CN114315916B - Bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures and application thereof - Google Patents
Bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures and application thereof Download PDFInfo
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- CN114315916B CN114315916B CN202111660930.6A CN202111660930A CN114315916B CN 114315916 B CN114315916 B CN 114315916B CN 202111660930 A CN202111660930 A CN 202111660930A CN 114315916 B CN114315916 B CN 114315916B
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- methyl
- butyl
- catalyst
- alkyl
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 59
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 32
- 239000011593 sulfur Substances 0.000 title claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 29
- 239000001301 oxygen Substances 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- 239000005977 Ethylene Substances 0.000 claims abstract description 53
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 154
- 238000006116 polymerization reaction Methods 0.000 claims description 56
- -1 cumyl Chemical group 0.000 claims description 42
- 238000002360 preparation method Methods 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000007334 copolymerization reaction Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 229920000098 polyolefin Polymers 0.000 claims description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 125000003670 adamantan-2-yl group Chemical group [H]C1([H])C(C2([H])[H])([H])C([H])([H])C3([H])C([*])([H])C1([H])C([H])([H])C2([H])C3([H])[H] 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 35
- 125000003118 aryl group Chemical group 0.000 abstract description 25
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 18
- 125000003107 substituted aryl group Chemical group 0.000 abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 239000010703 silicon Chemical group 0.000 abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 abstract description 7
- 150000003624 transition metals Chemical class 0.000 abstract description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract description 6
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 abstract description 5
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 3
- 125000005843 halogen group Chemical group 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 78
- 238000006243 chemical reaction Methods 0.000 description 77
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 68
- 239000000243 solution Substances 0.000 description 52
- 238000001914 filtration Methods 0.000 description 32
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 30
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 30
- 239000003446 ligand Substances 0.000 description 27
- 150000004696 coordination complex Chemical class 0.000 description 23
- 239000012299 nitrogen atmosphere Substances 0.000 description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 18
- 239000012074 organic phase Substances 0.000 description 18
- 229910001510 metal chloride Inorganic materials 0.000 description 17
- 238000005259 measurement Methods 0.000 description 15
- 238000003780 insertion Methods 0.000 description 14
- 230000037431 insertion Effects 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 238000004364 calculation method Methods 0.000 description 13
- 238000000921 elemental analysis Methods 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 13
- 238000002390 rotary evaporation Methods 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 150000002367 halogens Chemical group 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000717 retained effect Effects 0.000 description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 4
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 2
- QGEFGPVWRJCFQP-UHFFFAOYSA-M magnesium;methanidylbenzene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C1=CC=CC=C1 QGEFGPVWRJCFQP-UHFFFAOYSA-M 0.000 description 2
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures, which has a structure shown in a formula (I): wherein R is 1 Is C1-C4 alkyl; r is R 2 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; r is R 3 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; r is R 4 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; x is halogen, C1-C30 alkyl, silicon base, amino or C6-C30 aryl; m is a fourth subgroup transition metal. The metallocene compound with the nitrogen-containing and sulfur heterocyclic structures has the characteristics of good heat stability, low cocatalyst usage amount, high catalytic activity, good heat stability and long catalytic life when in use, and the catalyst can catalyze ethylene to polymerize to obtain ultra-high molecular weight polyethylene, and ethylene and 1-octene are copolymerized.
Description
Technical Field
The invention relates to the technical field of olefin polymerization catalysts, in particular to a bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures and application thereof.
Background
As an important polymer material, the polyethylene has become an integral part of human life, and the demand of the market for polyolefin materials is continuously increasing. In recent years, new technologies such as high-efficiency catalysis, metallocene technology, copolymerization technology, bimodal technology and the like are continuously innovated, and the application of various modification, compounding and alloy technologies is further widened, so that the application fields of the original engineering resins are greatly utilized. The great demand has driven the rapid development of the polyolefin industry, while advances in the polyolefin industry technology have greatly benefited from advances in catalysts. The catalyst has an important effect on both the micro-and macro-structures of the polyolefin resin, which in turn determine the product properties in the target application. Therefore, there is a great deal of attention in the industry and academia to find a new catalyst which is applicable to the industrial conditions at the present stage, has a higher catalytic activity, and can control the properties of the polyolefin more effectively, particularly a catalyst having a technical front such as a metallocene complex or a non-metallocene complex.
The publication of prior art Moscow State University (Organometallics 2002,21,2842-2855) reports a variety of novel half-sandwich type PHENICS catalysts having excellent high temperature resistance, which are used as main catalysts for catalyzing the copolymerization of ethylene with 1-hexene to obtain high insertion rate copolymer products; patents WO2018122693A1, WO2019132523A1 and WO2019038605A1 filed by the korean SK company are partial modifications based on the PHENICS catalyst filed by the Sumitomo company, japan, which investigated the effect of the modifying group on the copolymerization of ethylene and 1-hexene catalyzed by the modified PHENICS catalyst, and resulted in a series of polymer products with high comonomer insertion rate under high temperature polymerization conditions; although these reported catalysts are capable of ensuring high comonomer insertion rates under high temperature polymerization conditions, the molecular weight of the resulting polymers is generally low, while the copolymerization of ethylene with 1-hexene has been mainly studied in literature reports.
The invention aims to design and synthesize a polymer product with high catalytic activity, high thermal stability and long catalytic life, and the polymer product with high molecular weight and high comonomer insertion rate can be obtained by catalyzing ethylene to homopolymerize to produce linear low-density polyethylene with higher molecular weight and catalyzing ethylene to copolymerize with alpha-olefin through reasonably optimizing catalyst substituent groups and polymerization conditions.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures, which has the characteristics of high catalytic activity and good thermal stability as a catalyst.
The invention provides a bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures, which has a structure shown in a formula (I):
wherein R is 1 Is C1-C4 alkyl; r is R 2 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; r is R 3 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; r is R 4 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; x is halogen, C1-C30 alkyl, silicon base, amino or C6-C30 aryl;
m is a fourth subgroup transition metal.
Preferably, said R 1 Methyl or ethyl; r is R 2 Methyl, tert-butyl, phenyl, cumyl, carbazolyl or adamantyl; r is R 3 Methyl or tert-butyl; r is R 4 Is methyl or tert-butyl.
Preferably, X is Cl, methyl or benzyl; m is any one of titanium, zirconium or hafnium.
