CN110386955B - Early transition metal compound, preparation method and intermediate thereof, and application in olefin polymerization - Google Patents
Early transition metal compound, preparation method and intermediate thereof, and application in olefin polymerization Download PDFInfo
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- CN110386955B CN110386955B CN201810361321.2A CN201810361321A CN110386955B CN 110386955 B CN110386955 B CN 110386955B CN 201810361321 A CN201810361321 A CN 201810361321A CN 110386955 B CN110386955 B CN 110386955B
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- butyl
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 63
- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 63
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 216
- 239000013078 crystal Substances 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 128
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 86
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 57
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 54
- 239000000460 chlorine Substances 0.000 claims description 49
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 48
- 238000006467 substitution reaction Methods 0.000 claims description 48
- 229910052801 chlorine Inorganic materials 0.000 claims description 44
- 150000002430 hydrocarbons Chemical group 0.000 claims description 43
- 229910052735 hafnium Inorganic materials 0.000 claims description 41
- 229910052719 titanium Inorganic materials 0.000 claims description 41
- 229910052726 zirconium Inorganic materials 0.000 claims description 41
- 229910052794 bromium Inorganic materials 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 37
- 229910052736 halogen Inorganic materials 0.000 claims description 35
- 150000002367 halogens Chemical class 0.000 claims description 35
- -1 methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy Chemical group 0.000 claims description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 25
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 239000005977 Ethylene Substances 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 19
- 229930195733 hydrocarbon Natural products 0.000 claims description 19
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 18
- 125000001624 naphthyl group Chemical group 0.000 claims description 18
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 239000012190 activator Substances 0.000 claims description 16
- 239000003446 ligand Substances 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 239000004711 α-olefin Substances 0.000 claims description 13
- 239000007818 Grignard reagent Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 12
- 150000004795 grignard reagents Chemical class 0.000 claims description 12
- 125000001979 organolithium group Chemical group 0.000 claims description 12
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 9
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 239000011630 iodine Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 238000003800 Staudinger reaction Methods 0.000 claims description 7
- 125000001246 bromo group Chemical group Br* 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 125000002346 iodo group Chemical group I* 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 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 claims description 4
- 230000000536 complexating effect Effects 0.000 claims description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- NMVXHZSPDTXJSJ-UHFFFAOYSA-L 2-methylpropylaluminum(2+);dichloride Chemical compound CC(C)C[Al](Cl)Cl NMVXHZSPDTXJSJ-UHFFFAOYSA-L 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 2
- DFGSACBYSGUJDZ-UHFFFAOYSA-M chloro(dihexyl)alumane Chemical compound [Cl-].CCCCCC[Al+]CCCCCC DFGSACBYSGUJDZ-UHFFFAOYSA-M 0.000 claims description 2
- RFUDQCRVCDXBGK-UHFFFAOYSA-L dichloro(propyl)alumane Chemical compound [Cl-].[Cl-].CCC[Al+2] RFUDQCRVCDXBGK-UHFFFAOYSA-L 0.000 claims description 2
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- CPDVHGLWIFENDJ-UHFFFAOYSA-N dihexylalumane Chemical compound C(CCCCC)[AlH]CCCCCC CPDVHGLWIFENDJ-UHFFFAOYSA-N 0.000 claims description 2
- TUTOKIOKAWTABR-UHFFFAOYSA-N dimethylalumane Chemical compound C[AlH]C TUTOKIOKAWTABR-UHFFFAOYSA-N 0.000 claims description 2
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 2
- XOCWTYIVWYOSGQ-UHFFFAOYSA-N dipropylalumane Chemical compound C(CC)[AlH]CCC XOCWTYIVWYOSGQ-UHFFFAOYSA-N 0.000 claims description 2
- ZMXPNWBFRPIZFV-UHFFFAOYSA-M dipropylalumanylium;chloride Chemical compound [Cl-].CCC[Al+]CCC ZMXPNWBFRPIZFV-UHFFFAOYSA-M 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 claims description 2
- VMLUVDHAXSZZSR-UHFFFAOYSA-L hexylaluminum(2+);dichloride Chemical compound CCCCCC[Al](Cl)Cl VMLUVDHAXSZZSR-UHFFFAOYSA-L 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
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 claims description 2
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 claims description 2
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 claims description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 2
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 claims description 2
- LZJHACNNMBYMSO-UHFFFAOYSA-N 1,1-dimethyl-3-propylurea Chemical compound CCCNC(=O)N(C)C LZJHACNNMBYMSO-UHFFFAOYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 78
- 239000010936 titanium Substances 0.000 description 35
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 29
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 10
- RQNAPXJOFAMGPJ-UHFFFAOYSA-N xanthene Chemical compound C1=CC=C2[CH]C3=CC=CC=C3OC2=C1 RQNAPXJOFAMGPJ-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000002390 rotary evaporation Methods 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 150000001555 benzenes Chemical group 0.000 description 5
- 229950005499 carbon tetrachloride Drugs 0.000 description 5
- 229960001701 chloroform Drugs 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- HWEQKSVYKBUIIK-UHFFFAOYSA-N cyclobuta-1,3-diene Chemical class C1=CC=C1 HWEQKSVYKBUIIK-UHFFFAOYSA-N 0.000 description 5
- CHVJITGCYZJHLR-UHFFFAOYSA-N cyclohepta-1,3,5-triene Chemical class C1C=CC=CC=C1 CHVJITGCYZJHLR-UHFFFAOYSA-N 0.000 description 5
