CN114426561B - Front transition metal compound, preparation method and application - Google Patents
Front transition metal compound, preparation method and application Download PDFInfo
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- CN114426561B CN114426561B CN202011090780.5A CN202011090780A CN114426561B CN 114426561 B CN114426561 B CN 114426561B CN 202011090780 A CN202011090780 A CN 202011090780A CN 114426561 B CN114426561 B CN 114426561B
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- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 105
- 150000001336 alkenes Chemical class 0.000 claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 120
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 229910052736 halogen Inorganic materials 0.000 claims description 27
- 150000002367 halogens Chemical class 0.000 claims description 27
- 150000002430 hydrocarbons Chemical group 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 125000001979 organolithium group Chemical group 0.000 claims description 14
- SEDZOYHHAIAQIW-UHFFFAOYSA-N trimethylsilyl azide Chemical compound C[Si](C)(C)N=[N+]=[N-] SEDZOYHHAIAQIW-UHFFFAOYSA-N 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 2
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 18
- 239000002685 polymerization catalyst Substances 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 50
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 35
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 229930192474 thiophene Natural products 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
- 239000005977 Ethylene Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000003446 ligand Substances 0.000 description 12
- ZCSQKFUQLUJERT-UHFFFAOYSA-K cyclopenta-1,3-diene titanium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Ti+3].C1C=CC=C1 ZCSQKFUQLUJERT-UHFFFAOYSA-K 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000178 monomer Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000012190 activator Substances 0.000 description 9
- -1 polyethylene Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000004679 31P NMR spectroscopy Methods 0.000 description 6
- 230000003712 anti-aging effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229910001848 post-transition metal Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- ZVQXQPNJHRNGID-UHFFFAOYSA-N tetramethylsuccinonitrile Chemical compound N#CC(C)(C)C(C)(C)C#N ZVQXQPNJHRNGID-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000005303 weighing 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
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- KXSFECAJUBPPFE-UHFFFAOYSA-N 2,2':5',2''-terthiophene Chemical compound C1=CSC(C=2SC(=CC=2)C=2SC=CC=2)=C1 KXSFECAJUBPPFE-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- YMDGNZIBYXLHDH-UHFFFAOYSA-N diphenyl(thiophen-2-yl)phosphane Chemical compound C1=CSC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 YMDGNZIBYXLHDH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention relates to the field of olefin polymerization catalysts, and discloses a pre-transition metal compound, a preparation method and application thereof, wherein the compound has a structure shown in a formula (1) or a formula (2). The catalyst containing the pre-transition metal compound provided by the invention has the advantages of high catalytic activity, good stability and low catalyst cost.
Description
Technical Field
The invention relates to the field of olefin polymerization catalysts, in particular to a pre-transition metal compound, a preparation method and application thereof.
Background
Polyolefins are a widely used and very important class of polymeric materials, including homopolymers and copolymers of ethylene and alpha olefins. The polyolefin plays a role in the synthetic resin industry and can be used as films, pipes, wires and cables.
Advances in olefin polymerization catalyst technology are a direct impetus for advances in polyolefin industry technology. Catalytic polymerization of olefins has been the focus of attention by researchers and manufacturers, ranging from traditional Ziegler-Natta catalysts to single-site metallocene catalysts that occur at the end of the 80 s of the 20 th century, to highly active "post-metallocene" and late transition metal catalysts at the end of the 20 th century.
The traditional Ziegler-Natta catalyst has the defects of low catalytic activity, wide molecular weight distribution and high content of residual catalyst in a polymerization product obtained by solution polymerization. The discovery of group IV metallocene catalysts solves this problem well, since it has a single site, enabling one to obtain polymers of the desired structure by changing the structure of the catalyst as desired (W.Kaminsky et al, adv. Organomet. Chem.1980, 18, 99; H.H.Brintzinger et al, angew.chem. Int. Ed. Engl.1995, 34, 1143). In recent decades, the research on the use of ligands containing N, O, P coordination atoms instead of metal complexes obtained by coordination of cyclopentadiene and transition metals as olefin polymerization catalysts has been vigorously developed, and the catalysts are collectively called as 'post-metallocene' catalysts.
Post transition metal (Fe, co, ni, pd, etc.) catalysts can catalyze the polymerization of ethylene to yield a variety of polyethylene products, such as polyethylene ranging from highly linear to highly branched structures, polyethylene ranging from unimodal to broad or bimodal, and copolymers of ethylene with polar monomers, polyolefin block copolymers, and the like.
In 1998, brookhart and Gibson reported that Fe, co diimine pyridine complex (structure shown in the following formula) has high activity on ethylene polymerization under activation of Methyl Aluminoxane (MAO) as a cocatalyst, and linear High Density Polyethylene (HDPE) was obtained. It has been found that iron catalytic systems are generally an order of magnitude more active than cobalt catalytic systems.
US5557023 discloses the oligomerization of alpha olefins of post transition metal compounds containing phosphamines having the general structure:
US6762258B2 discloses phosphine-containing, nitrogen-tridentate ligand Fe, co, ni pyridine complexes having the structure shown below, and in addition US6239237B1 discloses that thiophene-containing biphosphinimine post transition metal Fe, co, ni, pd, both of which are useful for olefin polymerization, but the activity of both complexes to catalyze ethylene polymerization only appears to be high under specific reaction conditions (e.g., high pressure, etc.), thus not being detrimental to its wide use as a catalyst:
the olefin polymerization catalysts provided by the prior art are all late transition metal complexes.
Disclosure of Invention
The invention aims to provide a novel pre-transition metal compound, an olefin polymerization catalyst prepared from the compound is used for olefin homo-polymerization or copolymerization reaction, especially for ethylene homo-polymerization and copolymerization of ethylene and alpha-olefin, so that the catalyst has high catalytic activity and catalytic stability, and high-density polyethylene and ethylene-alpha-olefin elastomer can be obtained.
In order to achieve the above object, a first aspect of the present invention provides a pre-transition metal compound having a structure represented by formula (1) or formula (2),
wherein in the formulas (1) and (2),
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently selected from the group consisting of H, C 1-20 C is a hydrocarbon group of (C) 1-20 A group consisting of alkoxy and halogen;
R 1 、R 2 、R 3 and R is 4 Each independently selected from the group consisting of H, C 1-10 C is a hydrocarbon group of (C) 6-12 Aryl and C 1-4 Is substituted with hydrocarbyl group of C 7-16 A group selected from the group consisting of aryl groups;
mt is a group IVB metal element;
x is an atom or group bonded to the Mt element, each X is independently selected from the group consisting of C 1-10 At least one group selected from the group consisting of hydrocarbon groups and halogens; n is an integer to satisfy the valence of X to Mt bond.
