invention provides a main catalyst of an olefin polymerization catalyst, which is a compound shown in a general formula (I),
in the general formula (1), R 1 、R 2 Each independently selected from one of C1-C20 linear alkyl, C3-C20 cycloalkyl, C6-C20 aryl; x is selected from F, cl, br, I or C1-C20 alkyl; m represents a transition metal atom selected from one of group IVB elements.
The compound shown in the general formula (I) is a heterocyclic metallocene catalyst compound, the main ring structure of the compound is a heterocyclic ring composed of C, N, si and a transition metal atom M, and a plurality of substituents are arranged on the ring.
The main catalyst of the olefin polymerization catalyst of the present invention, wherein X is preferably selected from Cl, br, me or Et; m is selected from one of titanium, zirconium and hafnium.
The main catalyst of the olefin polymerization catalyst of the present invention is preferably one of the following compounds:
compound 1: m=titanium, x=cl, R 1 Phenyl group, R 2 Phenyl;
compound 2: m=zirconium, x=cl, R 1 =benzyl, R 2 Methyl group;
compound 3: m=titanium, x=me, R 1 =cyclohexyl, R 2 Methyl group;
compound 4: m=zirconium, x=cl, R 1 =2, 4, 6-trimethylphenyl, R 2 Phenyl;
compound 5: m=hafnium, x=cl, R 1 =cyclopentyl, R 2 Methyl group;
compound 6: m=titanium, x=br, R 1 =2, 6-dimethylphenyl, R 2 Phenyl;
compound 7: m=zirconium, x=cl, R 1 =isopropyl, R 2 =isopropyl;
compound 8: m=hafnium, x=cl, R 1 =2, 6-dimethylphenyl, R 2 =2, 6-dimethylphenyl;
compound 9: m=titanium, x=cl, R 1 =2, 6-difluorophenyl, R 2 Methyl group;
compound 10: m=hafnium, x=et, R 1 =2, 4, 6-trifluorophenyl, R 2 Ethyl.
In particular, therein M, X, R 1 And R is 2 Each having the following group definitions, see table 1:
table 1 Compounds according to the general formula (1)
Further, the main catalyst is specifically selected from the following compounds (1) to (10), but is not limited thereto:
to this end, the present invention provides a method for preparing a main catalyst for an olefin polymerization catalyst, comprising the steps of:
(1) Adding an organic solvent into a ligand compound which accords with the general formula (II), adding n-butyllithium, stirring, and carrying out a third reaction; the general formula (II) is shown as the following formula:
in the general formula (II), R 1 、R 2 Each independently selected from one of C1-C20 linear alkyl, C3-C20 cycloalkyl, C6-C20 aryl;
preferably, wherein R 1 And R is 2 Each having the group definitions as shown in table 2:
table 2 Compounds according to the general formula (2)
(2) Continuously adding a transition metal compound, stirring, carrying out a fourth reaction, then removing the organic solvent, washing the remainder with the organic solvent, and pumping to obtain the (Si-N) multi-heterocyclic metallocene catalyst which accords with the general formula (1);
preferably, the molar ratio of n-butyllithium to the ligand compound is 0.5-4:1, and the molar ratio of the ligand compound to the transition metal compound is 1:1-2, more preferably 1:1-1.5.
The production method of the present invention, wherein preferably, the production of the ligand compound conforming to the general formula (2) comprises the steps of: dissolving aryl primary amine or substituted aryl primary amine compound in an organic solvent, adding a Grignard reagent for a first reaction, wherein the mole ratio of the Grignard reagent to the aryl primary amine or substituted aryl primary amine compound is 0.3-6:1; then adding an organic silicon compound, adding sodium cyclopentadiene, and carrying out a second reaction to obtain the ligand compound which is in accordance with the general formula (II), wherein the molar ratio of the organic silicon compound to the aryl primary amine or the substituted aryl primary amine compound is 0.3-6:1, and the molar ratio of the sodium cyclopentadiene to the aryl primary amine compound is 0.2-10:1.
The preparation process according to the invention, wherein preferably the organosilicon compound corresponds to the general formula: r is R 2 R 2 SiHX (III), wherein R 2 Selected from one of C1-C20 linear alkyl, C3-C20 cycloalkyl and C6-C20 aryl, and X is selected from F, cl, br, I or C1-C20 alkyl.
The preparation method of the present invention, wherein preferably, the conditions of the first reaction are: the temperature is between 50 ℃ below zero and 70 ℃ below zero for 2 to 10 hours; further preferably, the temperature is 10-50 ℃ for 2-4 hours;
the conditions of the second reaction are as follows: the temperature is between 50 ℃ below zero and 80 ℃ below zero for 1 to 8 hours;
the conditions of the third reaction are as follows: the temperature is 0-60 ℃ and the time is 3-10 hours;
the conditions for the fourth reaction are: the temperature is 20-80 ℃ and the time is 3-10 hours.
The preparation method of the present invention, wherein preferably the organic solvents are the same or different and are each independently selected from C 5 ～C 15 Saturated hydrocarbon of C 5 ～C 10 Alicyclic hydrocarbon of (C) 6 ～C 15 Aromatic hydrocarbon of C 2 ～C 10 At least one of the saturated heterocyclic hydrocarbons of (2).
The invention also provides an olefin polymerization catalyst, which comprises a main catalyst and a cocatalyst, wherein the main catalyst is the compound, the cocatalyst is an organic metal aluminum compound, preferably alkylaluminum or alkylaluminoxane which is a hydrolysate of alkylaluminum, and the mol ratio of the cocatalyst to the main catalyst is (100-5000): 1, preferably (150 to 1000): 1.
the olefin polymerization catalyst according to the present invention, wherein the cocatalyst is preferably at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and methylaluminoxane.