- 150000004306 cyclooctatetraenes Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SEDZOYHHAIAQIW-UHFFFAOYSA-N trimethylsilyl azide Chemical compound C[Si](C)(C)N=[N+]=[N-] SEDZOYHHAIAQIW-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MTVNAPYHLASOSX-UHFFFAOYSA-N 9,9-dimethylxanthene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3OC2=C1 MTVNAPYHLASOSX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- 239000002685 polymerization catalyst Substances 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
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- FEYDZHNIIMENOB-UHFFFAOYSA-N 2,6-dibromopyridine Chemical compound BrC1=CC=CC(Br)=N1 FEYDZHNIIMENOB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- RMDKEBZUCHXUER-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C)C2 RMDKEBZUCHXUER-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DONDZHOLANRXGJ-UHFFFAOYSA-N P.P.C1=CC=NC=C1 Chemical compound P.P.C1=CC=NC=C1 DONDZHOLANRXGJ-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- NDVFUVDXDDUZCH-UHFFFAOYSA-N [SiH4].[N-]=[N+]=[N-] Chemical compound [SiH4].[N-]=[N+]=[N-] NDVFUVDXDDUZCH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical class C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- VGGNVBNNVSIGKG-UHFFFAOYSA-N n,n,2-trimethylaziridine-1-carboxamide Chemical compound CC1CN1C(=O)N(C)C VGGNVBNNVSIGKG-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
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- 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
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
- C07F9/65522—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring condensed with carbocyclic rings or carbocyclic ring systems
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- C—CHEMISTRY; METALLURGY
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
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- C07—ORGANIC CHEMISTRY
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Abstract
The invention relates to the field of catalysts for olefin polymerization, in particular to an early transition metal compound, a preparation method and an intermediate thereof, and application of the early transition metal compound in olefin polymerization. The early transition metal compound is a compound represented by the formula (1). The olefin catalyzed by the early transition metal compound or the crystal thereof has high catalytic activity and excellent catalytic activity under wide polymerization reaction conditions, and the catalyst has low cost and is beneficial to industrial production.
Description
Technical Field
The invention relates to the field of catalysts for olefin polymerization, in particular to an early transition metal compound, a preparation method and an intermediate thereof, and application of the early transition metal compound in olefin polymerization.
Background
Polyolefins are a widely used and very important class of polymeric materials, including homopolymers and copolymers of ethylene, alpha olefins. Polyolefins are important in the synthetic resin industry and are useful as films, pipes, wires and cables.
Advances in olefin polymerization catalyst technology are a direct driving force for advances in the polyolefin industry. The catalytic polymerization of olefins has been the focus of attention by researchers and manufacturers, from traditional Ziegler-Natta catalysts to single-site metallocene catalysts that appeared in the end of the 80 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 residual catalyst content in a polymerization product obtained by solution polymerization. The discovery of group IV metallocene catalysts has better solved this problem by having a single site of activity, allowing one to obtain polymers of the desired structure by altering the structure of the catalyst as required (W.Kaminsky et al, adv.Organomet.Chem.1980, 18, 99; H.H.Brintzingger et al, Angew.Chem.int.Ed.Engl.1995, 34, 1143). In recent decades, a metal complex obtained by coordinating cyclopentadiene with a transition metal with a ligand containing a coordinating atom such as N, O, P has been actively studied as an olefin polymerization catalyst, and such a catalyst is collectively referred to as a "post-metallocene" catalyst.
Late transition metal (Fe, Co, Ni, Pd, etc.) catalysts can catalyze ethylene polymerization to obtain various polyethylene products, such as polyethylene with a highly linear to highly branched structure, polyethylene with a monomodal distribution to a broad or bimodal distribution, and copolymers of ethylene and polar monomers, polyolefin block copolymers, etc.
US006133387A discloses the use of late transition metals Fe, Co, Ni, Pd containing pyridine bisphosphine for the copolymerization of olefins, the structure of which is shown below, but the activity of the complex to catalyze ethylene polymerization is only high under specific reaction conditions (e.g. high pressure), and thus the wide application of the catalyst is not facilitated:
disclosure of Invention
The invention aims to provide a novel early transition metal compound, a preparation method and an intermediate thereof and application in olefin polymerization.
In order to achieve the above object, one aspect of the present invention provides an early transition metal compound, which is a compound represented by formula (1):
wherein R is1、R2、R3And R4Each independently selected from H, C1-20A hydrocarbon group of1-20Alkoxy and halogen of (a);
R1and R2Each independently selected from H, C1-4And substituted or unsubstituted C6-16Aryl of (a), the substituted C6-16The substituents on the aryl group of (A) are selected from C1-4A hydrocarbon group of (a);
R3is-MtXnor-Mt (X') XnWherein, in the step (A),
mt is a group IVB metal element;
n X are each independentlyIs selected from C1-10And halogen, and n ═ n '-1, n' is the valence of element Mt; x' is a ligand of the metal element Mt.
The second aspect of the present invention provides an intermediate of the above-mentioned early transition metal compound, wherein the intermediate of the early transition metal compound is a compound represented by formula (2):
each R is4Each independently selected from C1-20And C is a hydrocarbon group1-20Alkoxy group of (2).