The second aspect of the present invention provides a method for producing a pre-transition metal compound having a structure represented by formula (1),
the method comprises the following steps:
1) Subjecting a compound represented by the formula (13 a) to a first reaction in the presence of a first organolithium initiator in the presence of a first organic solvent;
2) Carrying out a second reaction on the product of the first reaction, a compound shown in a formula (11) and a compound shown in a formula (12);
3) Carrying out a third reaction on the product obtained by the second reaction and trimethyl azidosilane to obtain an intermediate compound shown in a formula (14 a);
4) Combining the intermediate compound represented by the formula (14 a) with MtX (n+1) Carrying out a fourth reaction;
wherein the definition of the substituents in formula (1), formula (11), formula (12), formula (13 a) and formula (14 a) are correspondingly the same as those in the foregoing first aspect;
in the formula (13 a), X 1 And X 2 Each independently selected from H and halogen;
in the formula (11) and the formula (12), X 3 And X 4 Each independently selected from H and halogen.
In a third aspect, the present invention provides a method for producing a pre-transition metal compound having a structure represented by formula (2),
the method comprises the following steps:
a) First contacting a compound represented by formula (13 b) in the presence of a second organolithium initiator in the presence of a second organic solvent;
b) Subjecting the product of the first contact to a second contact with a compound represented by formula (11) and a compound represented by formula (12);
c) Carrying out third contact on the product of the second contact and trimethyl azidosilane to obtain an intermediate compound shown in a formula (14 b);
d) Combining the intermediate compound represented by the formula (14 b) with MtX (n+1) Performing a fourth contact;
wherein the definition of the substituents in formula (2), formula (11), formula (12), formula (13 b) and formula (14 b) are correspondingly the same as those in the foregoing first aspect;
in formula (13 b), X 1 And X 2 Each independently selected from H and halogen;
in the formula (11) and the formula (12), X 3 And X 4 Each independently selected from H and halogen.
In a fourth aspect, the present invention provides a pre-transition metal compound prepared by the process described in the second and third aspects above.
In a fifth aspect, the present invention provides the use of a pre-transition metal compound according to the first or fourth aspect in the polymerisation of olefins.
The catalyst containing the pre-transition metal compound containing phosphine and nitrogen (monodentate ligand) provided by the invention has the advantage of high catalytic activity, has excellent catalytic activity under wide polymerization reaction conditions, and can prepare high-density polyethylene and ethylene-alpha olefin elastomer.
In addition, the thiophene heterocyclic compound containing sulfur atoms is conjugated with olefin double bonds to form delocalized pi bonds, so that a large pi conjugated electron system is further formed, and the stability of a catalytic center is enhanced. Compared with the monothiophene heterocycle, the oligothiophene containing multiple rings has better pi electron fluxion, and the metal center is farther away, so that the catalyst center is stabilized, and the catalytic stability is improved.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a pre-transition metal compound having a structure represented by formula (1) or formula (2),
wherein in the formulas (1) and (2),
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently selected from the group consisting of H, C 1-20 C is a hydrocarbon group of (C) 1-20 A group consisting of alkoxy and halogen;
R 1 、R 2 、R 3 and R is 4 Each independently selected from the group consisting of H, C 1-10 C is a hydrocarbon group of (C) 6-12 Aryl and C 1-4 Is substituted with hydrocarbyl group of C 7-16 A group selected from the group consisting of aryl groups;
mt is a group IVB metal element;
x is an atom or group bonded to the Mt element, each X is independently selected from the group consisting of C 1-10 At least one group selected from the group consisting of hydrocarbon groups and halogensThe method comprises the steps of carrying out a first treatment on the surface of the n is an integer to satisfy the valence of X to Mt bond.
The halogen of the present invention includes fluorine, chlorine, bromine and iodine.
The n X's of the present invention may be the same or different.
The C is 1-20 The hydrocarbon group of (C) means a hydrocarbon group having 1 to 20 carbon atoms in total, and may be C 1 、C 2 、C 3 、C 4 、C 5 、C 6 、C 7 、C 8 、C 9 、C 10 、C 11 、C 12 、C 13 、C 14 、C 15 、C 16 、C 17 、C 18 、C 19 Or C 20 Is a hydrocarbon group of (a). For example, the C 1-20 The hydrocarbon radical of (2) may be C 1-20 Alkyl or C of (2) 2-20 Alkenyl groups of (c).
The C is 1-20 Alkoxy of (2) refers to an alkoxy group having a total of 1 to 20 carbon atoms, and may be C 1 、C 2 、C 3 、C 4 、C 5 、C 6 、C 7 、C 8 、C 9 、C 10 、C 11 、C 12 、C 13 、C 14 、C 15 、C 16 、C 17 、C 18 、C 19 Or C 20 Alkoxy groups of (a).
The C is 1-10 The hydrocarbon group of (C) means a hydrocarbon group having 1 to 10 carbon atoms in total, and may be C 1 、C 2 、C 3 、C 4 、C 5 、C 6 、C 7 、C 8 、C 9 、C 10 Is a hydrocarbon group of (a). For example, it may be C 1-10 Alkyl or C of (2) 2-10 Alkenyl groups of (c).
The C is 6-12 The aryl group of (a) means an aryl group having 6 to 12 carbon atoms in total, and may be, for example, phenyl, naphthyl or biphenyl.
The said C 1-4 Is substituted with hydrocarbyl group of C 7-16 Refers to aryl groups having a total of 7 to 16 carbon atoms, and at least one H on the aryl group is C 1-4 Can be substituted by hydrocarbon groups of, for example, C 1-4 Is a hydrocarbyl-substituted phenyl, naphthaleneA group, biphenyl, anthryl or phenanthryl group. For example, it may be C 1-4 Alkyl and/or C of (C) 2-4 Alkenyl-substituted C of (2) 7-16 Aryl groups of (a).
The group IVB metal element is Ti, zr or Hf.
According to a first preferred embodiment of the invention,in the formulas (1) and (2),
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently selected from the group consisting of H, C 1-16 C is a hydrocarbon group of (C) 1-16 A group consisting of alkoxy and halogen;
R 1 、R 2 、R 3 and R is 4 Each independently selected from the group consisting of H, C 1-8 C is a hydrocarbon group of (C) 6-10 Aryl and C 1-4 Is substituted with hydrocarbyl group of C 7-14 A group selected from the group consisting of aryl groups;
mt is Ti, zr or Hf;
each X is independently selected from C 1-8 At least one group selected from the group consisting of hydrocarbon groups, fluorine, chlorine, bromine and iodine.