Preferably, the compound having the structure shown in formula (I) is specifically the structure shown in the following C1 to C13:
C1：R 1 methyl, R 2 Methyl, R 3 Methyl, R 4 Methyl, x=cl;
C2：R 1 methyl, R 2 T-butyl, R 3 Methyl, R 4 Methyl, x=cl;
C3：R 1 methyl, R 2 Adamantyl group, R 3 Methyl, R 4 Methyl, x=cl;
C4：R 1 the number of methyl groups is =,R 2 =cumyl, R 3 Methyl, R 4 Methyl, x=cl;
C5：R 1 methyl, R 2 Carbazolyl group, R 3 Methyl, R 4 Methyl, x=cl;
C6：R 1 methyl, R 2 Phenyl group, R 3 Methyl, R 4 Methyl, x=cl;
C7：R 1 methyl, R 2 T-butyl, R 3 T-butyl, R 4 Methyl, x=cl;
C8：R 1 =ethyl, R 2 T-butyl, R 3 Methyl, R 4 Methyl, x=cl;
C9：R 1 =ethyl, R 2 Methyl, R 3 Methyl, R 4 Methyl, x=cl;
C10：R 1 methyl, R 2 T-butyl, R 3 T-butyl, R 4 Methyl, x=benzyl;
C11：R 1 methyl, R 2 T-butyl, R 3 Methyl, R 4 T-butyl, x=benzyl;
C12：R 1 methyl, R 2 Methyl, R 3 Methyl, R 4 Methyl, x=me;
C13：R 1 Methyl, R 2 T-butyl, R 3 Methyl, R 4 Methyl, x=me;
the invention provides a catalyst for olefin polymerization, which comprises a main catalyst and a cocatalyst; the main catalyst comprises the bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures in any one of the technical schemes.
Preferably, the cocatalyst comprises one or more of a mixture of an alkyl aluminium and a boron agent, an alkyl aluminoxane, a modified alkyl aluminoxane or a haloalkylaluminium.
Preferably, the molar ratio of the aluminum atoms in the cocatalyst to the metal atoms in the main catalyst is (5 to 10000): 1, a step of;
the molar ratio of boron atoms in the cocatalyst to metal atoms in the main catalyst is (0-2): 1.
the invention provides a preparation method of polyolefin, which comprises the following steps:
homopolymerizing ethylene in the presence of a catalyst to obtain polyolefin;
the catalyst comprises a main catalyst and a cocatalyst; the main catalyst comprises the bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures in any one of the technical schemes.
The invention provides a preparation method of polyolefin, which comprises the following steps:
copolymerizing ethylene and alpha-olefin in the presence of a catalyst to obtain polyolefin;
The catalyst comprises a main catalyst and a cocatalyst; the main catalyst comprises the bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures in any one of the technical schemes.
Preferably, the temperature of the homo-polymerization or copolymerization reaction is 0-200 ℃, and the ethylene pressure during polymerization is 0.1-10 MPa.
Compared with the prior art, the invention provides a bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures, which has a structure shown in a formula (I): wherein R is 1 Is C1-C4 alkyl; r is R 2 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; r is R 3 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; r is R 4 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; x is halogen, C1-C30 alkyl, silicon base, amino or C6-C30 aryl; m is a fourth subgroup transition metal. The metallocene compound with the nitrogen-containing and sulfur heterocyclic structures has the characteristics of good heat stability, low cocatalyst usage amount, high catalytic activity, good heat stability and long catalytic life when in use, and the catalyst can catalyze ethylene to polymerize to obtain ultra-high molecular weight polyethylene, ethylene and 1-octene are copolymerized, and the comonomer insertion rate is high.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of C1.
Detailed Description
The invention provides a bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures and application thereof, and a person skilled in the art can properly improve process parameters by referring to the content of the disclosure. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and they are intended to be within the scope of the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The invention provides a bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures, which has a structure shown in a formula (I):
wherein R is 1 Is C1-C4 alkyl; r is R 2 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; r is R 3 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; r is R 4 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; x is halogen, C1-C30 alkyl, silicon base, amino or C6-C30 aryl;
M is a fourth subgroup transition metal.
R 1 Is C1-C4 alkyl; preferably, R 1 Methyl, ethyl or propyl; more preferably, R 1 Methyl or ethyl;
R 2 is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; preferably, R 2 Is C1-C20 alkyl, C6-C20 aryl or C6-C20 substituted aryl; more preferably, R 2 Methyl, tert-butyl, phenyl, cumyl, carbazolyl or adamantyl;
R 3 is C1-C30 alkyl, C6-C30 aryl or C6-C30 substitutionAn aryl group; preferably, R 3 Is C1-C20 alkyl, C6-C20 aryl or C6-C20 substituted aryl; more preferably, R 3 Methyl, tert-butyl;
R 4 is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; preferably, R 4 Is C1-C20 alkyl, C6-C20 aryl or C6-C20 substituted aryl; more preferably, R 4 Methyl, tert-butyl;
x is halogen, C1-C30 alkyl, silicon base, amino or C6-C30 aryl; preferably, X is halogen, C1-C20 alkyl, silicon-based, amino or C6-C20 aryl; more preferably, X is Cl, methyl or benzyl.
M is a fourth subgroup transition metal; preferably, M is any one of titanium, zirconium or hafnium.
According to the invention, the compound with the structure shown in the formula (I) is specifically the structure shown in the following C1-C13:
C1：R 1 methyl, R 2 Methyl, R 3 Methyl, R 4 Methyl, x=cl, m=ti;
C2：R 1 methyl, R 2 T-butyl, R 3 Methyl, R 4 Methyl, x=cl, m=ti;
C3：R 1 methyl, R 2 Adamantyl group, R 3 Methyl, R 4 Methyl, x=cl, m=ti;
C4：R 1 methyl, R 2 =cumyl, R 3 Methyl, R 4 Methyl, x=cl, m=ti;
C5：R 1 methyl, R 2 Carbazolyl group, R 3 Methyl, R 4 Methyl, x=cl, m=ti;
C6：R 1 methyl, R 2 Phenyl group, R 3 Methyl, R 4 Methyl, x=cl, m=ti;
C7：R 1 methyl, R 2 T-butyl, R 3 T-butyl, R 4 Methyl, x=cl, m=zr;
C8：R 1 =ethyl, R 2 T-butyl, R 3 Methyl, R 4 Methyl, x=cl, m=hf;
C9：R 1 =ethyl, R 2 Methyl, R 3 Methyl, R 4 Methyl, x=cl, m=ti;
C10：R 1 methyl, R 2 T-butyl, R 3 T-butyl, R 4 Methyl, x=benzyl, m=ti;
C11：R 1 methyl, R 2 T-butyl, R 3 Methyl, R 4 T-butyl, x=benzyl, m=ti;
C12：R 1 methyl, R 2 Methyl, R 3 Methyl, R 4 Methyl, x=me, m=ti;
C13：R 1 methyl, R 2 T-butyl, R 3 Methyl, R 4 Methyl, x=me, m=ti;
the bridged oxygen-containing, sulfur heterocyclic metallocene compounds of the present invention can be synthesized by various methods known to those skilled in the art, and ligands and transition metal complexes having similar structures can also be synthesized with reference to examples 1 and 2 of the present invention.