The third aspect of the present invention provides the crystal of the aforementioned early transition metal compound, wherein the crystal system of the crystal is an orthorhombic system.
The fourth aspect of the present invention provides a method for producing an early transition metal compound, the method comprising:
(1) carrying out a first substitution reaction on a compound shown as a formula (4) and an organic lithium reagent;
(2) carrying out a second substitution reaction on the product of the first substitution reaction and the compound shown in the formula (a) to obtain a compound shown in a formula (3);
(3) carrying out a Staudinger reaction on a compound shown in a formula (3) and an azidosilane compound shown in a formula (b) to obtain a compound shown in a formula (2);
(4) carrying out a third substitution reaction on the compound shown in the formula (2) and the compound shown in the formula (c) to obtain a compound shown in the formula (1);
optionally, in the case that at least one of n X in the compound represented by formula (1) obtained in step (4) is halogen, the method further comprises: (5) performing a fourth substitution reaction on the compound shown in the formula (1) and a Grignard reagent or alkyl lithium, wherein the Grignard reagent is the compound shown in the formula (d), and the alkyl lithium is the compound shown in the formula (d');
Formula (d) R5-MgX '", formula (d') R5-Li,
Wherein R is1、R2、R3And R4Each independently selected from H, C1-20A hydrocarbon group of1-20Alkoxy and halogen of (a);
R1and R2Each independently selected from H, C1-4And substituted or unsubstituted C6-16Aryl of (a), the substituted C6-16The substituents on the aryl group of (A) are selected from C1-4A hydrocarbon group of (a);
each R is4Each independently selected from C1-20And C is a hydrocarbon group1-20Alkoxy group of (a);
R3is-MtXnor-Mt (X') XnWherein, in the step (A),
mt is a group IVB metal element;
n X are each independently selected from C1-10And halogen, and n ═ n '-1, n' is the valence of element Mt; x' is a ligand of a metal element Mt;
R5is selected from C1-10A hydrocarbon group of (a);
x "and X'" are each independently selected from halogen.
The fifth aspect of the present invention provides an early transition metal compound obtained by the above-mentioned method.
In a sixth aspect, the present invention provides use of the above-mentioned early transition metal compound or the above-mentioned crystal of the early transition metal compound for catalyzing ethylene homopolymerization and/or ethylene- α -olefin copolymerization.
In a seventh aspect, the present invention provides a catalyst composition suitable for the polymerisation of olefins, the composition comprising a procatalyst which is a compound of the aforementioned early transition metal or a crystal of a compound of the aforementioned early transition metal and an activator comprising one or more of an aluminium-containing compound and optionally an organoboron compound.
The eighth aspect of the present invention provides the use of the above composition in the catalysis of ethylene homopolymerization and/or ethylene-alpha olefin copolymerization.
The ninth aspect of the present invention provides a process for producing an olefin polymer, which comprises: in an organic solvent, in the presence of a catalyst, carrying out a polymerization reaction on an olefin monomer;
wherein the catalyst is the composition.
The olefin polymerization catalyzed by the early transition metal compound or the crystal thereof shows high catalytic activity, has excellent catalytic activity under wide polymerization reaction conditions, and is low in cost and beneficial to industrial production.
Drawings
FIG. 1 shows a complex structure diagram (ORTEP diagram) and corresponding atom numbers of a single crystal of a compound represented by the formula (1-Ti-1) confirmed by single crystal diffraction analysis.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In one aspect of the present invention, there is provided an early transition metal compound, which is a compound represented by formula (1):
wherein R is1、R2、R3And R4Each independently selected from H, C1-20A hydrocarbon group of1-20Alkoxy and halogen of (a);
R1and R2Each independently selected fromH、C1-4And substituted or unsubstituted C6-12Aryl of (a), the substituted C6-12The substituents on the aryl group of (A) are selected from C1-4A hydrocarbon group of (a);
R3is-MtXnor-Mt (X') XnWherein, in the step (A),
mt is a group IVB metal element;
n X are each independently selected from C1-10And halogen, and n ═ n '-1, n' is the valence of element Mt; x' is a ligand of the metal element Mt.
In the present invention, said C1-20The hydrocarbon group (C) is a hydrocarbon group having 1 to 20 carbon atoms in total, and may be a linear or branched alkyl group, or a linear or branched alkenyl group having an unsaturated carbon-carbon double bond, and may be, for example, C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19Or C20A hydrocarbon group of (1). For example, the C1-20The hydrocarbon group of (A) may be C1-20Alkyl or C2-20Alkenyl groups of (a). For C1-16A hydrocarbon group of1-10A hydrocarbon group of1-8A hydrocarbon group of1-6The hydrocarbon group of (1) can also be explained by the above definition, and the number of carbon atoms is different, but as long as the specific hydrocarbon group within the range of the number of carbon atoms can be selected from the suitable hydrocarbon groups of the number of carbon atoms specifically enumerated above.
Said C is1-20The alkoxy group (C) means an alkoxy group having 1 to 20 carbon atoms in total, and may be, for example, C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19Or C20Alkoxy group of (2). For C1-16Alkoxy group of (C)1-10Alkoxy group of (C)1-8Alkoxy group of (C)1-6The alkoxy group (b) may be defined as above, and the number of carbon atoms may be different, but as long as the specific alkoxy group within the range of the number of carbon atoms is selected from the suitable alkoxy groups having the number of carbon atoms specifically listed above.