The olefin polymerization catalyst of the present invention is preferably used for catalyzing olefin homo-polymerization or olefin copolymerization, and the polymerized monomer is selected from ethylene and C 3 ～C 20 Alpha-olefins, C 3 ～C 20 Non-conjugated diolefins, C 3 ～C 20 At least one of polar olefinic monomers; further preferably, the olefin polymerization catalyst is used for catalyzing ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar vinyl monomer copolymerization, and propylene and polar vinyl monomer copolymerization; the alpha-olefin being C 3 -C 20 Further preferred are propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene, styrene, alpha-methylstyrene, norbornene, 1, 7-bicyclooctene or 1, 8-bicyclononene; the polar vinyl monomer contains a carbon-carbon double bond and also has a polar group, and further preferably acrylonitrile, 4-cyanostyrene, methyl methacrylate, methyl acrylate or butyl acrylate.
The olefin polymerization catalyst of the invention is preferably used for catalyzing olefin polymerization, wherein the polymerization temperature is 20-90 ℃, the polymerization time is 5 min-3 h, the pressure of monomer ethylene or propylene is 0.1-5 MPa, and the solvent comprises at least one of n-hexane, heptane and toluene.
The main ring of the main catalyst of the olefin polymerization catalyst provided by the invention is composed of hetero atoms (N, si) and transition metal atoms IVB besides carbon atoms. The heterocyclic metallocene catalyst can effectively catalyze ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar olefin monomer copolymerization or propylene and polar olefin monomer copolymerization, and has high catalyst activity; the heterocyclic metallocene catalyst can also be loaded on a carrier to prepare a supported catalyst, so that ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar olefin monomer copolymerization and propylene and polar olefin monomer copolymerization are effectively catalyzed, and the catalyst activity is high.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and the experimental methods of specific conditions are not noted in the following examples, and generally, the% is weight% according to conventional conditions.
Example 1
(1) Synthesis of ligand compound A1 [ A1 structure: r in the general formula (2) 1 ，R 2 All select phenyl groups]
30ml of toluene, 1.82ml of aniline and 6.67ml of methyl magnesium chloride (3M) in THF are taken in a 300ml schlenk flask and heated to 35 ℃ for reaction for 2 hours; 4.38g of diphenyl chlorosilane is added for reaction for 3 hours; 1.86ml of cyclopentadienyl sodium was further added, and after reacting at 35℃for 4 hours, the mixture was drained, 100ml of n-hexane was added to the remaining solid, dissolved and filtered, and the filtrate was recrystallized to give 4.41g of ligand compound A1, yield: 65%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝7.47(d,4H,Si-Ph)；7.35(d,6H,Si-Ph)；7.25(d,2H,N-Ph)；7.06(d,2H,N-Ph)；6.92(t,1H,N-Ph)；5.67(s,1H,N-H)；4.90(d,1H,Cp)；4.32(s,1H,Cp)；3.81(d,1H,Cp)；3.38(s,1H,Si-H)；Anal.Calcd.(％)for C 23 H 20 NSi(338):C,81.61；H,5.96；found:C,81.58；H,5.91；ESI-MS m/z calculated for[M+H] + .C 23 H 20 NSi:338.14,found,339.14。
(2) Preparation of the procatalyst
Under the protection of nitrogen, 0.43g of ligand compound A1 is dissolved in 30mL of toluene, equimolar amount of n-butyllithium is added, and the mixture is stirred and reacted for 5 hours at 30 ℃; and then0.14mL of titanium tetrachloride was added, the temperature was raised to 50℃and the reaction was carried out for 4 hours. The solvent was removed in vacuo, and the residue was washed 3 times with n-hexane and dried to give 0.36g of catalyst (1), yield: 67.2%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝7.40-7.32(m,10H,Si-Ph)；7.30-7.15(m,5H,N-Ph)；4.90(d,1H,Cp)；4.32(s,1H,Cp)；3.81(d,1H,Cp)；Anal.Calcd.(％)for C 23 H 18 ClNSiTi(419):C,65.80；H,4.32；found:C,65.74；H,4.28；ESI-MS m/z calculated for[M+H] + .C 23 H 18 ClNSiTi:419.04,found,420.04。
(3) Polymerization of ethylene:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 5mg of the main catalyst and 4ml of MAO solution (10 wt%) were added. The temperature was raised to 50℃and the ethylene pressure was 0.7MPa, and the polymerization was carried out for 120mins. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, and then air-dried at 50℃for 24 hours, collecting 330g of the polymerization product.
(4) Ethylene copolymerization:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 5mg of the main catalyst, 4ml of MAO solution (10 wt%) and 30ml of 1-butene. The temperature was raised to 50℃and the ethylene pressure was maintained at 0.7MPa for 30mins. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 323g of the product was collected.