In some embodiments of the invention, the general synthetic route for the ligand is as follows:
the following are preferred:
dissolving 500mmol of the corresponding raw material (formula II) in 500mL of dry dichloromethane at the temperature of minus 20 ℃, dropwise adding (600 mmol) of liquid bromine into the solution, stirring the solution for reaction for 2 hours, then removing the solution to room temperature, continuing the reaction for 2 hours, stopping the reaction, adding Na2SO3 until no more gas is discharged, filtering, removing the dichloromethane by rotary evaporation, adding 200mL of ethyl acetate and 250mL of water, separating the liquid to keep an organic phase, extracting the aqueous phase with the ethyl acetate for 3 times, merging the kept organic phase, drying the anhydrous magnesium sulfate, filtering, removing the solvent by rotary evaporation, and separating the compound of the formula III by column chromatography.
200mmol of the corresponding compound of formula III is dissolved in 500mL of dry acetonitrile at room temperature, the system is replaced by nitrogen atmosphere, KOH (240 mmol) solid is added, stirring reaction is carried out for 4h, 300mmol of methyl iodide (CH 3I) is then added, reaction is continued for 8h, reaction is stopped, filtration is carried out, 200mL of diethyl ether and 250mL of water are added, an organic phase is separated and retained, then the water phase is extracted with diethyl ether for 3 times, the retained organic phase is combined, anhydrous magnesium sulfate is dried, filtration is carried out, solvent is removed by rotary evaporation, and a methyl group protected raw material (shown as a formula IV) is obtained in a basically equivalent manner.
In a Schlenck bottle (500 mL) under nitrogen atmosphere, sequentially adding a compound (50 mmol) of formula IV and dry diethyl ether (200 mL), cooling to-78 ℃, dropwise adding n-butyllithium (60 mmol) solution into the mixture for about 30min, and heating to room temperature for continuous reaction for 3h; the above reaction clouds were added dropwise to a solution of fluorenone (50 mmol) in diethyl ether (200 mL) and reacted at room temperature for 24h; adding saturated ammonium chloride solution to quench the reaction, extracting the water phase with diethyl ether for 3 times, mixing the remaining organic phases, drying with anhydrous magnesium sulfate, filtering, removing the solvent by rotary evaporation, and separating by column chromatography to obtain the compound of formula V;
at room temperature, 100mmol of the corresponding compound of formula V is dissolved in 300mL of dry acetonitrile, the system is replaced by nitrogen atmosphere, KOH (120 mmol) solid is added into the system, stirring reaction is carried out for 4 hours, then 150mmol of R1I or R1Br is added, reaction is continued for 8 hours, the reaction is stopped, filtration is carried out, acetonitrile is removed by rotary evaporation, 200mL of diethyl ether and 250mL of water are added, an organic phase is separated and retained, then the diethyl ether is used for extracting the water phase for 3 times, the retained organic phase is combined, anhydrous magnesium sulfate is dried, filtration is carried out, solvent is removed by rotary evaporation, and the compound of the formula VI is obtained in a basically equivalent manner.
In a Schlenck bottle (250 mL) under nitrogen atmosphere, sequentially adding a compound (20 mmol) of the formula VI and dry diethyl ether (150 mL), cooling to 0 ℃, dropwise adding a solution of n-butyllithium (40.5 mmol) into the mixture for about 30min, and heating to room temperature for continuous reaction for 3h after the completion of dropwise addition; the reaction system is dripped into 1, 2-dibromoethane (100 mmol) and the reaction is continued for 18h at room temperature; extracting volatile components under vacuum, heating to 80deg.C, continuously extracting for 1.5 hr, cooling to room temperature, adding 30mL of dry diethyl ether, filtering to remove inorganic salts, extracting volatile components, and separating by column chromatography to obtain compound of formula VII;
In a Schlenck bottle (250 mL) under nitrogen atmosphere, the compound (20 mmol) of the formula I and dry diethyl ether (150 mL) are sequentially added, the mixture is cooled to 0 ℃, the solution of n-butyllithium (40.5 mmol) is dropwise added to the mixture for about 30min, and the mixture is heated to room temperature for continuous reaction for 3h after the dropwise addition; and (3) dripping an diethyl ether (50 mL) solution containing the compound (20 mmol) of the formula VII, which is cooled to the temperature of minus 40 ℃ in advance, into the system, after the dripping is completed for about 1h, then, heating to the room temperature, continuing to react for 12h to obtain a white turbid liquid system, adding a saturated ammonium chloride solution, quenching the reaction, then, adding concentrated hydrochloric acid, carrying out reflux reaction for 1h, cooling to the room temperature, separating the liquid, retaining an organic phase, washing for 3 times, merging the organic phases, removing the solvent in vacuum, and separating by column chromatography to obtain the ligand pure product.
The synthesis of the bridged oxygen-containing and sulfur heterocyclic metallocene compounds of the present invention is not limited to the aforementioned synthetic methods, and those skilled in the art can synthesize the metallocene compounds by various methods according to the existing chemical knowledge.
The invention provides a catalyst for olefin polymerization, which comprises a main catalyst and a cocatalyst; the main catalyst comprises the bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures in any one of the technical schemes.
The bridged oxygen-containing and sulfur heterocyclic metallocene compounds and the preparation method thereof have been described above for clarity and are not described in detail herein.
In the catalytic system, the cocatalyst may be various alkylaluminoxane, modified alkylaluminoxane, haloalkylaluminum, a mixture of alkylaluminum and boron agent, or other agents which can perform the same activation function. Wherein alkyl aluminoxanes include (but are not limited to): methylaluminoxane (MAO), modified Methylaluminoxane (MMAO), ethylaluminoxane, isobutylaluminoxane, alkylaluminum chlorides including, but not limited to: diethyl aluminum chloride, ethyl aluminum dichloride, sesquidiethyl aluminum chloride or ethyl dichloroAluminum, trialkylaluminum includes (but is not limited to): trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, organoboron compounds include (but are not limited to): b (C) 6 F 5 ) 3 、Ph 3 CB(C 6 F 5 ) 4 、Me 3 CB(C 6 F 5 ) 4 、PhMe 2 HNB(C 6 F 5 ) 4 PhR 2 HNB(C 6 F 5 ) 4 (R is alkyl of 2 to 18 carbon atoms). The cocatalyst is preferably Methylaluminoxane (MAO), modified Methylaluminoxane (MMAO), ethylaluminoxane, isobutylaluminoxane, triisobutylaluminum/tetra (pentafluorophenyl) borate composite cocatalyst.
According to the invention, the molar ratio of aluminium atoms in the cocatalyst to metal atoms in the main catalyst is 1: (5-10000); preferably 1:50 to 1:8000, more preferably 1:50 to 1:450;
The molar ratio of boron atoms in the cocatalyst to metal atoms in the main catalyst is (0-2): 1.
the bridged metallocene compounds with oxygen-containing and sulfur heterocyclic structures are used for catalyzing olefin polymerization reaction, can adopt a bulk polymerization process, a slurry polymerization process or a solution polymerization process, and can be carried out in a batch reactor or a continuous reaction device. When a slurry polymerization process or a solution polymerization process is employed, toluene, xylene, chlorobenzene, dichlorobenzene, hexane, octane, other high boiling alkanes, petroleum ether, liquid paraffin, etc. may be used as a solvent as required.