Said C is1-4The hydrocarbon group (C) means a hydrocarbon group having 1 to 4 carbon atoms in total, and may be, for example, C1、C2、C3Or C4A hydrocarbon group of (1). For example, may be C1-4Alkyl or C2-4Specific examples of the alkenyl group in (b) include methyl (which may be represented by Me), ethyl (which may be represented by Et), n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, allyl, and propenyl.
Said unsubstituted C6-16The aryl group of (2) means an aryl group having 6 to 16 carbon atoms in total, and may be a heteroaryl group or a non-heteroaryl group, and may be, for example, a phenyl group (may be represented by Ph), a naphthyl group, a biphenyl group, an anthryl group or a phenanthryl group.
Said substituted C6-16Aryl means that the number of carbon atoms of the aromatic ring, excluding the substituents, is always from 6 to 16, and may be heteroaryl or non-heteroaryl, the substituted aryl having at least one aromatic ring H substituted by C1-4May be substituted, for example, by C1-4Phenyl substituted by hydrocarbon radicals of (A), C1-4Alkyl-substituted naphthyl, by C1-4Biphenyl substituted by hydrocarbon radicals of (A), C1-4Or alkyl-substituted anthracenyl or by C1-4The hydrocarbyl-substituted phenanthryl of (1).
The group IVB metal element may be Ti, Zr or Hf.
The halogen may be fluorine, chlorine, bromine or iodine.
In the present invention, the groups represented by the same symbols may be independently selected within the defined ranges, and may be the same or different, for example, although in the formula (1), the substituents at two positions are both represented by R1Denotes, however, R at these two positions1May be the same or different and are each at R1Is independently selected from the definitions of (a). For example, n X's may be the same or different and each is independent of the otherGround is chosen within the definition of X.
Wherein n may be 2, 3 or 4.
X 'is a ligand of the metal element Mt, such ligand may be a pi-ligand, for example X' may be a substituted or unsubstituted 1, 3-cyclobutadiene, a substituted or unsubstituted cyclopentadiene, a substituted or unsubstituted indene, a substituted or unsubstituted fluorene, a substituted or unsubstituted benzene ring, a substituted or unsubstituted 1,3, 5-cycloheptatriene or a substituted or unsubstituted cyclooctatetraene; wherein, for example, the substituent on these ligands may be C1-6And halogen, and the like.
In a preferred embodiment of the invention, R1、R2、R3And R4Each independently selected from H, C1-16A hydrocarbon group of1-16Alkoxy and halogen of (a);
mt is Ti, Zr or Hf;
n X are each independently selected from C1-8A hydrocarbon group of (a), fluorine, chlorine, bromine and iodine.
In another preferred embodiment of the invention, R1、R2、R3And R4Each independently selected from H, C1-10A hydrocarbon group of1-10Alkoxy and halogen of (a);
R1and R2Each independently selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;
mt is Ti, Zr or Hf;
n X are each independently selected from methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, and iodo; x' is substituted or unsubstituted 1, 3-cyclobutanediene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, substituted or unsubstituted fluorene, substituted or unsubstituted benzene ring, substituted or unsubstituted 1,3, 5-cycloheptatriene or substituted or unsubstituted cyclooctatetraene.
In a more preferred embodiment of the invention, R1、R2、R3And R4Each independently selected from H, C1-6A hydrocarbon group of1-6Alkoxy and halogen of (a);
R1and R2Each independently selected from substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;
mt is Ti, Zr or Hf;
n X are each independently selected from methyl, ethyl, fluoro, chloro, bromo and iodo; x' is substituted or unsubstituted 1, 3-cyclobutanediene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, substituted or unsubstituted fluorene, substituted or unsubstituted benzene ring, substituted or unsubstituted 1,3, 5-cycloheptatriene or substituted or unsubstituted cyclooctatetraene.