According to a second preferred embodiment of the invention,in the formulas (1) and (2),
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently selected from the group consisting of H, C 1-10 C is a hydrocarbon group of (C) 1-10 A group consisting of alkoxy and halogen;
R 1 、R 2 、R 3 and R is 4 Each independently selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, phenyl, naphthyl, and C substituted with at least one substituent selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl 7-14 A group selected from the group consisting of aryl groups;
mt is Ti, zr or Hf;
each X is independently selected from at least one of the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopentadiene, fluorine, chlorine, bromine, and iodine.
According to a third preferred embodiment of the inventionIn the formula (1) and the formula (2),
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently selected from the group consisting of H, C 1-6 C is a hydrocarbon group of (C) 1-6 A group consisting of alkoxy and halogen;
R 1 、R 2 、R 3 and R is 4 Each independently selected from the group consisting of phenyl, naphthyl and C substituted with at least one substituent selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl 7-14 A group selected from the group consisting of aryl groups;
mt is Ti, zr or Hf;
n X are each halogen, or one of n X is cyclopentadiene and the remaining (n-1) X are halogen.
According to the present invention, preferably, n is 2 or 3.
According to a fourth preferred embodiment of the inventionThe compounds with the structures shown in the formula (1) and the formula (2) are at least one of the following compounds;
the present inventors have found that the compounds having the above preferred embodiments have higher catalytic efficiency when used as a main catalyst for olefin polymerization, and particularly, that the compounds having the structures represented by the above formulas (1A) - (4A) and (1B) - (4B) have higher catalytic efficiency when used as a main catalyst for olefin polymerization.
The pre-transition metal compound provided by the first aspect of the invention has the advantages of high catalytic activity, good catalytic stability and suitability for preparing high-density polyethylene and ethylene-alpha olefin elastomer when being used for the polymerization reaction of catalyst olefin by forming a catalyst together with an activator.
In addition, the thiophene heterocyclic compound containing sulfur atoms is conjugated with olefin double bonds to form delocalized pi bonds, so that a large pi conjugated electron system is further formed, and the stability of a catalytic center is enhanced. Compared with the monothiophene heterocycle, the oligothiophene containing multiple rings has better pi electron fluxion, and the metal center is farther away, so that the catalyst center is stabilized, and the catalytic stability is improved.
As described above, the second aspect of the present invention provides a method for producing a pre-transition metal compound having a structure represented by formula (1),
the method comprises the following steps:
1) Subjecting a compound represented by the formula (13 a) to a first reaction in the presence of a first organolithium initiator in the presence of a first organic solvent;
2) Carrying out a second reaction on the product of the first reaction, a compound shown in a formula (11) and a compound shown in a formula (12);
3) Carrying out a third reaction on the product obtained by the second reaction and trimethyl azidosilane to obtain an intermediate compound shown in a formula (14 a);
4) Combining the intermediate compound represented by the formula (14 a) with MtX (n+1) Carrying out a fourth reaction;
wherein the definition of the substituents in formula (1), formula (11), formula (12), formula (13 a) and formula (14 a) are correspondingly the same as those in the foregoing first aspect;
in the formula (13 a), X 1 And X 2 Each independently selected from H and halogen;
in the formula (11) and the formula (12), X 3 And X 4 Each independently selected from H and halogen.
As described above, the third aspect of the present invention provides a method for producing a pre-transition metal compound having a structure represented by formula (2),
the method comprises the following steps:
a) First contacting a compound represented by formula (13 b) in the presence of a second organolithium initiator in the presence of a second organic solvent;
b) Subjecting the product of the first contact to a second contact with a compound represented by formula (11) and a compound represented by formula (12);
c) Carrying out third contact on the product of the second contact and trimethyl azidosilane to obtain an intermediate compound shown in a formula (14 b);
d) Combining the intermediate compound represented by the formula (14 b) with MtX (n+1) Performing a fourth contact;
wherein the definition of the substituents in formula (2), formula (11), formula (12), formula (13 b) and formula (14 b) are correspondingly the same as those in the foregoing first aspect;
in formula (13 b), X 1 And X 2 Each independently selected from H and halogen;
in the formula (11) and the formula (12), X 3 And X 4 Each independently selected from H and halogen.
In the second and third aspects of the invention, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 1 、R 2 、R 3 、R 4 The definitions of Mt, X, n, L are the same as those described in the first aspect, and will not be repeated here.
In the second and third aspects of the present invention, the compound represented by formula (13 a), the compound represented by formula (13 b), the compound represented by formula (11) and the compound represented by formula (12) may be obtained commercially or may be self-prepared by methods known in the art.
In the second and third aspects of the present invention, preferably, the compound represented by the formula (11) and the formula (12) is diphenyl phosphine chloride.
In the second and third aspects of the invention, preferably, the formula MtX (n+1) The compound is at least one selected from cyclopentadiene titanium trichloride, titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride.
In the second and third aspects of the present invention, it is preferable that, in step 1) and step a), the compound represented by formula (13 a) or the compound represented by formula (13 b) and the organolithium initiator are each independently selected from 1: (1.5-2.5).
In the second and third aspects of the present invention, the product of the first reaction or the product of the first contact may be directly fed to the next step (step 2) or step b)) to react with the compound represented by formula (11) or the compound represented by formula (12), or may be separated and purified and then fed to the next step to react. The step of separation and purification according to the present invention is not particularly limited, and those skilled in the art can use methods conventionally used in the art, such as recrystallization and column chromatography, for example.
In the second and third aspects of the present invention, preferably, in step 2) and step b), the molar ratio of the product of the first reaction or the product of the first contact to the compound represented by the formula (11), formula (12) is each independently selected from (0.8-1.2): (0.8-1.2):1.
In the second and third aspects of the present invention, preferably, in step 3) and step c), the molar ratio of the product of the second reaction or the product of the second contact to the amount of trimethylazidosilane is each independently selected from 1: (0.8-5), preferably 1: (0.8-3).
In the second and third aspects of the present invention, preferably, in step 4) and step d), the intermediate compound represented by the formula (14 a) or the intermediate compound represented by the formula (14 b) is mixed with MtX (n+1) The molar ratio of the amount of (2) is each independently selected from 1: (1-2).