In the polymerization reaction, the molar ratio of the main catalyst to the aluminum-containing cocatalyst is in the range of 1: (5-10000); preferably 1:50 to 1:8000, more preferably 1:50 to 1:450.
The invention provides a preparation method of polyolefin, which comprises the following steps:
homopolymerizing ethylene in the presence of a catalyst to obtain polyolefin;
the catalyst comprises a main catalyst and a cocatalyst; the main catalyst comprises the bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures in any one of the technical schemes.
The invention provides a preparation method of polyolefin, which is characterized by comprising the following steps:
Copolymerizing ethylene and alpha-olefin in the presence of a catalyst to obtain polyolefin;
the catalyst comprises a main catalyst and a cocatalyst; the procatalyst comprising a bridged oxygen-containing, sulfur heterocyclic structured metallocene compound according to any of the claims 1-4.
The specific process of the invention for catalyzing olefin polymerization reaction is as follows: adding comonomer, main catalyst and cocatalyst into polymerization kettle under the condition of ethylene existence, stirring to make reaction for 0-600 min at 0-200 deg.C, then adding proper quantity of ethyl alcohol to terminate ethylene oligomerization reaction. And cooling the reaction system to room temperature, filtering, and drying in vacuum to constant weight to obtain the polymer.
The bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures can be used as an active component for catalyzing ethylene or alpha-olefin homopolymerization and ethylene and alpha-olefin copolymerization by being activated by a proper cocatalyst. The alpha-olefin is propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene or 1-octadecene, preferably propylene, 1-butene, 1-hexene, 1-octene or 1-decene, more preferably 1-octene. Under proper conditions, catalyzing ethylene homopolymerization to obtain high molecular weight and high impact strength polyethylene, wherein the impact strength of the polyethylene is close to that of the ultra-high molecular weight polyethylene; the ethylene and octene copolymerization is catalyzed to obtain the ethylene-octyl copolymer with medium molecular weight.
According to the invention, the polymerization temperature is from 0 to 200 ℃, preferably from 50 to 150 ℃; for non-bulk polymerization, the olefin concentration is greater than 0M or the pressure is greater than 0MPa, with the highest concentration or pressure reaching the bulk polymerization concentration or pressure. The polymerization time is greatly different according to the different factors such as the catalyst, the cocatalyst, the monomer type, the monomer concentration, the reaction temperature and the like; for ethylene, 1-octene polymerization, 0 to 180 minutes is required; for the polymerization of long chain alpha-olefins, 0 to 600 minutes are required.
The invention provides a bridged oxygen-containing and sulfur heterocyclic ringA metallocene compound having a structure represented by formula (I): wherein R is 1 Is C1-C4 alkyl; r is R 2 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; r is R 3 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; r is R 4 Is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; x is halogen, C1-C30 alkyl, silicon base, amino or C6-C30 aryl; m is a fourth subgroup transition metal. The metallocene compound with the nitrogen-containing and sulfur heterocyclic structures has the characteristics of good heat stability, low cocatalyst usage amount, high catalytic activity, good heat stability and long catalytic life when in use, and the catalyst can catalyze ethylene to polymerize to obtain ultra-high molecular weight polyethylene, ethylene and 1-octene are copolymerized, and the comonomer insertion rate is high.
The structure of the metal complex is convenient for modification; the catalyst disclosed by the invention has good stability and very high catalytic activity; the catalyst can catalyze ethylene polymerization with high activity to obtain ultra-high molecular weight linear polyethylene, and has high catalytic activity, good thermal stability and long catalytic life;
the catalyst of the invention catalyzes the copolymerization of ethylene and 1-hexene, ethylene and 1-octene, and can obtain polymer products with high molecular weight and high comonomer insertion rate.
The experimental results show that: the molecular weight of the ultra-high molecular weight polyethylene prepared by catalyzing ethylene polymerization by the complex provided by the invention can reach 228.8 multiplied by 10 4 g/mol above; the molecular weight of the polymer obtained by catalyzing the copolymerization of ethylene and 1-hexene is up to 23.9X10 4 g/mol, 1-hexene molar insertion rate up to 13.5%; the molecular weight of the polymer obtained by catalyzing the copolymerization of ethylene and 1-octene by the complex provided by the invention is up to 24.8x10 4 The molar insertion rate of 1-octene is up to 9.3% g/mol.
In order to further illustrate the present invention, the following examples are provided to illustrate in detail one bridged oxygen-containing, sulfur heterocyclic structure metallocene compound and its use.
Example 1: preparation of ligands
The ligand of the bridged metallocene compound with the oxygen-containing and sulfur heterocyclic structures has the following structural general formula:
in the present invention, the ligands prepared are more preferably ligands L1 to L10, L1 of the following 10 structures: r is R 1 Methyl, R 2 Methyl, R 3 Methyl, R 4 Methyl group;
L2：R 1 methyl, R 2 T-butyl, R 3 Methyl, R 4 Methyl group;
L3：R 1 methyl, R 2 Adamantyl group, R 3 Methyl, R 4 Methyl group;
L4：R 1 methyl, R 2 =cumyl, R 3 Methyl, R 4 Methyl group;
L5：R 1 methyl, R 2 Carbazolyl group, R 3 Methyl, R 4 Methyl group;
L6：R 1 methyl, R 2 Phenyl group, R 3 Methyl, R 4 Methyl group;
L7：R 1 methyl, R 2 T-butyl, R 3 T-butyl, R 4 Methyl group;
L8：R 1 =ethyl, R 2 T-butyl, R 3 Methyl, R 4 Methyl group;
L9：R 1 =ethyl, R 2 Methyl, R 3 Methyl, R 4 Methyl group;
L10：R 1 methyl, R 2 T-butyl, R 3 T-butyl, R 4 Methyl group.
The specific preparation process of the ligand is as follows:
(1) The compounds of formula I as desired in the present invention can be synthesized by reference to the prior art.
(2) General synthetic route for ligands in the present invention:
dissolving 500mmol of the corresponding raw material (formula II) in 500mL of dry dichloromethane at-20 ℃, dropwise adding (600 mmol) of liquid bromine into the solution, stirring and reacting for 2h, then removing the solution to room temperature, continuing to react for 2h, stopping the reaction, and adding Na 2 SO 3 Until no more gas is evolved, filtering, removing dichloromethane by rotary evaporation, adding 200mL of ethyl acetate and 250mL of water, separating the liquid to retain an organic phase, extracting the aqueous phase with ethyl acetate for 3 times, combining the retained organic phases, drying over anhydrous magnesium sulfate, filtering, removing the solvent by rotary evaporation, and separating by column chromatography to obtain the compound of formula III.