According to the invention, the early transition metal compound is preferably one of the compounds of the formula:
formula (1-Ti-1): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Ti, n X are Cl, n is 2, and X' is cyclopentadiene;
formula (1-Ti-2): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-MtXnMt is Ti, n X are Cl, and n is 3;
formula (1-Ti-3): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-Mt (X') XnWherein Mt is Ti, n X are methyl, n is 2, and X' is cyclopentadiene;
formula (1-Ti-4): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Ti, n X are Br, n is 2, and X' is cyclopentadiene;
formula (1-Ti-5): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-MtXnMt is Ti, n X are Br, and n is 3;
formula (1-Ti-6): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Ti, n X are all ethyl, n is 2, and X' is cyclopentadiene;
formula (1-Ti-7): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Ti, n X are Cl, n is 2, and X' is cyclopentadiene;
formula (1-Ti-8): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-MtXnMt is Ti, n X are Cl, and n is 3;
formula (1-Ti-9): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-Mt (X') XnWherein Mt is Ti, n X are methyl, n is 2, and X' is cyclopentadiene;
formula (1-Ti-10): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Ti, n X are Br, n is 2, and X' is cyclopentadiene;
formula (1-Ti-11): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-MtXnMt is Ti, n XAre both Br, n is 3;
formula (1-Ti-12): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Ti, n X are all ethyl, n is 2, and X' is cyclopentadiene;
formula (1-Ti-13): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Ti, n X are Cl, n is 2, and X' is cyclopentadiene;
formula (1-Ti-14): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-MtXnMt is Ti, n X are Cl, and n is 3;
formula (1-Ti-15): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-Mt (X') XnWherein Mt is Ti, n X are methyl, n is 2, and X' is cyclopentadiene;
formula (1-Ti-16): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Ti, n X are Br, n is 2, and X' is cyclopentadiene;
formula (1-Ti-17): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-MtXnMt is Ti, n X are Br, and n is 3;
formula (1-Ti-18): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Ti, n X are all ethyl, n is 2, and X' is cyclopentadiene;
formula (1-Ti-19): in the formula (1),R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Ti, n X are Cl, n is 2, and X' is cyclopentadiene;
formula (1-Ti-20): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-MtXnMt is Ti, n X are Cl, and n is 3;
formula (1-Ti-21): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-Mt (X') XnWherein Mt is Ti, n X are methyl, n is 2, and X' is cyclopentadiene;
formula (1-Ti-22): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Ti, n X are Br, n is 2, and X' is cyclopentadiene;
formula (1-Ti-23): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-MtXnMt is Ti, n X are Br, and n is 3;
formula (1-Ti-24): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Ti, n X are all ethyl, n is 2, and X' is cyclopentadiene;
formula (1-Zr-1): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Zr, n X are Cl, n is 2, and X' is cyclopentadiene;
formula (1-Zr-2): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-MtXnMt is Zr, n X are Cl, and n is 3;
formula (1-Zr-3): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Zr, n X are methyl, n is 2, X' is cyclopentadiene;
formula (1-Zr-4): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Zr, n X are Br, n is 2, and X' is cyclopentadiene;
formula (1-Zr-5): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-MtXnMt is Zr, n X are Br, and n is 3;
formula (1-Zr-6): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Zr, n X are all ethyl, n is 2, and X' is cyclopentadiene;
formula (1-Zr-7): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Zr, n X are Cl, n is 2, and X' is cyclopentadiene;
formula (1-Zr-8): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-MtXnMt is Zr, n X are Cl, and n is 3;
formula (1-Zr-9): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Zr, n X are methyl, n is 2, X' is cyclopentadiene;
formula (1-Zr-10): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Zr, n X are Br, n is 2, and X' is cyclopentadiene;
formula (1-Zr-11): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-MtXnMt is Zr, n X are Br, and n is 3;
formula (1-Zr-12): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Zr, n X are all ethyl, n is 2, and X' is cyclopentadiene;
formula (1-Zr-13): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Zr, n X are Cl, n is 2, and X' is cyclopentadiene;
formula (1-Zr-14): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-MtXnMt is Zr, n X are Cl, and n is 3;
formula (1-Zr-15): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Zr, n X are methyl, n is 2, X' is cyclopentadiene;
formula (1-Zr-16): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Zr, n X are Br, n is 2, and X' is cyclopentadiene;
formula (1-Zr-17): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are all made ofTert-butyl radical, R3is-MtXnMt is Zr, n X are Br, and n is 3;
formula (1-Zr-18): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Zr, n X are all ethyl, n is 2, and X' is cyclopentadiene;
formula (1-Zr-19): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Zr, n X are Cl, n is 2, and X' is cyclopentadiene;
formula (1-Zr-20): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-MtXnMt is Zr, n X are Cl, and n is 3;
formula (1-Zr-21): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Zr, n X are methyl, n is 2, X' is cyclopentadiene;
formula (1-Zr-22): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Zr, n X are Br, n is 2, and X' is cyclopentadiene;
formula (1-Zr-23): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-MtXnMt is Zr, n X are Br, and n is 3;
formula (1-Zr-24): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Zr, n X are all ethyl, n is 2, and X' is cyclopentadiene;
formula (1-Hf-1): formula (II)(1) In, R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Hf, n X are Cl, n is 2, and X' is cyclopentadiene;
formula (1-Hf-2): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-MtXnMt is Hf, n X are Cl, and n is 3;
formula (1-Hf-3): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Hf, n X are methyl, n is 2, X' is cyclopentadiene;
formula (1-Hf-4): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Hf, n X are Br, n is 2, and X' is cyclopentadiene;
formula (1-Hf-5): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-MtXnMt is Hf, n X are Br, and n is 3;
formula (1-Hf-6): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Hf, n X are all ethyl, n is 2, and X' is cyclopentadiene;
formula (1-Hf-7): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Hf, n X are Cl, n is 2, and X' is cyclopentadiene;
formula (1-Hf-8): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-MtXnMt is Hf, n X are Cl, and n is 3;
formula (1-Hf-9): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Hf, n X are methyl, n is 2, X' is cyclopentadiene;
formula (1-Hf-10): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Hf, n X are Br, n is 2, and X' is cyclopentadiene;
formula (1-Hf-11): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-MtXnMt is Hf, n X are Br, and n is 3;
formula (1-Hf-12): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each phenyl, R3is-Mt (X') XnMt is Hf, n X are all ethyl, n is 2, and X' is cyclopentadiene;
formula (1-Hf-13): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Hf, n X are Cl, n is 2, and X' is cyclopentadiene;
formula (1-Hf-14): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-MtXnMt is Hf, n X are Cl, and n is 3;
formula (1-Hf-15): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Hf, n X are methyl, n is 2, X' is cyclopentadiene;
formula (1-Hf-16): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Hf, n X are Br, n is 2, and X' is cyclopentadiene;
formula (1-Hf-17): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-MtXnMt is Hf, n X are Br, and n is 3;
formula (1-Hf-18): in the formula (1), R1、R2And R3Are all H, R4Are each methyl, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Hf, n X are all ethyl, n is 2, and X' is cyclopentadiene;
formula (1-Hf-19): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Hf, n X are Cl, n is 2, and X' is cyclopentadiene;
formula (1-Hf-20): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-MtXnMt is Hf, n X are Cl, and n is 3;
formula (1-Hf-21): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Hf, n X are methyl, n is 2, X' is cyclopentadiene;
formula (1-Hf-22): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-Mt (X') XnMt is Hf, n X are Br, n is 2, and X' is cyclopentadiene;
formula (1-Hf-23): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-MtXnMt is Hf, n X are Br, and n is 3;
formula (1-Hf-24): in the formula (1), R1、R2、R3And R4Are all H, R1And R2Are each tert-butyl, R3is-Mt (X') XnWhere Mt is Hf, n X are all ethyl groups, n ═ 2, and X' is cyclopentadiene.