Example 2
(1) Synthesis of ligand compound A2 [ A2 structure: r in the general formula (2) 1 Benzyl, R is selected 2 Methyl is selected]
30ml of toluene, 2.18ml of benzylamine and 6.67ml of methyl magnesium chloride (3M) in THF are taken in a 300ml schlenk flask and heated to 35 ℃ for reaction for 2 hours; 2.18ml of dimethylchlorosilane is added for reaction for 4 hours; then adding 1.86ml of cyclopentadienyl sodium, reacting for 4 hours at 35 ℃, pumping, adding 100ml of normal hexane into the residual solid, dissolving and filtering, recrystallizing the filtrate to obtain 3.25g of ligand compound A2The yield is 71%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝7.32-7.28(m,5H,Ph)；4.59(s,2H,-CH 2 )；4.25(d,1H,Cp)；4.01(s,1H,Cp)；3.98(s,1H,N-H)；3.59(s,1H,Si-H)；3.41(d,1H,Cp)；0.14(s,6H,-CH 3 )；Anal.Calcd.(％)for C 14 H 18 NSi(228):C,73.63；H,7.94；found:C,73.61；H,7.90；ESI-MS m/zcalculated for[M+H] + .C 14 H 18 NSi:228.12,found,229.12。
(2) Preparation of the procatalyst
Under the protection of nitrogen, 0.43g of ligand compound A2 is dissolved in 30mL of toluene, equimolar amount of n-butyllithium is added, and the mixture is stirred and reacted for 4 hours at 40 ℃; then 0.44g of zirconium tetrachloride was added thereto, the temperature was raised to 50℃and the reaction was carried out for 4 hours. The solvent was removed in vacuo, and the residue was washed 4 times with n-hexane and dried to give 0.45g of catalyst (2), yield: 68%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝7.30-7.27(d,5H,N-Ph)；4.25(d,1H,Cp)；4.01(s,1H,Cp)；3.94-3.85(m,2H,-CH 2 )；3.41(d,1H,Cp)；0.42(s,6H,-CH 3 )；Anal.Calcd.(％)for C 14 H 16 ClNSiZr(350):C,47.49；H,4.84；found:C,47.52；H,4.89；ESI-MS m/zcalculated for[M+H] + .C 14 H 16 ClNSiZr:350.98,found,351.98。
(3) Polymerization of propylene:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, and 9mg of a main catalyst, 12ml of triethylaluminum solution (1M) were sequentially added. The temperature was raised to 40℃and the propylene pressure was 2.5MPa, and the polymerization was continued for 100mins. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 331g of the product was collected.
(4) Propylene copolymerization:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by adding 7mg of the main catalyst, 10ml of triethylaluminum solution (1M), 60ml of 1-butene. The temperature was raised to 40℃and propylene pressure of 2.5MPa was maintained for 30mins of polymerization. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 346g of the product was collected.
Example 3
(1) Synthesis of ligand compound A3 [ A3 structure: r in the general formula (2) 1 The cyclohexyl radical R is selected 2 Methyl is selected]
30ml of toluene, 2.28ml of cyclohexylamine and 6.67ml of methyl magnesium chloride (3M) in THF are taken in a 300ml schlenk flask, heated to 35 ℃ and reacted for 2 hours; 2.18ml of dimethyl chlorosilane is added and reacted for 5 hours; 1.86ml of cyclopentadienyl sodium was further added, and after reacting at 35℃for 4 hours, the mixture was drained, 100ml of n-hexane was added to the remaining solid, dissolved and filtered, and the filtrate was recrystallized to obtain 2.84g of ligand compound A3, yield: 64.3%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝3.99(d,1H,Cp)；3.96(s,1H,Cp)；3.59(s,1H,N-H)；3.57(s,1H,Si-H)；3.36(d,1H,Cp)；2.96(m,1H,-C 6 H 12 )；1.72-1.10(m,10H,-C 6 H 12 )；0.13(s,6H,-CH 3 )；Anal.Calcd.(％)for C 13 H 22 NSi(220):C,70.84；H,10.06；found:C,70.80；H,10.09；ESI-MS m/z calculated for[M+H] + .C 13 H 22 NSi:220.15,found,221.15。
(2) Preparation of the procatalyst
Under the protection of nitrogen, 0.43g of ligand compound A3 is dissolved in 30mL of toluene, equimolar amount of n-butyllithium is added, and the mixture is stirred and reacted for 4 hours at 40 ℃; then 0.41g of zirconium methyl trichloride is added, the temperature is raised to 50 ℃ and the reaction is carried out for 4 hours. The solvent was removed in vacuo, and the residue was washed 3 times with n-hexane and dried to give 0.41g of catalyst (3), yield: 69%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝3.99(d,1H,Cp)；3.96(s,1H,Cp)；3.36(d,1H,Cp)；1.90(s,3H,-CH 3 )；1.72-1.49(m,11H,-C 6 H 12 )；0.29(s,6H,-CH 3 )；Anal.Calcd.(％)for C 14 H 23 NSiTi(281):C,59.78；H,8.24；found:C,59.75；H,8.27；ESI-MS m/z calculated for[M+H] + .C 14 H 23 NSiTi:281.11,found,282.11。
(3) Polymerization of ethylene:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 6mg of the main catalyst and 7ml of MAO solution (10 wt%) were added. The temperature was raised to 90℃and the ethylene pressure was 0.8MPa, and polymerized for 90mins. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 211g of the product was collected.
(4) Ethylene copolymerization:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 6mg of the main catalyst, 7ml of MAO solution (10 wt%) and 30ml of 1-hexene. The temperature was raised to 20℃and the ethylene pressure of 0.8MPa and the propylene pressure of 0.6MPa were maintained for 30mins of polymerization. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 339g of the product was collected.