In the second and third aspects of the present invention, preferably, the conditions of the first reaction and the first contact each independently include: the temperature is between minus 100 ℃ and minus 50 ℃ and the time is between 0.5 and 4 hours.
In the second and third aspects of the present invention, preferably, the conditions of the second reaction and the second contact each independently include: the temperature is between minus 100 ℃ and minus 50 ℃ and the time is between 2 and 16 hours.
In the second and third aspects of the present invention, preferably, the conditions of the third reaction and the third contact each independently include: the temperature is 80-120 ℃ and the time is 8-16h.
In the second and third aspects of the present invention, preferably, the conditions of the fourth reaction and the fourth contact each independently include: the temperature is 50-200deg.C, preferably 80-120deg.C; the reaction time is 2 to 30 hours, preferably 8 to 16 hours.
In the second and third aspects of the present invention, preferably, the first organic solvent and the second organic solvent are each independently selected from at least one of dehydrated ether, toluene, hexane, pentane, benzene, xylene, methylene chloride, chloroform, tetrachloromethane, and tetrahydrofuran.
In the second and third aspects of the present invention, preferably, the first organolithium initiator and the second organolithium initiator are each independently selected from at least one of n-butyllithium, sec-butyllithium, isobutyllithium, and tert-butyllithium.
More preferably, the first organolithium initiator and the second organolithium initiator are each independently selected from n-butyllithium and sec-butyllithium.
The steps of the foregoing process of the present invention may further comprise the necessary post-treatment steps, which may be performed by those skilled in the art using various steps conventionally used in the art to purify the crude product of each step. For example, the post-treatment step may include a solvent removal treatment, a washing treatment, a drying treatment, and the like.
As previously described, a fourth aspect of the present invention provides a pre-transition metal compound prepared by the methods described in the foregoing second and third aspects.
The structure and effect of the pre-transition metal compound provided in the fourth aspect of the present invention are consistent with those of the pre-transition metal compound provided in the aforementioned first aspect.
As previously described, the fifth aspect of the present invention provides the use of the pre-transition metal compound of the first or fourth aspect described above in an olefin polymerisation reaction.
The specific application of the compound in olefin polymerization is not particularly limited, for example, the pre-transition metal compound is compounded with an activator (e.g., aluminum-containing compound, organoboron compound, etc.) to obtain a catalyst for olefin polymerization, and the present invention is exemplified in the detailed examples section below as several specific application operations, and the person skilled in the art should not understand the limitation of the present invention.
In the present invention, unless otherwise specified, the pressures are all gauge pressures.
The invention will be described in detail below by way of examples.
In the following examples and comparative examples, various raw materials were used from commercial sources unless otherwise specified.
Organolithium initiator: 1.6M n-hexane solution of n-butyllithium (n-BuLi), available from Acros;
bithiophene was purchased from Acros corporation in a purity of 98% by weight; terthiophene was purchased from Acros corporation in 99% purity by weight;
diphenylphosphine chloride was purchased from Acros corporation in a purity of 98% by weight;
trimethylazidosilane was purchased from Acros corporation in 98% purity by weight;
MtX A/B converter (n+1) The compounds shown: titanium cyclopentadiene trichloride was purchased from Acros corporation in 99% by weight purity;
aluminum-containing compound: methylaluminoxane (MAO) was purchased from Albemarle company;
organoboron compound: triphenylcarbonium tetrakis (pentafluorophenyl) borate was purchased from Acros, with a purity of 98 wt%.
In the examples below, the properties referred to were tested as follows:
(1) Catalytic efficiency refers to the mass of polymer obtained per unit molar amount Mt expressed in units g polymer/mol metal h;
(2) Glass transition temperature Tg of copolymer: is measured by a DSC 822e differential scanning calorimeter of METTLEDO company, switzerland, test conditions: the temperature ranges from minus 100 ℃ to 150 ℃ and the temperature rising rate is as follows: 20 ℃/min; nitrogen atmosphere, 50mL/min;
(3) Melting temperature Tm of copolymer: obtained by testing with a DSC 822e differential scanning calorimeter from METTLEDO company, switzerland under the following conditions: the temperature ranges from minus 100 ℃ to 150 ℃ and the temperature rising rate is as follows: 20 ℃/min; and nitrogen atmosphere, 50mL/min.
Example 1
Preparation of Compounds of the Structure represented by formula (1A)
(1) Weighing 2.36g of bithiophene, dissolving in 100mL of anhydrous diethyl ether, dropwise adding n-BuLi (18.6 mL) of hexane solution at the temperature of minus 78 ℃ by using liquid nitrogen, reacting for 2 hours, and then heating to 25 ℃;
(2) Dissolving diphenyl phosphine chloride (28.4 mmol) in 20mL of toluene at the temperature of minus 78 ℃, slowly dropwise adding the solution obtained in the step (1), slowly heating the solution to 25 ℃, continuing to react for 12 hours, separating and purifying to obtain a ligand (5, 5'- [ di (diphenyl phosphino) ] -2,2' -bithiophene) shown in the formula (A1);
white solid 5.09g, 67% yield. 1H NMR (400 MHz, C) 6 D 6 )δ:7.46(ddd,J＝7.9,5.1,2.2Hz,8H,o-PPh 2 ) 7.10-6.99 (m, 14H, thiophene, m-PPh) 2 ,p-PPh 2 ) 6.75 (dd, J=3.6, 1.2Hz,2H, thiophene) ppm.13C NMR (101 MHz, C6D 6) delta: 143.70(s), 138.50(s), 138.23 (d, J=9.5 Hz), 137.61 (d, J=29.1 Hz), 133.35 (d, J=19.8 Hz), 129.00(s), 128.72 (d, J=6.9 Hz), 125.24 (d, J=8.1 Hz) ppm.31P NMR (162 MHz, C 6 D 6 ) Delta-5.38(s) ppm Anal calculated C 32 H 24 P 2 S 2 C,71.89; h,4.53. Found C,71.81; h,4.66.