In a preferred embodiment of the present invention, the early transition metal compound is one of compounds represented by the following formulae:
the second aspect of the present invention provides an intermediate of the above-mentioned early transition metal compound, wherein the intermediate of the early transition metal compound is a compound represented by formula (2):
each R is4Each independently selected from C1-20And C is a hydrocarbon group1-20Alkoxy group of (2).
The choice of the other groups in formula (2) will be made in accordance with the description of the groups of formula (1) hereinbefore, and the invention will not be described in any further detail here.
Preferably, each R4Each independently selected from C1-16And C is a hydrocarbon group1-16Alkoxy group of (2).
More preferably, each R4Each independently selected from C1-10And C is a hydrocarbon group1-10Alkoxy group of (2).
More preferably, each R4Each independently selected from C1-6And C is a hydrocarbon group1-6Alkoxy group of (2).
Even more preferably, each R4Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy.
The specific selection of the intermediate of the above-mentioned early transition metal compound represented by the formula (2) can be selected in accordance with the specific examples of the early transition metal compound described above.
In a preferred embodiment of the present invention, the intermediate represented by formula (2) is one of the compounds represented by the following formulae:
the third aspect of the present invention provides the crystal of the aforementioned early transition metal compound, wherein the crystal system of the crystal is an orthorhombic system.
Specifically, the single crystal of the early transition metal compound represented by the above formula (1-Ti-1) has a crystal system of an orthorhombic system and a space group of Pna21The unit cell parameters are as follows:α=90°,β=90°,γ=90°,Z=4,ρcalc=1.332g/cm3。
the single crystal of the present invention will have higher catalytic activity than that of the mixed crystal or non-single crystal form of the early transition metal compound.
The fourth aspect of the present invention provides a method for producing an early transition metal compound, the method comprising:
(1) carrying out a first substitution reaction on a compound shown as a formula (4) and an organic lithium reagent;
(2) carrying out a second substitution reaction on the product of the first substitution reaction and the compound shown in the formula (a) to obtain a compound shown in a formula (3);
(3) carrying out a Staudinger reaction on a compound shown in a formula (3) and an azidosilane compound shown in a formula (b) to obtain a compound shown in a formula (2);
(4) carrying out a third substitution reaction on the compound shown in the formula (2) and the compound shown in the formula (c) to obtain a compound shown in the formula (1);
optionally, in the case that at least one of n X in the compound represented by formula (1) obtained in step (4) is halogen, the method further comprises: (5) performing a fourth substitution reaction on the compound shown in the formula (1) and a Grignard reagent or alkyl lithium, wherein the Grignard reagent is the compound shown in the formula (d), and the alkyl lithium is the compound shown in the formula (d');
Formula (d) R5-MgX '", formula (d') R5-Li,
Wherein R is1、R2、R3And R4Each independently selected from H, C1-20A hydrocarbon group of1-20Alkoxy and halogen of (a);
R1and R2Each independently selected from H, C1-4And substituted or unsubstituted C6-16Aryl of (a), the substituted C6-16The substituents on the aryl group of (A) are selected from C1-4A hydrocarbon group of (a);
each R is4Each independently selected from C1-20And C is a hydrocarbon group1-20Alkoxy group of (a);
R3is-MtXnor-Mt (X') XnWherein, in the step (A),
mt is a group IVB metal element;
n X are each independently selected from C1-10And halogen, and n ═ n '-1, n' is the valence of element Mt; x' is a ligand of a metal element Mt;
R5is selected from C1-10A hydrocarbon group of (a);
x "and X'" are each independently selected from halogen.
According to the invention, the above groups can be selected according to the description hereinbefore, which is not repeated here.
Preferably, R1、R2、R3And R4Each independently selected from H, C1-16A hydrocarbon group of1-16Alkoxy and halogen of (a);
each R is4Each independently selected from C1-16And C is a hydrocarbon group1-16Alkoxy group of (a);
mt is Ti, Zr or Hf;
n X are each independently selected from C1-8A hydrocarbon group of (a), fluorine, chlorine, bromine and iodine;
R5is selected from C1-8A hydrocarbon group of (1).