Example 4
(1) Synthesis of ligand compound A4 [ A4 structure: r in the general formula (2) 1 2,4, 6-trimethylphenyl, R is selected 2 Phenyl is selected]
30ml of toluene, 2.7g of 2,4, 6-trimethylaniline and 6.67ml of methyl magnesium chloride (3M) in THF are taken in a 300ml schlenk flask, heated to 35 ℃ and reacted for 2 hours; adding 4.38g of diphenyl chlorosilane, and reacting for 6 hours; 1.86ml of cyclopentadienyl sodium was further added, and after reacting at 35℃for 4 hours, the mixture was drained, 100ml of n-hexane was added to the remaining solid, dissolved and filtered, and the filtrate was recrystallized to give 4.73g of ligand compound A4, yield: 62%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝7.46(s,4H,Si-Ph)；7.38(s,6H,Si-Ph)；6.77(s,2H,N-Ph)；5.67(s,1H,N-H)；4.87(d,1H,Cp)；4.35(s,1H,Cp)；3.88(d,1H,Cp)；3.37(s,1H,Si-H)；2.25(s,9H,-CH 3 )；Anal.Calcd.(％)for C 26 H 26 NSi(380):C,82.05；H,6.89；found:C,81.95；H,6.92；ESI-MS m/z calculated for[M+H] + .C 26 H 26 NSi:380.18,found,381.18。
(2) Preparation of the procatalyst
Under the protection of nitrogen, 0.43g of ligand compound A4 is dissolved in 30mL of toluene, equimolar amount of n-butyllithium is added, and the mixture is stirred and reacted for 6 hours at 50 ℃; then 0.26g of zirconium tetrachloride was added thereto, the temperature was raised to 50℃and the reaction was carried out for 4 hours. The solvent was removed in vacuo, and the residue was washed 3 times with n-hexane and dried to give 0.38g of catalyst (4), yield: 67.5%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝7.41-7.32(m,10H,Si-Ph)；7.02(s,2H,N-Ph)；4.87(d,1H,Cp)；4.35(s,1H,Cp)；3.88(d,1H,Cp)；2.28-2.21(s,9H,-CH 3 )；Anal.Calcd.(％)for C 26 H 24 ClNSiZr(503):C,61.81；H,4.79；found:C,61.85；H,4.86；ESI-MS m/z calculated for[M+H] + .C 26 H 24 ClNSiZr:503.04,found,504.04。
(3) Polymerization of ethylene:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 8mg of the main catalyst and 5ml of MAO solution (10 wt%) were added. The temperature was raised to 65℃and the ethylene pressure was 0.6MPa, and the polymerization was carried out for 120mins. The reaction was stopped with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 372g of the product was collected.
(4) Ethylene copolymerization:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by adding 7mg of the main catalyst, 4ml of MAO solution (10 wt%), and 15ml of 1-octene. The temperature was raised to 65℃and the ethylene pressure was maintained at 0.6MPa for 10mins of polymerization. The reaction was stopped with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 333g of the product was collected.
Example 5
(1) Synthesis of ligand compound A5 [ A5 structure: r in the general formula (2) 1 Cyclopentyl, R 2 Methyl is selected]
30ml of toluene, 1.98ml of cyclopentylamine and 6.67ml of methyl magnesium chloride (3M) in THF are taken in a 300ml schlenk bottle, heated to 35 ℃ and reacted for 2 hours; 2.18ml of dimethylchloride are addedSilane, reacting for 7 hours; 1.86ml of cyclopentadienyl sodium was further added, and after reacting at 35℃for 4 hours, the mixture was drained, 100ml of n-hexane was added to the remaining solid, dissolved and filtered, and the filtrate was recrystallized to give 2.65g of ligand compound A5, yield: 64%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝4.23(d,1H,Cp)；4.05(d,1H,Cp)；3.61(s,1H,N-H)；3.58(s,1H,Si-H)；3.46(d,1H,Cp)；3.03(m,1H,-C 5 H 10 )；1.82-1.57(m,8H,-C 5 H 10 )；0.13(s,6H,-CH 3 )；Anal.Calcd.(％)for C 12 H 20 NSi(206):C,69.84；H,9.77；found:C,69.80；H,9.72；ESI-MS m/zcalculated for[M+H] + .C 12 H 20 NSi:206.14,found,207.14。
(2) Preparation of the main catalyst:
under the protection of nitrogen, 0.43g of ligand compound A5 is dissolved in 30mL of toluene, equimolar amount of n-butyllithium is added, and the mixture is stirred and reacted for 5 hours at 40 ℃; then 0.66g of hafnium tetrachloride was added thereto, the temperature was raised to 50℃and the reaction was carried out for 4 hours. The solvent was removed in vacuo, and the residue was washed 3 times with n-hexane and dried to give 0.53g of catalyst (5), yield: 61%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝4.23(d,1H,Cp)；4.05(d,1H,Cp)；3.46(d,1H,Cp)；1.97-1.64(m,9H,-C 5 H 10 )；0.41(s,6H,-CH 3 )；Anal.Calcd.(％)for C 12 H 18 ClNSiHf(419):C,34.46；H,4.34；found:C,34.41；H,4.29；ESI-MS m/z calculated for[M+H] + .C 12 H 18 ClNSiHf:419.04,found,420.04。
(3) Polymerization of ethylene:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 5mg of the main catalyst and 4ml of MAO solution (10 wt%) were added. The temperature was raised to 50℃and the ethylene pressure was 0.5MPa, and the polymerization was carried out for 120mins. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 251g of the product was collected.
(4) Ethylene copolymerization:
after a2 liter stainless steel autoclave was fully replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 5mg of the main catalyst, 4ml of MAO solution (10 wt%) and 10ml of 1-decene. The temperature was raised to 70℃and the ethylene pressure was maintained at 0.5MPa for 10mins. The reaction was stopped with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 227g of the product was collected.