(3) To trimethyl azidosilane N 3 SiMe 3 (0.015 mol) was slowly added to a solution of the ligand of formula (A1) in toluene (5 mmol of 5,5' - [ bis (diphenylphosphino))]-2,2' -bithiophene+20 mL toluene), the reaction mixture was taken upHeated to 100 ℃ and refluxed for 12 hours. Vacuum was applied to remove solvent and excess azido trimethylsilane TMSN 3 Obtaining a white crystalline solid to obtain an intermediate compound represented by formula (A2);
the yield was 95%.1H NMR (400 MHz, C) 6 D 6 )δ:7.84-7.72(m,8H,o-PPh 2 ) 7.12-6.96 (m, 14H, thiophene, m-PPh) 2 ,p-PPh 2 ) 6.75-6.70 (m, 2H, thiophene), 0.40 (s, 18H, -SiMe) 3 )ppm.13C NMR(101MHz,C 6 D 6 )δ:141.53(d,J＝6.1Hz),136.54(d,J＝104.3Hz),134.68(s),134.44(d,J＝8.9Hz),133.60(s),129.91(d,J＝10.9Hz),129.25(d,J＝2.9Hz),127.25(s),126.38(d,J＝12.6Hz),123.67(d,J＝12.2Hz),2.24(d,J＝3.5Hz)ppm.31P NMR(162MHz,C 6 D 6 ) Delta 3.23(s) ppm Anal calculated C 38 H 42 N 2 P 2 S 2 Si 2 C,64.37; h,5.97; n,3.95. Found C,64.91; h,5.44; n,4.37.
(4) Dissolving the prepared ligand (1 mmol) shown in the formula (A2) in 15mL of toluene, uniformly stirring, slowly dripping 5mL of toluene solution containing cyclopentadiene titanium trichloride (2 mmol), heating to 110 ℃, reacting for 12 hours, cooling to 25 ℃, separating to obtain 0.81g of yellow powder, and obtaining a compound with a structure shown in the formula (1A);
yield 87%;1H NMR (400 MHz, CD) 2 Cl 2 )δ:7.76(dd,J＝13.6,7.3Hz,8H,o-PPh 2 ),7.62-7.48(m,14H,m-PPh 2 ,p-PPh 2 Thiophene), 7.34 (dd, j=3.6, 2.0hz,2h, thiophene), 6.24 (s, 10h, cp) ppm.13c NMR (101 mhz, cd) 2 Cl 2 )δ:139.70(d,J＝8.9Hz),133.72(s),132.58(d,J＝11.2Hz),130.16(s),129.61(d,J＝13.2Hz),129.10(s),119.60(s),116.19(s)ppm.31P NMR(162MHz,CD 2 Cl 2 ) Delta-4.68(s) ppm Anal calculated C 42 H 34 Cl 4 N 2 P 2 S 2 Ti 2 C,54.22; h,3.68; n,3.01. Found C,53.89; h,3.97; n,3.27.
Example 2
Preparation of the Compound represented by formula (1B)
(1) Weighing 3.72g of tertiarythiophene, dissolving in 100mL of anhydrous diethyl ether, dropwise adding n-BuLi (20.6 mL) of hexane solution at the temperature of minus 78 ℃ by using liquid nitrogen, reacting for 2 hours, and then heating to the temperature of 25 ℃;
(2) Dissolving diphenyl phosphine chloride (30 mmol) in 20mL of toluene at the temperature of minus 78 ℃, slowly dripping the solution into the solution obtained in the step (1), slowly heating the solution to 25 ℃, continuing to react for 12 hours, separating and purifying to obtain ligand (5, 5 '-bis (diphenyl phosphino) -2,2':5', 2' -trithiophene) shown in the formula (B1);
pale yellow crystalline solid, 71% yield. 143-144 deg.c. 1H NMR (400 MHz, C) 6 D 6 )δ:7.49(td,J＝7.9,1.8Hz,8H,o-PPh 2 ) 7.13-7.01 (m, 14H, thiophene, m-PPh) 2 ,p-PPh 2 ) 6.87 (dd, J=3.6, 1.2Hz,2H, thiophene), 6.56 (s, 2H, thiophene) ppm.13C NMR (101 MHz, C) 6 D 6 )δ:143.77(s),138.22(d,J＝9.5Hz),137.94(s),137.62(d,J＝28.9Hz),136.35(s),133.39(d,J＝19.8Hz),129.05(s),128.76(d,J＝6.9Hz),125.11(s),124.81(d,J＝8.0Hz)ppm.31P NMR(162MHz,C 6 D 6 ) Delta-5.33(s) ppm Anal calculated C 36 H 26 P 2 S 3 C,70.11; h,4.25. Found C,71.01; h,4.56.
(3) To trimethyl azidosilane N 3 SiMe 3 (0.02 mol) was slowly added to a solution of 5,5 "-bis (diphenylphosphino) -2,2':5',2" -trithiophene in toluene (5 mmol of 5,5 "-bis (diphenylphosphino) -2,2':5',2" -trithiophene +20mL toluene) and the reaction mixture was heated to 100℃under reflux for 12h. Removing the solvent and excess azido trimethylsilane TMSN when evacuating 3 In this case, a white solid, namely, an intermediate compound (yellowish green solid) represented by the formula (B2) was obtained;
the yield was 95%;1H NMR (400 MHz, C) 6 D 6 )δ:7.74-7.66(m,8H,o-PPh 2 ) 7.05-7.01 (m, 2H, thiophene), 6.98-6.91 (m, 12H, m-PPh) 2 ,p-PPh 2 ) 6.70 (dd, j=3.7, 1.7hz,2H, thiophene), 6.49 (s, 2H, thiophene), 0.31 (s, 18H, -SiMe 3 )ppm.13C NMR(101MHz,C 6 D 6 )δ:142.09(d,J＝4.8Hz),135.78(d,J＝105.1Hz),134.76(s),134.42(d,J＝8.8Hz),133.68(s),129.95(d,J＝10.9Hz),129.25(d,J＝2.8Hz),127.25(s),126.40(d,J＝12.7Hz),123.81(s),122.79(d,J＝12.4Hz),2.28(d,J＝3.4Hz)ppm.31P NMR(162MHz,C 6 D 6 ) Delta 3.39(s) ppm Anal calculated C 42 H 44 N 2 P 2 S 3 Si 2 C,63.77; h,5.61; n,3.54. Found C,64.11; h,5.33; n,4.19.
(4) Dissolving the intermediate compound (1 mmol) shown in the formula (B2) prepared in the step (3) in 10mL of toluene, uniformly stirring, slowly dropwise adding 5mL of toluene solution containing cyclopentadiene titanium trichloride (2 mmol), heating to 110 ℃, reacting for 12h, and then cooling to 25 ℃ to obtain the compound shown in the formula (1B).