200mmol of the corresponding compound of formula III are dissolved in 500mL of dry acetonitrile at room temperature, the system is replaced by nitrogen, KOH (240 mmol) solids are added thereto, the reaction is stirred for 4h, and then 300mmol of iodomethane (CH) 3 I) Continuing the reaction for 8 hours, stopping the reaction, filtering, removing acetonitrile by rotary evaporation, adding 200mL of diethyl ether and 250mL of water, separating the liquid to remain an organic phase, extracting the aqueous phase with diethyl ether for 3 times, combining the remaining organic phase, drying the anhydrous magnesium sulfate, filtering, removing the solvent by rotary evaporation, and obtaining a raw material with a methyl group protection in a basically equivalent manner (shown as a formula IV).
In a Schlenck bottle (500 mL) under nitrogen atmosphere, sequentially adding a compound (50 mmol) of formula IV and dry diethyl ether (200 mL), cooling to-78 ℃, dropwise adding n-butyllithium (60 mmol) solution into the mixture for about 30min, and heating to room temperature for continuous reaction for 3h; the above reaction clouds were added dropwise to a solution of fluorenone (50 mmol) in diethyl ether (200 mL) and reacted at room temperature for 24h; adding saturated ammonium chloride solution to quench the reaction, extracting the water phase with diethyl ether for 3 times, mixing the remaining organic phases, drying with anhydrous magnesium sulfate, filtering, removing the solvent by rotary evaporation, and separating by column chromatography to obtain the compound of formula V;
At room temperature, 100mmol of the corresponding compound of formula V was dissolved in 300mL of dry acetonitrile, the system was replaced with nitrogen atmosphere, KOH (120 mmol) solid was added thereto, and the reaction was stirred for 4 hours, followed by 150mmol of R 1 I or R 1 Br, continuing to react for 8 hours, stopping the reaction, filtering, removing acetonitrile by rotary evaporation, adding 200mL of diethyl ether and 250mL of water, separating the liquid to remain an organic phase, extracting the aqueous phase with diethyl ether for 3 times, combining the remaining organic phase, drying the anhydrous magnesium sulfate, filtering, and removing the solvent by rotary evaporation to obtain the compound of the formula VI in a basically equivalent amount.
In a Schlenck bottle (250 mL) under nitrogen atmosphere, sequentially adding a compound (20 mmol) of the formula VI and dry diethyl ether (150 mL), cooling to 0 ℃, dropwise adding a solution of n-butyllithium (40.5 mmol) into the mixture for about 30min, and heating to room temperature for continuous reaction for 3h after the completion of dropwise addition; the reaction system is dripped into 1, 2-dibromoethane (100 mmol) and the reaction is continued for 18h at room temperature; extracting volatile components under vacuum, heating to 80deg.C, continuously extracting for 1.5 hr, cooling to room temperature, adding 30mL of dry diethyl ether, filtering to remove inorganic salts, extracting volatile components, and separating by column chromatography to obtain compound of formula VII;
in a Schlenck bottle (250 mL) under nitrogen atmosphere, the compound (20 mmol) of the formula I and dry diethyl ether (150 mL) are sequentially added, the mixture is cooled to 0 ℃, the solution of n-butyllithium (40.5 mmol) is dropwise added to the mixture for about 30min, and the mixture is heated to room temperature for continuous reaction for 3h after the dropwise addition; and (3) dripping an diethyl ether (50 mL) solution containing the compound (20 mmol) of the formula VII, which is cooled to the temperature of minus 40 ℃ in advance, into the system, after the dripping is completed for about 1h, then, heating to the room temperature, continuing to react for 12h to obtain a white turbid liquid system, adding a saturated ammonium chloride solution, quenching the reaction, then, adding concentrated hydrochloric acid, carrying out reflux reaction for 1h, cooling to the room temperature, separating the liquid, retaining an organic phase, washing for 3 times, merging the organic phases, removing the solvent in vacuum, and separating by column chromatography to obtain the ligand pure product.
Example 2: the preparation method of the bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures comprises the following steps:
(1) Preparation method of metal complex (metal chloride, complex C1)
Under nitrogen atmosphere, 1mmol of ligand L1 was dissolved in 30mL of toluene, cooled to-10℃and 2mmol of n-butyllithium solution was added dropwise thereto, the low temperature was removed, the reaction was continued at room temperature for 3 hours, and it was slowly transferred to TiCl cooled to-40℃beforehand with a double-ended solvent transfer needle 4 (1 mmol) toluene (10 mL), keeping the low temperature for reaction for 1h, slowly heating to room temperature, and continuing the reaction for 3h, wherein oily insoluble matters are generated in the system; filtering to remove insoluble substances, vacuum removing volatile components from the filtrate to obtain CH 2 Cl 2 Recrystallisation of the product to give the metal complex, yield: 0.1994g, yield: 29.4%, elemental analysis: actual measurement (calculation) C:70.71 (70.70) H:4.75 (4.75) O:2.36 (2.35) S:4.72 (4.72);
(2) Preparation method of metal complex (metal chloride, complex C2)
1mmol of ligand L2 was dissolved in 30mL of toluene under nitrogen atmosphere, cooled to-10℃and 2mmol of n-butyllithium solution was added dropwise thereto, the low temperature was removed, the reaction was continued at room temperature for 3 hours, and it was slowly transferred to TiCl cooled to-40℃beforehand with a double-ended solvent transfer needle 4 (1 mmol) toluene (10 mL), keeping the low temperature for reaction for 1h, slowly heating to room temperature, and continuing the reaction for 3h, wherein oily insoluble matters are generated in the system; filtering to remove insoluble substances, vacuum removing volatile components from the filtrate to obtain CH 2 Cl 2 Recrystallisation of the product to give the metal complex, yield: 0.1692g, yield: 23.5%, elemental analysis: actual measurement (calculation) C:71.57 (71.57) H:5.31 (5.31) O:2.22 (2.22) S:4.44 (4.44);
(3) Preparation method of metal complex (metal chloride, complex C3)
Under nitrogen atmosphere, 1mmol of ligand L3 is dissolved in 30mL of toluene, cooled to-10 ℃, 2mmol of n-butyllithium solution is added dropwise thereto, the low temperature is removed, and the reaction is continued at room temperature for 3h, slowly transferring the mixture to TiCl which is cooled to-40 ℃ in advance by using a double-head solvent transfer needle 4 (1 mmol) toluene (10 mL), keeping the low temperature for reaction for 1h, slowly heating to room temperature, and continuing the reaction for 3h, wherein oily insoluble matters are generated in the system; filtering to remove insoluble substances, vacuum removing volatile components from the filtrate to obtain CH 2 Cl 2 Recrystallisation of the product to give the metal complex, yield: 0.1269g, yield: 15.9%, elemental analysis: actual measurement (calculation) C:73.59 (73.59) H:5.54 (5.55) O:2.00 (2.00) S:4.01 (4.01);
(4) Preparation method of metal complex (metal chloride, complex C4)
1mmol of ligand L4 was dissolved in 30mL of toluene under nitrogen atmosphere, cooled to-10℃and 2mmol of n-butyllithium solution was added dropwise thereto, the low temperature was removed, the reaction was continued at room temperature for 3 hours, and it was slowly transferred to TiCl cooled to-40℃beforehand with a double-ended solvent transfer needle 4 (1 mmol) toluene (10 mL), keeping the low temperature for reaction for 1h, slowly heating to room temperature, and continuing the reaction for 3h, wherein oily insoluble matters are generated in the system; filtering to remove insoluble substances, vacuum removing volatile components from the filtrate to obtain CH 2 Cl 2 Recrystallisation of the product to give the metal complex, yield: 0.1048g, yield: 13.4%, elemental analysis: actual measurement (calculation) C:73.59 (73.57) H:5.14 (5.14) O:2.06 (2.04) S:4.09 (4.09);