Example 6
(1) Synthesis of ligand compound A6 [ A6 structure: r in the general formula (2) 1 2, 6-dimethylphenyl, R 2 Phenyl is selected]
30ml of toluene, 2.46ml of 2, 6-dimethylaniline and 6.67ml of methyl magnesium chloride (3M) in THF are taken in a 300ml schlenk flask and are heated to 35 ℃ for reaction for 2 hours; adding 4.38g of diphenyl chlorosilane, and reacting for 8 hours; 1.86ml of cyclopentadienyl sodium was further added, and after reacting at 35℃for 4 hours, the mixture was drained, 100ml of n-hexane was added to the remaining solid, dissolved and filtered, and the filtrate was recrystallized to give 4.74g of ligand compound A6, yield: 64.5%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝7.47(d,4H,Si-Ph)；7.36(d,6H,Si-Ph)；7.12(m,1H,N-Ph)；7.06(d,2H,N-Ph)；5.67(s,1H,N-H)；4.34(d,2H,Cp)；3.95(d,1H,Cp)；3.42(s,1H,Si-H)；2.26(s,6H,-CH 3 )；Anal.Calcd.(％)for C 25 H 24 NSi(366):C,81.92；H,6.60；found:C,81.85；H,6.65；ESI-MS m/z calculated for[M+H] + .C 25 H 24 NSi:366.17,found,367.17。
(2) Preparation of the main catalyst:
under the protection of nitrogen, 0.43g of ligand compound A6 is dissolved in 30mL of toluene, equimolar amount of n-butyllithium is added, and the mixture is stirred and reacted for 7 hours at 35 ℃; then 0.43g of titanium tetrabromide is added, the temperature is raised to 50 ℃ and the reaction is carried out for 4 hours. The solvent was removed in vacuo, and the residue was washed 3 times with n-hexane and dried to give 0.38g of catalyst (6), yield: 66%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝7.39-7.32(m,10H,Si-Ph)；7.18(t,1H,N-Ph)；7.02(d,2H,N-Ph)；4.32(d,2H,Cp)；3.95(d,1H,Cp)；2.23(s,6H,-CH 3 )；Anal.Calcd.(％)for C 25 H 22 BrNSiTi(491):C,60.99；H,4.50；found:C,60.92；H,4.59；ESI-MS m/z calculated for[M+H] + .C 25 H 22 BrNSiTi:491.02,found,492.02。
(3) Polymerization of propylene:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of n-hexane was added to the autoclave, followed by 7mg of a main catalyst and 7ml of a triisobutylaluminum solution (1M). The temperature was raised to 35℃and the propylene pressure was 2.8MPa, and polymerized for 80mins. The reaction was stopped with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 254g of the product was collected.
(4) Propylene copolymerization:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 6mg of a main catalyst, 6ml of triisobutylaluminum solution (1M) and 25ml of styrene. The temperature was raised to 35℃and the propylene pressure of 2.8MPa and the ethylene pressure of 2.4MPa were maintained for 30mins of polymerization. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 271g of the product was collected.
Example 7
(1) Synthesis of ligand compound A7 [ A7 structure: r in the general formula (2) 1 Isopropyl, R is selected 2 Isopropyl group is selected]
30ml of toluene, 1.71ml of isopropylamine and 6.67ml of methyl magnesium chloride (3M) in THF are taken in a 300ml schlenk flask, heated to 35 ℃ and reacted for 2 hours; 3g of diisopropyl chlorosilane is added and reacted for 5 hours; 1.86ml of cyclopentadienyl sodium was further added, and after reacting at 35℃for 4 hours, the mixture was drained, 100ml of n-hexane was added to the remaining solid, dissolved and filtered, and the filtrate was recrystallized to obtain 3.33g of ligand compound A7, yield: 70.2%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝4.34(m,1H,N-CH)；4.11(s,1H,Cp)；3.97(d,1H,Cp)；3.59(s,1H,N-H)；3.57(s,1H,Si-H)；3.45(d,1H,Cp)；1.45(m,2H,Si-CH)；1.18(d,6H,N-CH 3 )；0.98(d,12H,Si-CH 3 )；Anal.Calcd.(％)for C 14 H 26 NSi(236):C,71.11；H,11.08；found:C,71.06；H,11.15；ESI-MS m/z calculated for[M+H] + .C 14 H 26 NSi:236.18,found,237.18。
(2) Preparation of the main catalyst:
under the protection of nitrogen, 0.43g of ligand compound A7 is dissolved in 30mL of toluene, equimolar amount of n-butyllithium is added, and the mixture is stirred and reacted for 5 hours at 40 ℃; then 0.42g zirconium tetrachloride was added thereto, the temperature was raised to 50℃and the reaction was carried out for 4 hours. The solvent was removed in vacuo, and the residue was washed 3 times with n-hexane and dried to give 0.41g of catalyst (7), yield: 63%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝4.11(s,1H,Cp)；3.97(d,1H,Cp)；3.45(d,1H,Cp)；3.15(m,1H,N-CH 2 )；1.36(d,2H,Si-CH 2 )；1.31(d,6H,N-CH 3 )；1.17(d,12H,Si-CH 3 )；Anal.Calcd.(％)for C 14 H 24 ClNSiZr(359):C,46.57；H,6.70；found:C,46.50；H,6.74；ESI-MS m/zcalculated for[M+H] + .C 14 H 24 ClNSiZr:359.04,found,360.04。
(3) Polymerization of ethylene:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 6mg of the main catalyst and 6ml of MAO solution (10 wt%) were added. The temperature was raised to 55℃and the ethylene pressure was 0.8MPa, and the polymerization was carried out for 120mins. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, and then dried under vacuum at 50℃for 24 hours, to collect 351g of the product.