The yield thereof was found to be 88%.1H NMR (400 MHz, C) 6 D 6 )δ:7.74-7.66(m,8H,o-PPh 2 ) 7.05-7.01 (m, 2H, thiophene), 6.98-6.91 (m, 12H, m-PPh) 2 ,p-PPh 2 ) 6.70 (dd, j=3.7, 1.7hz,2H, thiophene), 6.49 (s, 2H, thiophene), 0.31 (s, 18H, -SiMe 3 )ppm.13C NMR(101MHz,C 6 D 6 )δ:142.09(d,J＝4.8Hz),135.78(d,J＝105.1Hz),134.76(s),134.42(d,J＝8.8Hz),133.68(s),129.95(d,J＝10.9Hz),129.25(d,J＝2.8Hz),127.25(s),126.40(d,J＝12.7Hz),123.81(s),122.79(d,J＝12.4Hz),2.28(d,J＝3.4Hz)ppm.31P NMR(162MHz,C 6 D 6 ) Delta 3.39(s) ppm Anal calculated C 42 H 44 N 2 P 2 S 3 Si 2 C,63.77; h,5.61; n,3.54. Found C,64.11; h,5.33; n,4.19.
Example 3
Preparation of the Compound represented by formula (2A)
In a similar manner to example 1, except that in step (4), titanium tetrachloride was used instead of titanium cyclopentadiene trichloride in example 1, in particular:
the ligand (1 mmol) of the formula (A2) prepared in example 1 was dissolved in 10mL of toluene, stirred uniformly, slowly added to 5mL of toluene solution containing titanium tetrachloride (2 mmol), heated to 100℃and reacted for 15 hours, and then cooled to 25 ℃.
Example 4
Preparation of the Compound represented by formula (2B)
In a similar manner to example 2, except that in step (4), the same moles of titanium tetrachloride were used instead of the titanium cyclopentadiene trichloride in example 2, the following is adopted:
the ligand (1 mmol) of the formula (B2) prepared in example 2 was dissolved in 10mL of toluene, stirred uniformly, slowly added to 5mL of toluene solution containing titanium tetrachloride (2 mmol), heated to 120℃and reacted for 10 hours, and then cooled to 25 ℃.
Other embodiments
The compound represented by formula (3A), the compound represented by formula (3B), the compound represented by formula (4A) and the compound represented by formula (4B) were produced by a method similar to example 1 or example 2, except that: the raw materials are different only, and the specific steps are as follows:
example 5: in a similar manner to example 1, except that in step (1), the same mole was used(Acros Co., purity 98 wt%) instead of the dithiophene in step (1), and in step (4), the same mol of zirconium tetrachloride was used instead of the titanium cyclopentadiene trichloride in example 1, to prepare a compound represented by formula (3A).
Example 6: in a similar manner to example 1, except that in step (1), the same mole was used(Acros Co., purity 98 wt%) instead of the dithiophene in step (1), and in step (4), the same mol of zirconium tetrachloride was used instead of the titanium cyclopentadiene trichloride in example 1, to prepare a compound represented by formula (3A).
Example 7: in a similar manner to example 1, except that in step (4), the same mol of hafnium tetrachloride was used instead of the titanium cyclopentadiene trichloride in example 1, the compound represented by formula (4A) was produced.
Example 8: in a similar manner to example 2, except that in step (4), the same mol of hafnium tetrachloride was used instead of the titanium cyclopentadiene trichloride in example 2, the compound represented by formula (4B) was produced.
Test examples are provided to illustrate the use of the compounds of the present invention to prepare catalysts for olefin polymerization.
Test example 1: ethylene homo-polymerization (MAO as activator)
To 150mL of toluene under the protection of nitrogen at 50℃was added 2mL of a toluene solution of MAO (available from Albemarle Co., ltd., hereinafter, the same applies; the amount of toluene solution of MAO was such that the content of Al was 10. Mu. Mol/mL) and continuously fed with ethylene monomer at a volume flow rate of 50L/h and keeping the gauge pressure at 0.6MPa, then the compound (0.03 mmol) represented by the formula (1A) was added to polymerize for 15 minutes, and the supply of ethylene monomer was stopped. The reaction was terminated with isopropanol, and the resulting polymer was freed from the solvent and oven dried.
The results are shown in Table 1.
Test example 1-1
The procedure of test example 1 was followed except that the reaction was carried out at 120 ℃. The results are shown in Table 1.
Test example 2: ethylene homo-polymerization (MAO and organoboron compound as activator)
Under the protection of nitrogen and at 50 ℃, 0.5mL of a toluene solution of MAO (from Albemarle, the same applies below; the amount of toluene solution of MAO is such that the Al content is 10. Mu. Mol/mL) was added to 150mL of toluene under the protection of nitrogen and continuously fed with ethylene monomer at a volume flow rate of 50L/h and with a gauge pressure of 0.6MPa, and [ CPh 3 ][B(C 6 F 5 ) 4 ]Compound cocatalyst B/ti=2/1 (molar ratio) (dissolved in toluene solution), then compound (0.02 mmol) represented by formula (1B) was added and polymerized for 15min, stopping the supply of monomer. The reaction was terminated with isopropanol, and the resulting polymer was freed from the solvent and oven dried.
The results are shown in Table 1.
Test example 2-1
The procedure of test example 2 was followed except that the reaction was carried out at 120 ℃. The results are shown in Table 1.
Test example 3: ethylene homo-polymerization (MAO and organoboron compound as activator)
Under the protection of nitrogen and at 50 ℃, 0.5mL of a toluene solution of MAO (from Albemarle, the same applies below; the amount of toluene solution of MAO is such that the Al content is 10. Mu. Mol/mL) was added to 150mL of toluene under the protection of nitrogen and continuously fed with ethylene monomer at a volume flow rate of 50L/h and with a gauge pressure of 0.6MPa, and [ CPh 3 ][B(C 6 F 5 ) 4 ]Compound cocatalyst B/ti=1/1 (molar ratio) (dissolved in toluene solution), then the compound (0.02 mmol) represented by formula (2A) was added and polymerized for 15min, stopping the supply of monomer. CollectingThe reaction was stopped with isopropanol and the resulting polymer was freed from solvent and oven dried.
The results are shown in Table 1.