(5) Preparation method of metal complex (metal chloride, complex C5)
1mmol of ligand L5 was dissolved in 30mL of toluene under nitrogen atmosphere, cooled to-10℃and 2mmol of n-butyllithium solution was added dropwise thereto, the low temperature was removed, the reaction was continued at room temperature for 3 hours, and it was slowly transferred to TiCl cooled to-40℃beforehand with a double-ended solvent transfer needle 4 (1 mmol) toluene (10 mL), keeping the low temperature for reaction for 1h, slowly heating to room temperature, and continuing the reaction for 3h, wherein oily insoluble matters are generated in the system; filtering to remove insoluble substances, vacuum removing volatile components from the filtrate to obtain CH 2 Cl 2 Recrystallisation of the product to give the metal complexCompound, yield: 0.1028g, yield: 12.4%, elemental analysis: actual measurement (calculation) C:73.74 (73.74) H:4.49 (4.49) O:1.93 (1.93) S:3.86 (3.86);
(6) Preparation method of metal complex (metal chloride, complex C6)
1mmol of ligand L6 was dissolved in 30mL of toluene under nitrogen atmosphere, cooled to-10℃and 2mmol of n-butyllithium solution was added dropwise thereto, the low temperature was removed, the reaction was continued at room temperature for 3 hours, and it was slowly transferred to TiCl cooled to-40℃beforehand with a double-ended solvent transfer needle 4 (1 mmol) toluene (10 mL), keeping the low temperature for reaction for 1h, slowly heating to room temperature, and continuing the reaction for 3h, wherein oily insoluble matters are generated in the system; filtering to remove insoluble substances, vacuum removing volatile components from the filtrate to obtain CH 2 Cl 2 Recrystallisation of the product to give the metal complex, yield: 0.1843g, yield: 24.9%, elemental analysis: actual measurement (calculation) C:72.88 (72.88) H:4.63 (4.62) O:2.16 (2.16) S:4.32 (4.32);
(7) Preparation method of metal complex (metal chloride, complex C7)
1mmol of ligand L7 was dissolved in 30mL of toluene under nitrogen atmosphere, cooled to-10℃and 2mmol of n-butyllithium solution was added dropwise thereto, the low temperature was removed, the reaction was continued at room temperature for 3 hours, and it was slowly transferred to ZrCl previously cooled to-40℃with a double-ended solvent transfer needle 4 (1 mmol) toluene (10 mL), keeping the low temperature for reaction for 1h, slowly heating to room temperature, and continuing the reaction for 3h, wherein oily insoluble matters are generated in the system; filtering to remove insoluble substances, vacuum removing volatile components from the filtrate to obtain CH 2 Cl 2 Recrystallisation of the product to give the metal complex, yield: 0.1867g, yield: 24.5%, elemental analysis: actual measurement (calculation) C:72.35 (72.35) H:5.81 (5.81) O:2.09 (2.09) S:4.21 (4.20);
(8) Preparation method of metal complex (metal chloride, complex C8)
1mmol of ligand L8 was dissolved in 30mL of toluene under nitrogen atmosphere, cooled to-10℃and 2mmol of n-butyllithium solution was added dropwise thereto, the low temperature was removed,the reaction was continued at room temperature for 3h, which was slowly transferred to HfCl previously cooled to-40℃with a double-ended solvent transfer needle 4 (1 mmol) toluene (10 mL), keeping the low temperature for reaction for 1h, slowly heating to room temperature, and continuing the reaction for 3h, wherein oily insoluble matters are generated in the system; filtering to remove insoluble substances, vacuum removing volatile components from the filtrate to obtain CH 2 Cl 2 Recrystallisation of the product to give the metal complex, yield: 0.1916g, yield: 26.1%, elemental analysis: actual measurement (calculation) C:71.84 (71.84) H:5.48 (5.48) O:2.17 (2.17) S:4.36 (4.36);
(9) Preparation method of metal complex (metal chloride, complex C9)
1mmol of ligand L9 was dissolved in 30mL of toluene under nitrogen atmosphere, cooled to-10℃and 2mmol of n-butyllithium solution was added dropwise thereto, the low temperature was removed, the reaction was continued at room temperature for 3 hours, and it was slowly transferred to TiCl cooled to-40℃beforehand with a double-ended solvent transfer needle 4 (1 mmol) toluene (10 mL), keeping the low temperature for reaction for 1h, slowly heating to room temperature, and continuing the reaction for 3h, wherein oily insoluble matters are generated in the system; filtering to remove insoluble substances, vacuum removing volatile components from the filtrate to obtain CH 2 Cl 2 Recrystallisation of the product to give the metal complex, yield: 0.1654g, yield: 23.9%, elemental analysis: actual measurement (calculation) C:71.02 (71.00) H:4.94 (4.94) O:2.31 (2.31) S:4.62 (4.62);
(10) Preparation of metal complexes (Metal benzyl, complex C10)
The ligand metal chloride L7 (X=Cl on the metal M at this time) is obtained according to the preparation method, the ligand metal chloride (1 mmol) is taken to be dissolved in toluene (30 mL) under the nitrogen atmosphere, the solution is cooled to 0 ℃, benzyl magnesium bromide solution (4 mmol) is dripped into the solution, the solution is cooled to room temperature for reaction for 2 hours, insoluble matters are removed by filtration, and the filtrate is pumped to be dried, thus obtaining the target metal complex C10, the yield is: 0.1967g, yield: 22.5%, elemental analysis: actual measurement (calculation) C:82.36 (82.36) H:6.68 (6.68) O:1.83 (1.83) S:3.66 (3.66);
(11) Preparation of metal complexes (Metal benzyl, complex C11)
The ligand metal chloride L10 (X=Cl on the metal M at this time) is obtained according to the preparation method, the ligand metal chloride (1 mmol) is taken to be dissolved in toluene (30 mL) under the nitrogen atmosphere, the solution is cooled to 0 ℃, benzyl magnesium bromide solution (4 mmol) is dripped into the solution, the solution is cooled to room temperature for reaction for 2 hours, insoluble matters are removed by filtration, and the filtrate is pumped to be dried, thus obtaining the target metal complex C11, the yield is: 0.2055g, yield: 23.5%, elemental analysis: actual measurement (calculation) C:82.35 (82.36) H:6.68 (6.68) O:1.83 (1.83) S:3.66 (3.66);
(12) Preparation of metal complexes (metal methide, complex C12)
The ligand metal chloride L1 (X=Cl on the metal M at this time) is obtained according to the preparation method, the ligand metal chloride (1 mmol) is taken to be dissolved in toluene (30 mL) under the nitrogen atmosphere, the solution is cooled to 0 ℃, a methyl magnesium bromide solution (2 mmol) is dripped into the solution, the solution is cooled to room temperature for reaction for 2 hours, insoluble matters are removed by filtration, and the filtrate is pumped to be dried, thus obtaining the target metal complex C12, the yield is: 0.1793g, yield: 28.1%, elemental analysis: actual measurement (calculation) C:78.99 (78.98) H:5.98 (6.00) O:2.50 (2.50) S:5.02 (5.02);
(13) Preparation of metal complexes (metal methide, complex C13)
The ligand metal chloride L2 (X=Cl on the metal M at this time) is obtained according to the preparation method, the ligand metal chloride (1 mmol) is taken to be dissolved in toluene (30 mL) under the nitrogen atmosphere, the solution is cooled to 0 ℃, a methyl magnesium bromide solution (2 mmol) is dripped into the solution, the solution is cooled to room temperature for reaction for 2 hours, insoluble matters are removed by filtration, and the filtrate is pumped to be dried, thus obtaining the target metal complex C13, the yield is: 0.1891g, yield: 27.8%, elemental analysis: actual measurement (calculation) C:79.39 (79.39) H:6.51 (6.51) O:2.35 (2.35) S:4.71 (4.71).