(4) Ethylene copolymerization:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 6mg of the main catalyst, 6ml of MAO solution (10 wt%) and 6ml of acrylonitrile. The temperature was raised to 55℃and the ethylene pressure was maintained at 0.8MPa for 10mins. The reaction was stopped with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 48g of the product was collected.
Example 8
(1) Synthesis of ligand compound A8 [ A8 structure: r in the general formula (2) 1 2, 6-dimethylphenyl, R 2 2, 6-dimethylphenyl is selected]
30ml of toluene, 2.46ml of 2, 6-dimethylaniline and 6.67ml of methyl magnesium chloride (3M) in THF are taken in a 300ml schlenk flask, heated to 35 ℃ and reacted for 3 hours; then 5.48g of di (2, 6-dimethylphenyl) chlorosilane is added for reaction for 5 hours; 1.86ml of cyclopentadienyl sodium was further added, and after reacting at 35℃for 4 hours, the mixture was drained, 100ml of n-hexane was added to the remaining solid, dissolved and filtered, and the filtrate was recrystallized to give 5.77g of ligand compound A8, yield: 68.2%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝7.54(m,2H,Si-Ph)；7.14(m,4H,Si-Ph)；7.13(m,1H,N-Ph)；7.06(d,2H,N-Ph)；5.67(s,1H,N-H)；4.95(d,1H,Cp)；4.41(s,1H,Cp)；4.24(d,1H,Cp)；3.39(s,1H,Si-H)；2.26-2.32(s,18H,-CH 3 )；Anal.Calcd.(％)for C 29 H 32 NSi(422):C,82.41；H,7.63；found:C,82.38；H,7.59；ESI-MS m/zcalculated for[M+H] + .C 29 H 32 NSi:422.23,found,423.23。
(2) Preparation of the procatalyst
Under the protection of nitrogen, 0.43g of ligand compound A8 is dissolved in 30mL of toluene, equimolar amount of n-butyllithium is added, and the mixture is stirred and reacted for 3 hours at 50 ℃; then 0.33g of hafnium tetrachloride was added thereto, the temperature was raised to 50℃and the reaction was carried out for 4 hours. The solvent was removed in vacuo, and the residue was washed 3 times with n-hexane and dried to give 0.4g of catalyst (8), yield: 62%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝7.53(d,4H,Si-Ph)；7.21(m,1H,N-Ph)；7.18(m,2H,Si-Ph)；7.05(d,2H,N-Ph)；4.95(d,1H,Cp)；4.41(s,1H,Cp)；4.24(d,1H,Cp)；2.29(s,12H,-CH 3 )；2.22(s,6H,-CH 3 )；Anal.Calcd.(％)for C 29 H 30 ClNSiHf(635):C,54.89；H,4.77；found:C,54.85；H,4.72；ESI-MS m/z calculated for[M+H] + .C 29 H 30 ClNSiHf:635.13,found,636.13。
(3) Polymerization of propylene:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by adding 7mg of the main catalyst and 4ml of MAO solution (10 wt%) in sequence. The temperature was raised to 50℃and the propylene pressure was 3.1MPa, and polymerized for 120mins. The reaction was stopped with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 368g of the product was collected.
(4) Propylene copolymerization:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 6mg of the main catalyst, 4ml of MAO solution (10 wt%), and 8ml of 3-methyl-1-butene. The temperature was raised to 50℃and propylene pressure of 3.1MPa was maintained for polymerization for 10mins. The reaction was stopped with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 335g of the product was collected.
Example 9
(1) Synthesis of ligand compound A9 [ A9 structure: r in the general formula (2) 1 2, 6-difluorophenyl is selected and used, R 2 Methyl is selected]
30ml of toluene, 2ml of 2, 6-difluoroaniline and 6.67ml of methyl magnesium chloride (3M) in THF are taken in a 300ml schlenk flask and heated to 35 ℃ for reaction for 4 hours; 2.18ml of dimethyl chlorosilane is added and reacted for 5 hours; 1.86ml of cyclopentadienyl sodium was further added, and after reacting at 35℃for 4 hours, the mixture was drained, 100ml of n-hexane was added to the remaining solid, dissolved and filtered, and the filtrate was recrystallized to obtain 3.67g of ligand compound A9, yield: 73%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝6.95(m,1H,N-Ph)；6.81(m,2H,N-Ph)；5.67(s,1H,N-H)；4.25(s,1H,Cp)；3.79(d,1H,Cp)；3.45(d,1H,Cp)；3.58(s,1H,Si-H)；0.13(s,6H,-CH 3 )；Anal.Calcd.(％)for C 13 H 14 F 2 NSi(250):C,62.37；H,5.64；found:C,62.31；H,5.67；ESI-MS m/z calculated for[M-H] - .C 13 H 14 F 2 NSi:250.09,found,249.09。
(2) Preparation of the main catalyst:
under the protection of nitrogen, 0.43g of ligand compound A9 is dissolved in 30mL of toluene, equimolar amount of n-butyllithium is added, and the mixture is stirred and reacted for 6 hours at 40 ℃; 0.19ml of titanium tetrachloride was added thereto, and the temperature was raised to 50℃to effect a reaction for 4 hours. Vacuum pumping the solvent to removeThe residue was washed 3 times with n-hexane and dried to give 0.38g of catalyst (9), yield: 66.3%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝7.42(t,1H,N-Ph)；7.02(d,2H,N-Ph)；4.25(s,1H,Cp)；3.78(d,1H,Cp)；3.47(d,1H,Cp)；0.46(s,6H,Si-CH 3 )；Anal.Calcd.(％)for C 13 H 12 ClF 2 NSiTi(330):C,47.08；H,3.65；found:C,47.02；H,3.60；ESI-MS m/z calculated for[M-H] - .C 13 H 12 ClF 2 NSiTi:330.99,found,329.99。
(3) Polymerization of ethylene:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 6mg of the main catalyst and 6ml of MAO solution (10 wt%) were added. The temperature was raised to 40℃and the ethylene pressure was 0.8MPa, and the polymerization was carried out for 100mins. The reaction was stopped with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 312g of the product was collected.