Test example 4: ethylene-propylene copolymerization (MAO as activator)
To 150mL of toluene under the protection of nitrogen at 50℃was added 2mL of a toluene solution of MAO (available from Albemarle Co., hereinafter, the same applies; the amount of toluene solution of MAO was such that the Al content was 10. Mu. Mol/mL) and an ethylene/propylene/hydrogen mixture (molar ratio: 1:1.5:0.05, volume flow: 50L/h) was continuously fed and the gauge pressure was maintained at 0.6MPa, followed by addition of the compound (0.03 mmol) represented by the formula (1A) and polymerization was stopped for 15 minutes, and the supply of the monomer was stopped. The reaction was stopped with isopropanol and an anti-aging agent such as lrganox 1520 (in an amount such that the content of anti-aging agent in the polymer was 0.2% by weight, available from BASF company, below). The resulting polymer was freed from the solvent and oven dried.
The results are shown in Table 1.
Test example 4-1
The procedure of test example 4 was followed except that the reaction was carried out at 120 ℃. The results are shown in Table 1.
Test example 5: ethylene-propylene copolymerization (MAO as activator)
This test example was conducted in a similar manner to test example 4, except that the compound represented by formula (1A) in test example 4 was replaced with an equal molar amount of the compound represented by formula (2A).
The remainder was the same as in test example 1.
The results are shown in Table 1.
Test example 6: ethylene-propylene copolymerization (MAO and organoboron Compound as activator)
To 150mL of toluene under nitrogen at 70℃was added 0.5mL of a toluene solution of MAO (available from Albemarle, the same applies below; the amount of toluene solution of MAO was such that the Al content was 10. Mu. Mol/mL) and an ethylene/propylene/hydrogen mixture (molar ratio: 1:1.5:0.01, volume flow: 50L/h) was continuously fed in while maintaining a gauge pressure of 0.6MPa, and [ CPh 3 ][B(C 6 F 5 ) 4 ]Compound cocatalyst B/ti=1/1 (molar ratio) (dissolved in toluene solution), then compound (0.02 mmol) represented by formula (2B) was added and polymerized for 15min, stopping the supply of monomer. The reaction is stopped with isopropanol and an anti-ageing agent such as lrganox 1520 is added (in an amount such that the content of anti-ageing agent in the polymer is 0.2 wt%). The resulting polymer was freed from the solvent and oven dried.
The results are shown in Table 1.
Test example 7
This test example was conducted in a similar manner to test example 3, except that the compound represented by formula (2A) in test example 3 was replaced with an equal molar amount of the compound represented by formula (3A).
The remainder was the same as in test example 3.
The results are shown in Table 1.
Test example 8
This test example was conducted in a similar manner to test example 3, except that the compound represented by formula (2A) in test example 3 was replaced with an equal molar amount of the compound represented by formula (3B).
The remainder was the same as in test example 3.
The results are shown in Table 1.
Test example 9
This test example was conducted in a similar manner to test example 3, except that the compound represented by formula (2A) in test example 3 was replaced with an equal molar amount of the compound represented by formula (4A).
The remainder was the same as in test example 3.
The results are shown in Table 1.
Test example 10
This test example was conducted in a similar manner to test example 3, except that the compound represented by formula (2A) in test example 3 was replaced with an equal molar amount of the compound represented by formula (4B).
The remainder was the same as in test example 3.
The results are shown in Table 1.
Comparative test example 1
This comparative example was conducted in a similar manner to test example 1 except that the compound represented by the formula (1A) in test example 1 was replaced with an equivalent molar amount of the complex disclosed in example 18 of U.S. Pat. No. 3,262B 1 (hereinafter referred to as: complex 18).
The remainder was the same as in test example 1.
The results are shown in Table 1.
Comparative test example 2
This comparative example was conducted in a similar manner to test example 3 except that the compound represented by the formula (2A) in test example 3 was replaced with an equivalent molar amount of the complex 18 (the complex disclosed in example 18 of US6239237B 1).
The remainder was the same as in test example 3.
The results are shown in Table 1.
Comparative test example 3
Preparation of ligand of formula (D1), 2- (Ph) 2 P=ntms) thiophene
To trimethyl azidosilane N 3 SiMe 3 (0.02 mol) was slowly added to a solution of 2- (diphenylphosphino) thiophene (0.01 mol) and 20mL of toluene, and the reaction mixture was heated at reflux for 12h. Removing the solvent and excess TMSN when evacuating 3 In this case, a white solid, namely, a ligand represented by (D1) was obtained.
The yield thereof was found to be 92%; 1 H NMR(400MHz,C 6 D 6 )δ:7.70(m,4H,o-PPh 2 ),7.17(m,1H,pt),6.98(s,7H,m-PPh 2 ,p-PPh 2 ,pt),6.60(s,1H,pt),0.33(s,9H,-SiMe 3 ).
preparation of the Compound represented by formula (1D)
The ligand (5 mmol) represented by the formula (D1) was dissolved in 10mL of toluene, stirred well, and 5mL of toluene solution containing cyclopentadiene titanium trichloride (5 mmol) was added, heated to 110℃and reacted for 12 hours, followed by cooling to 25 ℃.
The yield thereof was found to be 92%; 1 H NMR(400MHz,C 6 D 6 )δ:7.66(m,4H,o-PPh 2 ),7.36(m,1H,tp),6.92–6.79(m,7H,m-PPh 2 ,p-PPh 2 ,tp),6.45(m,1H,tp),6.15(s,5H,Cp).
ethylene-propylene copolymerization (MAO as activator)
To 150mL of toluene under the protection of nitrogen at 50℃was added 2mL of a toluene solution of MAO (available from Albemarle Co., hereinafter, the same applies; the amount of toluene solution of MAO was such that the Al content was 10. Mu. Mol/mL) and an ethylene/propylene/hydrogen mixture (molar ratio: 1:1.5:0.05, volume flow: 50L/h) was continuously fed and the gauge pressure was maintained at 0.6MPa, followed by addition of the compound (0.06 mmol) represented by the formula (1D) and polymerization was stopped for 15 minutes, and the supply of the monomer was stopped. The reaction was stopped with isopropanol and an anti-aging agent such as lrganox 1520 (in an amount such that the content of anti-aging agent in the polymer was 0.2% by weight, available from BASF company) was added. The resulting polymer was freed from the solvent and oven dried.
The results are shown in Table 1.
Comparative test example 3-1
The procedure of comparative test example 3 was followed except that the ethylene propylene copolymerization was carried out at 120℃and the results are shown in Table 1.
TABLE 1
From the above results, it can be seen that the use of the pre-transition metal compound provided by the present invention can obtain an ethylene homopolymer and an ethylene- α -olefin copolymer elastomer (ethylene-propylene copolymer elastomer) with a higher catalytic activity in a wider range, i.e., under flexible operating conditions (low pressure, wide temperature range), and in particular, the complex provided by the present invention has a higher catalytic activity even at a lower reaction pressure than an industrial apparatus, and the complex provided by the present invention has a higher catalytic activity even at a higher reaction temperature, e.g., 120 ℃.