Example 3: catalytic ethylene polymerization studies
And accurately weighing a certain mass of metal complex in a glove box, adding a certain amount of dry toluene solution, and preparing a 2 mu mol/mL solution for later use. Two single-port ampoule bottles baked overnight in a 120 ℃ oven are connected to a vacuum line for air extraction, and are repeatedly baked by a gas lamp, and are transferred into a glove box after being cooled, a pipette is used for accurately measuring the required amount of catalyst, the catalyst is placed in one ampoule bottle, 15mL of dry toluene is added, the required amount of cocatalyst and 45mL of dry toluene are added into the other ampoule bottle, and the two ampoule bottles are fully shaken for uniform mixing for standby. The polymerization reaction is carried out in a 150mL normal pressure glass reaction kettle, the polymerization kettle with mechanical stirring is heated to 120 ℃, the vacuum pumping is carried out for 1h, and the system is adjusted to the temperature condition required by polymerization; maintaining the vacuumizing state, removing heating, slowly cooling to the temperature required by polymerization, transferring the polymerization kettle into an oil bath, maintaining the constant temperature, introducing ethylene gas of 0.1MPa, starting stirring, then sequentially and rapidly adding a cocatalyst solution and a catalyst solution, rapidly introducing ethylene gas of 0.5MPa, maintaining the constant pressure, and polymerizing for a period of time; after the completion, the ethylene air inlet valve is closed, the air outlet valve is opened to release residual pressure, the kettle is opened, the mixture in the kettle is poured into a quenching agent (ethanol: 3M/L concentrated hydrochloric acid=1:1 according to the volume ratio) prepared in advance, stirred for 30min, the polymer is filtered out, and after natural airing for a period of time, the mixture is transferred into a vacuum oven at 60 ℃ to be dried to constant weight.
TABLE 1 polymerization data for ethylene catalyzed by C1-C13 as the primary catalyst a ；
a Polymerization conditions: the dosage of the main catalyst C1-C13 is 0.2 mu mol, the cocatalyst is MAO, and the polymerization temperature is as follows: the polymerization time was 5min at 80 ℃.
Example 4: catalytic ethylene and 1-hexene copolymerization research
The polymerization reaction is carried out in a 500mL stainless steel high-pressure reaction kettle, the polymerization kettle with mechanical stirring is heated to 150 ℃, vacuum pumping is carried out for 1h, a system is adjusted to a temperature condition required by polymerization, ethylene gas with the pressure of 0.1MPa is filled, a mixed isoparaffin (Isopar E) solution (the total volume of the final solution is 400 mL) containing a certain amount of Modified Methylaluminoxane (MMAO) and 1-hexene with the concentration is added into the polymerization kettle, the temperature is kept constant for a period of time until the temperature is constant, ethylene gas with the pressure of 3.5MPa is filled, the reaction kettle is waited for 10min, so that the ethylene reaches dissolution balance, then a main catalyst is added, and the reaction kettle is stirred for a period of time. And (3) discharging residual ethylene gas after the polymerization reaction is finished, cooling to 40 ℃, opening the reaction kettle, pouring the obtained polymerization reaction mixture into a mixed solution of 3M hydrochloric acid and ethanol in a volume ratio of 1:1, stirring for 5min, filtering, and drying a polymer product in a vacuum oven. The mass was weighed, the molecular weight and molecular weight distribution were measured, and the comonomer insertion rate was measured by carbon spectroscopy.
TABLE 2 copolymerization data of ethylene and 1-hexene catalyzed by C1-C13 as the main catalyst a ；
a Polymerization conditions: the dosage of the main catalyst C1-C13 is 2.5 mu mol, the cocatalyst is MMAO-7, the Al/M= 400,1-hexene concentration is 0.90mol/L, the polymerization pressure is 3.0MPa, and the polymerization temperature is as follows: polymerization time is 20min at 80 ℃; b molecular weight, molecular weight distribution, as measured by GPC; c from the following components 13 CNMR measurement.
Example 5: catalytic ethylene and 1-octene copolymerization research
The polymerization reaction is carried out in a 500mL stainless steel high-pressure reaction kettle, the polymerization kettle with mechanical stirring is heated to 150 ℃, vacuum pumping is carried out for 1h, a system is adjusted to a temperature condition required by polymerization, ethylene gas with the pressure of 0.1MPa is filled into the polymerization kettle, a mixed isoparaffin (Isopar E) solution (the total volume of the final solution is 400 mL) containing a certain amount of Modified Methylaluminoxane (MMAO) and 1-octene with the concentration is added into the polymerization kettle, the temperature is kept constant for a period of time until the temperature is constant, ethylene gas with the pressure of 3.5MPa is filled into the polymerization kettle, the reaction kettle waits for 10min, so that the ethylene reaches dissolution balance, then a main catalyst is added into the polymerization kettle, and the reaction kettle is stirred for a period of time. And (3) discharging residual ethylene gas after the polymerization reaction is finished, cooling to 40 ℃, opening the reaction kettle, pouring the obtained polymerization reaction mixture into a mixed solution of 3M hydrochloric acid and ethanol in a volume ratio of 1:1, stirring for 5min, filtering, and drying a polymer product in a vacuum oven. The mass was weighed, the molecular weight and molecular weight distribution were measured, and the comonomer insertion rate was measured by carbon spectroscopy.