(4) Ethylene copolymerization:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 6mg of the main catalyst, 6ml of MAO solution (10 wt%) and 20ml of 4-methyl-1-pentene. The temperature was raised to 40℃and the ethylene pressure was maintained at 0.8MPa for 30mins. The reaction was stopped with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 289g of the product was collected.
Example 10
(1) Synthesis of ligand compound a10 [ a10 structure: r in the general formula (2) 1 2,4, 6-trifluoro phenyl and R are selected 2 Ethyl group is selected]
30ml of toluene, 2.08ml of 2,4, 6-trifluoroaniline and 6.67ml of methyl magnesium chloride (3M) in THF are taken in a 300ml schlenk flask, heated to 35 ℃ and reacted for 2 hours; 2.45g of diethyl chlorosilane is added and reacted for 6 hours; then adding 1.86ml of cyclopentadienyl sodium, reacting for 4 hours at 35 ℃, pumping, adding 100ml of normal hexane into the residual solid, dissolving and filtering, recrystallizing the filtrate to obtain 4.25g of ligand compoundSubstance a10, yield: 71.5%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝6.40(m,2H,N-Ph)；5.69(s,1H,N-H)；4.05(d,1H,Cp)；4.03(s,1H,Cp)；3.58(s,1H,Si-H)；3.30(s,1H,Cp)；0.92(t,6H,-CH 3 )；0.69(m,4H,-CH 2 )；Anal.Calcd.(％)for C 15 H 17 F 3 NSi(296):C,60.79；H,5.78；found:C,60.74；H,5.82；ESI-MS m/zcalculated for[M-H] - .C 15 H 17 F 3 NSi:296.11,found,295.11。
(2) Preparation of the main catalyst:
under the protection of nitrogen, 0.43g of ligand compound A10 is dissolved in 30mL of toluene, equimolar amount of n-butyllithium is added, and the mixture is stirred and reacted for 5 hours at 40 ℃; then 0.46g of hafnium ethyl trichloride was added thereto, the temperature was raised to 50℃and the reaction was carried out for 4 hours. The solvent was removed in vacuo, and the residue was washed 3 times with n-hexane and dried to give 0.48g of catalyst (10), yield: 65.4%. 1 H NMR(600MHz,CDCl 3 :7.26ppm):δ＝7.05(s,2H,N-Ph)；4.05(d,1H,Cp)；4.02(s,1H,Cp)；3.31(s,1H,Cp)；2.45(m,2H,M-CH 2 )；1.23(m,4H,Si-CH 2 )；1.05(t,3H,M-CH 3 )；0.93(t,6H,Si-CH 3 )；Anal.Calcd.(％)for C 17 H 20 F 3 NSiHf(503):C,40.68；H,4.02；found:C,40.61；H,4.08；ESI-MS m/z calculated for[M-H] - .C 17 H 20 F 3 NSiHf:503.08,found,502.08。
(3) Polymerization of ethylene:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 6mg of the main catalyst and 4ml of MAO solution (10 wt%) were added. The temperature was raised to 80℃and the ethylene pressure was 0.8MPa, and polymerized for 90mins. The reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 291g of the product was collected.
(4) Ethylene copolymerization:
after a2 liter stainless steel autoclave was sufficiently replaced with nitrogen under anhydrous and anaerobic conditions, 1L of toluene was added to the autoclave, followed by 6mg of a main catalyst, 4ml of MAO solution (10 wt%), 6ml of acrylonitrile and 10ml of 1-octene. The temperature was raised to 80℃and the ethylene pressure was maintained at 0.8MPa for 20mins. The reaction was stopped with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, then dried under vacuum at 50℃for 24 hours, and 58g of the product was collected.
The results of the catalyst polymerization of the examples are shown in Table 3.
Table 3 results of the catalyst polymerization of examples
As can be seen from Table 3, the olefin polymerization catalyst obtained in the examples of the present invention has a high polymerization activity.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.
Claims (12)
1. A main catalyst of an olefin polymerization catalyst, characterized in that the main catalyst is a compound represented by the general formula (I),
in the general formula (I), R 1 、R 2 Each independently selected from one of C1-C20 linear alkyl, C3-C20 cycloalkyl, C6-C20 aryl; x is selected from F, cl, br, I or C1-C20 alkyl; m represents a transition metal atom selected from one of group IVB elements.
2. The procatalyst of an olefin polymerization catalyst according to claim 1, wherein X is selected from Cl, br, me or Et; m is selected from one of titanium, zirconium and hafnium.