Meanwhile, when the compound is used for olefin polymerization reaction, the obtained polymer has a melting point (Tm) of about 135 ℃, which indicates that the pre-transition metal compound provided by the invention can be used for obtaining high-density polyethylene and ethylene-alpha olefin copolymer elastomer.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A transition metal compound characterized by having a structure represented by the formula (1) or the formula (2),
(1),
(2),
wherein in the formulas (1) and (2),
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently selected from the group consisting of H, C 1-20 C is a hydrocarbon group of (C) 1-20 A group consisting of alkoxy and halogen;
R 1 、R 2 、R 3 and R is 4 Each independently selected from the group consisting of H, C 1-10 C is a hydrocarbon group of (C) 6-12 Aryl and C 1-4 Is substituted with hydrocarbyl group of C 7-16 A group selected from the group consisting of aryl groups;
mt is a group IVB metal element;
x is an atom or group bonded to the Mt element, each X is independently selected from the group consisting of C 1-10 Of the group consisting of hydrocarbyl groups and halogenAt least one group; n is an integer to satisfy the valence of X to Mt bond.
2. The compound according to claim 1, wherein, in the formula (1) and the formula (2),
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently selected from the group consisting of H, C 1-16 C is a hydrocarbon group of (C) 1-16 A group consisting of alkoxy and halogen;
R 1 、R 2 、R 3 and R is 4 Each independently selected from the group consisting of H, C 1-8 C is a hydrocarbon group of (C) 6-10 Aryl and C 1-4 Is substituted with hydrocarbyl group of C 7-14 A group selected from the group consisting of aryl groups;
mt is Ti, zr or Hf;
each X is independently selected from C 1-8 At least one group selected from the group consisting of hydrocarbon groups, fluorine, chlorine, bromine and iodine.
3. The compound according to claim 1, wherein, in the formula (1) and the formula (2),
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently selected from the group consisting of H, C 1-10 C is a hydrocarbon group of (C) 1-10 A group consisting of alkoxy and halogen;
R 1 、R 2 、R 3 and R is 4 Each independently selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, phenyl, naphthyl, and C substituted with at least one substituent selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl 7-14 A group selected from the group consisting of aryl groups;
mt is Ti, zr or Hf;
each X is independently selected from at least one of the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopentadiene, fluorine, chlorine, bromine, and iodine.
4. The compound according to claim 1, wherein, in the formula (1) and the formula (2),
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently selected from the group consisting of H, C 1-6 C is a hydrocarbon group of (C) 1-6 A group consisting of alkoxy and halogen;
R 1 、R 2 、R 3 and R is 4 Each independently selected from the group consisting of phenyl, naphthyl and C substituted with at least one substituent selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl 7-14 A group selected from the group consisting of aryl groups;
mt is Ti, zr or Hf;
n X are each halogen, or one of n X is cyclopentadiene and the remaining (n-1) X are halogen.
5. The compound according to any one of claims 1 to 4, wherein the compound of the structures represented by formula (1) and formula (2) is selected from at least one of the following compounds;
formula (1A); />Formula (1B);
formula (2A); />Formula (2B);
formula (3A); />(3B)）；
Formula (4A); />Formula (4B).
6. A process for producing a pre-transition metal compound, characterized in that the pre-transition metal compound has a structure represented by the formula (1),
(1),
(13 a),
(14 a),
(11),>(12),
the method comprises the following steps:
1) Subjecting a compound represented by the formula (13 a) to a first reaction in the presence of a first organolithium initiator in the presence of a first organic solvent;
2) Carrying out a second reaction on the product of the first reaction, a compound shown in a formula (11) and a compound shown in a formula (12);
3) Carrying out a third reaction on the product obtained by the second reaction and trimethyl azidosilane to obtain an intermediate compound shown in a formula (14 a);
4) Will beThe intermediate compound shown in the formula (14 a) and MtX (n+1) Carrying out a fourth reaction;
wherein the definition of the substituents in formula (1), formula (11), formula (12), formula (13 a) and formula (14 a) is correspondingly the same as the definition as defined in any one of claims 1 to 5;
in the formula (13 a), X 1 And X 2 Each independently selected from H and halogen;
in the formula (11) and the formula (12), X 3 And X 4 Each independently selected from H and halogen.
7. A process for producing a pre-transition metal compound having a structure represented by the formula (2),
(2),
formula (13 b),
(14 b),
(11),>(12),
the method comprises the following steps:
a) First contacting a compound represented by formula (13 b) in the presence of a second organolithium initiator in the presence of a second organic solvent;
b) Subjecting the product of the first contact to a second contact with a compound represented by formula (11) and a compound represented by formula (12);
c) Carrying out third contact on the product of the second contact and trimethyl azidosilane to obtain an intermediate compound shown in a formula (14 b);
d) Combining the intermediate compound represented by the formula (14 b) with MtX (n+1) Performing a fourth contact;
wherein the definition of the substituents in formula (2), formula (11), formula (12), formula (13 b) and formula (14 b) is correspondingly the same as the definition as defined in any one of claims 1 to 5;
in formula (13 b), X 1 And X 2 Each independently selected from H and halogen;
in the formula (11) and the formula (12), X 3 And X 4 Each independently selected from H and halogen.
8. The method according to claim 6 or 7, wherein the first organic solvent and the second organic solvent are each independently selected from at least one of anhydrous diethyl ether, toluene, hexane, pentane, benzene, xylene, dichloromethane, chloroform, tetrachloromethane, and tetrahydrofuran;
the first organolithium initiator and the second organolithium initiator are each independently selected from at least one of n-butyllithium, sec-butyllithium, isobutyllithium, and tert-butyllithium.
9. The method of claim 6 or 7, wherein the conditions of the first reaction and the first contact each independently comprise: the temperature is 100 ℃ below zero to 50 ℃ below zero for 0.5-4h;
the conditions of the second reaction and the second contact each independently include: the temperature is 100 ℃ below zero to 50 ℃ above zero for 2-16h;
the conditions of the third reaction and the third contact each independently include: the temperature is 80-120 ℃ and the time is 8-16h;
the conditions of the fourth reaction and the fourth contact each independently comprise: the temperature is 50-200 ℃, and the reaction time is 2-30h.
10. Use of the pre-transition metal compound according to any one of claims 1 to 5 in olefin polymerization.
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