More preferably, R1、R2、R3And R4Each independently selected from H, C1-10A hydrocarbon group of1-10Alkoxy and halogen of (a);
R1and R2Each independently selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;
each R is4Each independently selected from C1-10And C is a hydrocarbon group1-10Alkoxy group of (a);
mt is Ti, Zr or Hf;
n X are each independently selected from methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, and iodo; x' is substituted or unsubstituted 1, 3-cyclobutanediene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, substituted or unsubstituted fluorene, substituted or unsubstituted benzene ring, substituted or unsubstituted 1,3, 5-cycloheptatriene or substituted or unsubstituted cyclooctatetraene;
R5selected from methyl, ethyl, n-propyl or isopropyl.
Even more preferably, R1、R2、R3And R4Each independently selected from H, C1-6A hydrocarbon group of1-6Alkoxy and halogen of (a);
R1and R2Each independently selected from substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;
each R is4Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy;
mt is Ti, Zr or Hf;
n X are each independently selected from methyl, ethyl, fluoro, chloro, bromo and iodo; x' is substituted or unsubstituted 1, 3-cyclobutanediene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, substituted or unsubstituted fluorene, substituted or unsubstituted benzene ring, substituted or unsubstituted 1,3, 5-cycloheptatriene or substituted or unsubstituted cyclooctatetraene;
R5selected from methyl or ethyl;
x "and X'" are each independently selected from the group consisting of fluorine, chlorine, bromine, and iodine.
In the above production method, the compound for reaction may be one or more of the compounds represented by the above formulae, and the compound represented by the formula (1) thus produced may be one of the compounds represented by the formula (1), or a mixture of a plurality of compounds represented by the formula (1), and this is within the scope of the present invention.
Wherein, the specific examples of the compound represented by the formula (3) may be selected from one or more of the compounds represented by the following formulae:
specific examples of the compound represented by the formula (4) may be selected from one or more compounds represented by the following formulae:
specific examples of the compound represented by the formula (a) may be selected from one or more compounds represented by the following formulae:
formula (a-1): in the formula (a), R1And R2Are each phenyl, X3Is chlorine (also known as diphenyl phosphine chloride);
formula (a-2): in the formula (a), R1And R2Are each tert-butyl, X3Is chlorine;
formula (a-3): in the formula (a), R1And R2Are each phenyl, X3Is H;
formula (a-4): in the formula (a), R1And R2Are each tert-butyl, X3Is H;
formula (a-5): in the formula (a), R1And R2Are each phenyl, X3Is bromine;
formula (a-2): in the formula (a), R1And R2Are each tert-butyl, X3Is bromine.
Specific examples of the compound represented by the formula (b) may be selected from one or more compounds represented by the following formulae:
formula (b-1): in the formula (b), R4Are both methyl (also known as azidotrimethylsilane);
formula (b-2): in the formula (b), R4Are all ethyl;
formula (b-3): in the formula (b), R4Are both methoxy;
formula (b-2): in the formula (b), R4Are all ethoxy groups.
Specific examples of the compound represented by the formula (c) may be selected from one or more compounds represented by the following formulae:
formula (c-Ti-1): in the formula (c), X' is Cl, R3is-Mt (X') XnWhere Mt is Ti, n X are Cl, n ═ 2, and X' is cyclopentadiene (also denoted as CpTiCl)3);
Formula (c-Ti-2): in the formula (c), X' is Cl, R3is-MtXnWhere Mt is Ti, n X are Cl, and n is 3 (which may also be represented by TiCl)4);
Formula (c-Ti-3): in the formula (c), X' is Br, R3is-Mt (X') XnMt is Ti, n X are Br, n is 2, and X' is cyclopentadiene;
formula (c-Ti-4): in the formula (c), X' is Br, R3is-MtXnMt is Ti, n X are Br, and n is 3;
formula (c-Zr-1): in the formula (c), X' is chlorine, R3is-Mt (X') XnWhere Mt is Zr, n X are each Cl, n ═ 2, and X' is cyclopentadiene (also denoted as CpZrCl)3);
Formula (c-Zr-2): in the formula (c), X' is chlorine, R3is-MtXnWhere Mt is Zr, n X are Cl, and n is 3 (may also be represented as ZrCl)4);
Formula (c-Zr-3): in the formula (c), X' is Br, R3is-Mt (X') XnMt is Zr, n X are Br, n is 2, and X' is cyclopentadiene;
formula (c-Zr-4): in the formula (c), X' is Br, R3is-MtXnMt is Zr, n X are Br, and n is 3;
formula (c-Hf-1): in the formula (c), X' is chlorine, R3is-Mt (X') XnWhere Mt is Hf, n X are Cl, n ═ 2, and X' is cyclopentadiene (also denoted as CpHfCl)3);
Formula (c-Hf-2): in the formula (c), X' is chlorine, R3is-MtXnWhere Mt is Hf, n X are Cl, and n is 3 (may also be represented as HfCl)4);
Formula (c-Hf-3): in the formula (c)X' is Br, R3is-Mt (X') XnMt is Hf, n X are Br, n is 2, and X' is cyclopentadiene;
formula (c-Hf-4): in the formula (c), X' is Br, R3is-MtXnWhere Mt is Hf, n X are Br, and n is 3.
Specific examples of the compound represented by the formula (d) may be selected from one or more compounds represented by the following formulae:
formula (d-1): in the formula (d), R5Is methyl, X' "is Br (also denoted MeMgBr);
formula (d-2): in the formula (d), R5Is methyl, X' "is Cl (also represented by MeMgCl);
formula (d-3): in the formula (d), R5Is ethyl, X' "is Br (also denoted by EtMgBr);
formula (d-4): in the formula (d), R5For ethyl, X' "is Cl (also denoted by EtMgCl).