3. The procatalyst of an olefin polymerization catalyst according to claim 1, wherein the procatalyst is one of the following compounds:
compound 1: m=titanium, x=cl, R 1 Phenyl group, R 2 Phenyl;
compound 2: m=zirconium, x=cl, R 1 =benzyl, R 2 Methyl group;
compound 3: m=titanium, x=me, R 1 =cyclohexyl, R 2 Methyl group;
compound 4: m=zirconium, x=cl, R 1 =2, 4, 6-trimethylphenyl, R 2 Phenyl;
compound 5: m=hafnium, x=cl, R 1 =cyclopentyl, R 2 Methyl group;
compound 6: m=titanium, x=br, R 1 =2, 6-dimethylphenyl, R 2 Phenyl;
compound 7: m=zirconium, x=cl, R 1 =isopropyl, R 2 =isopropyl;
compound 8: m=hafnium, x=cl, R 1 =2, 6-dimethylphenyl, R 2 =2, 6-dimethylphenyl;
compound 9: m=titanium, x=cl, R 1 =2, 6-difluorophenyl, R 2 Methyl group;
compound 10: m=hafnium, x=et, R 1 =2, 4, 6-trifluorophenyl, R 2 Ethyl.
4. A process for preparing a procatalyst for an olefin polymerization catalyst, comprising the steps of:
(1) Adding an organic solvent into a ligand compound which accords with the general formula (II), adding n-butyllithium, stirring, and carrying out a third reaction; the general formula (II) is shown as the following formula:
in the general formula (II), R 1 、R 2 Each independently selected from one of C1-C20 linear alkyl, C3-C20 cycloalkyl, C6-C20 aryl;
(2) Continuously adding a transition metal compound, stirring, carrying out a fourth reaction, then removing the organic solvent, washing the remainder with the organic solvent, and pumping to obtain the (Si-N) multi-heterocyclic metallocene catalyst which accords with the general formula (1);
preferably, the molar ratio of n-butyllithium to the ligand compound is 0.5-4:1, and the molar ratio of the ligand compound to the transition metal compound is 1:1-2, more preferably 1:1-1.5.
5. The method of preparing according to claim 4, wherein the preparation of the ligand compound according to formula (2) comprises the steps of: dissolving aryl primary amine or substituted aryl primary amine compound in an organic solvent, adding a Grignard reagent for a first reaction, wherein the mole ratio of the Grignard reagent to the aryl primary amine or substituted aryl primary amine compound is 0.3-6:1; then adding an organic silicon compound, adding sodium cyclopentadiene, and carrying out a second reaction to obtain the ligand compound which is in accordance with the general formula (II), wherein the molar ratio of the organic silicon compound to the aryl primary amine or the substituted aryl primary amine compound is 0.3-6:1, and the molar ratio of the sodium cyclopentadiene to the aryl primary amine compound is 0.2-10:1.
6. The method of claim 5, wherein the organosilicon compound corresponds to the general formula: r is R 2 R 2 SiHX (III), wherein R 2 Selected from one of C1-C20 linear alkyl, C3-C20 cycloalkyl and C6-C20 aryl, and X is selected from F, cl, br, I or C1-C20 alkyl.
7. The method according to claim 5, wherein,
the conditions of the first reaction are as follows: the temperature is between 50 ℃ below zero and 70 ℃ below zero for 2 to 10 hours; preferably, the temperature is 10-50 ℃ and the time is 2-4 hours;
the conditions of the second reaction are as follows: the temperature is between 50 ℃ below zero and 80 ℃ below zero for 1 to 8 hours;
the conditions of the third reaction are as follows: the temperature is 0-60 ℃ and the time is 3-10 hours;
the conditions for the fourth reaction are: the temperature is 20-80 ℃ and the time is 3-10 hours.
8. The process according to claim 4 and 5, wherein the organic solvents are identical or different and are each independently selected from C 5 ～C 15 Saturated hydrocarbon of C 5 ～C 10 Alicyclic hydrocarbon of (C) 6 ～C 15 Aromatic hydrocarbon of C 2 ～C 10 At least one of the saturated heterocyclic hydrocarbons of (2).
9. An olefin polymerization catalyst comprising a main catalyst which is a compound according to any one of claims 1 to 3 and a cocatalyst which is an organometallic aluminium compound, preferably an alkylaluminum or alkylaluminoxane which is a hydrolysate of alkylaluminum, the molar ratio of the cocatalyst to the main catalyst being (100 to 5000): 1, preferably (150 to 1000): 1.
10. the olefin polymerization catalyst according to claim 9, wherein the cocatalyst is at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, methylaluminoxane.
11. The olefin polymerization catalyst of claim 9, wherein the olefin polymerization catalyst is used for catalyzing olefin homo-polymerization or olefin copolymerization, and the polymerized monomer is selected from ethylene and C 3 ～C 20 Alpha-olefins, C 3 ～C 20 Non-conjugated diolefins, C 3 ～C 20 At least one of polar olefinic monomers; preferably, the olefin polymerization catalyst is used for catalyzing ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar olefin monomer copolymerization, and propylene and polar olefin monomer copolymerization; the alpha-olefin being C 3 -C 20 Preferably propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene, styrene, alpha-methylstyrene, norbornene, 1, 7-bicyclooctene or 1, 8-bicyclononene; the polar vinyl monomer contains a carbon-carbon double bond and also has a polar group, preferably acrylonitrile, 4-cyanostyrene, methyl methacrylate, methyl acrylate or butyl acrylate.
12. The olefin polymerization catalyst according to claim 9, wherein when the olefin polymerization catalyst is used for catalyzing olefin polymerization, the polymerization temperature is 20-90 ℃ and the polymerization time is 5 min-3 h, wherein the pressure of monomer ethylene or propylene is 0.1-5 MPa, and the solvent comprises at least one of n-hexane, heptane and toluene.
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