TABLE 3 copolymerization data of ethylene and 1-octene catalyzed by C1-C13 as the main catalyst a ；
a Polymerization conditions: the dosage of the main catalyst C1-C13 is 2.5 mu mol, the cocatalyst is MMAO-7, the Al/M= 400,1-octene concentration is 0.90mol/L, the polymerization pressure is 3.0MPa, and the polymerization temperature is as follows: polymerization time is 10min at 80 ℃; b molecular weight, molecular weight distribution, as measured by GPC; c from the following components 13 CNMR measurement; d the cocatalyst was MMAO-7, al/m=300, the organoboron cocatalyst was 3 μmol Ph 3 CB(C 6 F 5 ) 4 。
As can be seen from the above examples, the present invention provides a bridged metallocene compound with oxygen-containing and sulfur heterocyclic structures, which has good stability, can maintain high catalytic activity at 80deg.C, and the complex can be used as a main catalyst to catalyze ethylene polymerization to obtain ultra-high molecular weight linear polyethylene, and has high catalytic activity, good thermal stability, long catalytic life, and molecular weight up to 228.8 ×10 4 g/mol above; the complex is used as a main catalyst for catalyzing the copolymerization of ethylene, 1-hexene and 1-octene, and has high activity, high molecular weight of polymer and high comonomer insertion rate. The experimental results show that: the molecular weight of the polymer obtained by catalyzing the copolymerization of ethylene and 1-hexene by the complex provided by the invention is up to 23.9x10 4 g/mol, 1-hexene molar insertion rate up to 13.5%; the molecular weight of the polymer obtained by catalyzing the copolymerization of ethylene and 1-octene by the complex provided by the invention is up to 24.8x10 4 The molar insertion rate of 1-octene is up to 9.3% g/mol.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A bridged oxygen-containing, sulfur heterocyclic structure metallocene compound having the structure of formula (I):
wherein the R is 1 Methyl or ethyl; r is R 2 Methyl, tert-butyl, phenyl, cumyl, carbazolyl or adamantyl; r is R 3 Methyl or tert-butyl; r is R 4 Methyl or tert-butyl;
x is Cl, methyl or benzyl; m is any one of titanium, zirconium or hafnium.
2. The compound according to claim 1, wherein the compound having a structure represented by formula (I) is specifically a structure represented by the following C1 to C13:
C1：R 1 methyl, R 2 Methyl, R 3 Methyl, R 4 Methyl, x=cl; m=ti;
C2：R 1 methyl, R 2 T-butyl, R 3 Methyl, R 4 Methyl, x=cl; m=ti;
C3：R 1 methyl, R 2 Adamantyl group, R 3 Methyl, R 4 Methyl, x=cl; m=ti;
C4：R 1 methyl, R 2 =cumyl, R 3 Methyl, R 4 Methyl, x=cl; m=ti;
C5：R 1 methyl, R 2 Carbazolyl group, R 3 Methyl, R 4 Methyl, x=cl; m=ti;
C6：R 1 methyl, R 2 Phenyl group, R 3 Methyl, R 4 =JiaA radical, x=cl; m=ti;
C7：R 1 methyl, R 2 T-butyl, R 3 T-butyl, R 4 Methyl, x=cl; m=zr;
C8：R 1 =ethyl, R 2 T-butyl, R 3 Methyl, R 4 Methyl, x=cl; m=hf;
C9：R 1 =ethyl, R 2 Methyl, R 3 Methyl, R 4 Methyl, x=cl; m=ti; c10: r is R 1 Methyl, R 2 T-butyl, R 3 T-butyl, R 4 Methyl, x=benzyl; m=ti; c11: r is R 1 Methyl, R 2 T-butyl, R 3 Methyl, R 4 T-butyl, x=benzyl; m=ti; and C12: r is R 1 Methyl, R 2 Methyl, R 3 Methyl, R 4 Methyl, x=me; m=ti;
C13：R 1 methyl, R 2 T-butyl, R 3 Methyl, R 4 Methyl, x=me, m=ti.
3. A catalyst for olefin polymerization, which is characterized by comprising a main catalyst and a cocatalyst; the procatalyst is selected from the group consisting of bridged oxygen-containing, sulfur heterocyclic structured metallocene compounds of any of claims 1-2;
The cocatalyst is one or more of a mixture of alkyl aluminum and a boron agent, alkyl aluminoxane, modified alkyl aluminoxane or halogenated alkyl aluminum.
4. The catalyst for olefin polymerization according to claim 3, wherein the molar ratio of the aluminum atom in the cocatalyst to the metal atom in the main catalyst is (5 to 10000): 1, a step of;
the molar ratio of boron atoms in the cocatalyst to metal atoms in the main catalyst is (0-2): 1.
5. a process for the preparation of a polyolefin comprising:
homopolymerizing ethylene in the presence of a catalyst to obtain polyolefin;
the catalyst comprises a main catalyst and a cocatalyst; the procatalyst is selected from the group consisting of bridged oxygen-containing, sulfur heterocyclic structured metallocene compounds of any of claims 1-2;
the cocatalyst is one or more of a mixture of alkyl aluminum and a boron agent, alkyl aluminoxane, modified alkyl aluminoxane or halogenated alkyl aluminum.
6. A process for the preparation of a polyolefin, comprising:
copolymerizing ethylene and alpha-olefin in the presence of a catalyst to obtain polyolefin;
the catalyst comprises a main catalyst and a cocatalyst; the procatalyst is selected from the group consisting of bridged oxygen-containing, sulfur heterocyclic structured metallocene compounds of any of claims 1-2;
The cocatalyst is one or more of a mixture of alkyl aluminum and a boron agent, alkyl aluminoxane, modified alkyl aluminoxane or halogenated alkyl aluminum.
7. The process according to claim 5 or 6, wherein the temperature of the homo-or copolymerization reaction is 0 to 200℃and the ethylene pressure during polymerization is 0.1 to 10MPa.
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| CN111247157A (en) * | 2017-08-21 | 2020-06-05 | 沙特基础工业爱思开Nexlene私人有限公司 | Novel transition metal compound, catalyst composition comprising the same, and method for preparing ethylene homopolymer or copolymer of ethylene and α -olefin using the same |
| CN113354690A (en) * | 2021-07-09 | 2021-09-07 | 山东京博石油化工有限公司 | Bridged nitrogen-containing heterocyclic structure metallocene compound and application thereof |
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| CN111247157A (en) * | 2017-08-21 | 2020-06-05 | 沙特基础工业爱思开Nexlene私人有限公司 | Novel transition metal compound, catalyst composition comprising the same, and method for preparing ethylene homopolymer or copolymer of ethylene and α -olefin using the same |
| CN113354690A (en) * | 2021-07-09 | 2021-09-07 | 山东京博石油化工有限公司 | Bridged nitrogen-containing heterocyclic structure metallocene compound and application thereof |
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