Specific examples of the compound represented by the formula (d') may be selected from one or more compounds represented by the following formulae:
formula (d' -1): in the formula (d'), R5Is methyl;
formula (d' -2): in the formula (d'), R5Is ethyl.
According to the present invention, the compound represented by formula (4) will be caused to form a lithium salt, i.e., X represented by formula (4), by the first substitution reaction of step (1)1And X2A lithium salt is formed at the group. Wherein the organolithium reagent may be selected from a plurality of organolithium compounds, preferably the organolithium reagent is of formula R6-one or more of the compounds represented by Li, wherein R6Is C1-8Alkyl group of (1). More preferably, the organolithium reagent is one or more of methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium.
According to the present invention, the amount of the organolithium reagent may vary within a wide range as long as the compound represented by formula (4) can be sufficiently formed into the corresponding lithium salt, and preferably, the molar ratio of the compound represented by formula (4) to the organolithium reagent is 1: 1.8 to 3, preferably 1: 2-2.5.
According to the present invention, in order to allow the first substitution reaction to proceed more smoothly, it is preferable that the first substitution reaction is performed in the presence of a complexing additive which is one or more of N, N' -Tetramethylethylenediamine (TMEDA), hexamethylphosphoric triamide (HMPA), and N, N-Dimethylpropyleneurea (DMPU). The dosage of the coordination additive can be adjusted according to the dosage of the organic lithium reagent, and preferably, the molar ratio of the coordination additive to the organic lithium reagent is 0.5-2: 1, more preferably 0.8 to 1.5: 1.
according to the present invention, the solvent used in the first substitution reaction may be various solvents having good solubility for the compound represented by formula (4), for example, one or more selected from toluene, n-hexane, n-pentane, benzene, xylene, dichloromethane, chloroform, tetrachloromethane, and tetrahydrofuran. The amount of the solvent to be used may be varied within a wide range, and for example, the amount of the solvent to be used is 10 to 200mL relative to 10mmol of the compound represented by the formula (4).
According to the present invention, preferably, the conditions of the first substitution reaction include: the reaction is carried out for 0.5 to 2 hours at the temperature of between 90 ℃ below zero and 50 ℃ below zero, and then for 10 to 24 hours at the temperature of between 10 and 40 ℃. More preferably, the conditions of the first substitution reaction include: the reaction is carried out for 0.5 to 1.5 hours at the temperature of between 80 ℃ below zero and 70 ℃ below zero, and then the reaction is carried out for 12 to 20 hours at the temperature of between 20 and 30 ℃. The compound represented by the formula (4) and the complexing additive may be mixed with a solvent, and then the organolithium reagent may be introduced (for example, in the form of dropwise addition) at-90 ℃ to-50 ℃ (preferably, -80 ℃ to-70 ℃) to perform the first substitution reaction.
According to the invention, the compound shown in the formula (3) is formed in the step (2) through a second substitution reaction, wherein the substitution product obtained in the step (1) can be extracted to perform the second substitution reaction with the compound shown in the formula (a), but preferably the substitution product obtained in the step (1) is not extracted, and the compound shown in the formula (a) is directly introduced into the system of the first substitution reaction to perform the second substitution reaction. Wherein the amount of the compound represented by formula (a) may be varied within a wide range as long as the compound represented by formula (3) can be obtained, and preferably, the molar ratio of the compound represented by formula (4) to the compound represented by formula (a) is 1: 1.8 to 3, preferably 1: 2-2.5.
According to the present invention, the compound represented by the formula (a) may be provided as a pure compound, but in order to promote the second substitution reaction to proceed more sufficiently, the compound represented by the formula (a) is provided as a solution thereof, and the solvent used may be, for example, one or more of toluene, n-hexane, n-pentane, benzene, xylene, dichloromethane, trichloromethane, tetrachloromethane, and tetrahydrofuran, and may be used in an amount such that the concentration of the solution of the compound represented by the formula (a) is, for example, 0.5 to 10 mmol/mL.
According to the present invention, preferably, the conditions of the second substitution reaction include: the temperature is 10-40 ℃ and the time is 10-24 h. More preferably, the conditions of the second substitution reaction include: the temperature is 20-30 ℃ and the time is 12-20 h. Wherein, the operation process of the step (2) may include: under the ice-bath condition, the compound solution shown in the formula (a) is introduced into the system of the first substitution reaction (for example, in a dropwise manner), and then the reaction is carried out under the conditions of the second substitution reaction.
According to the present invention, in order to extract the compound represented by the formula (3), the compound represented by the formula (3) can be obtained by removing the solvent (for example, by rotary evaporation) after the completion of the second substitution reaction, washing (for example, washing with acetone), and then drying.
According to the present invention, the compound represented by formula (2) can be obtained by reacting the compound represented by formula (3) with the azidosilane compound represented by formula (b) via the Staudinger reaction of step (3). The amount ratio of the compound represented by the formula (3) to the azidosilane compound represented by the formula (b) may be varied within a wide range, and in order to allow the compound represented by the formula (3) to react more sufficiently, it is preferable that the molar ratio of the compound represented by the formula (3) to the azidosilane compound represented by the formula (b) is 1: 1-5, preferably 1: 2-4.
According to the invention, the reaction can be carried out in the presence of one or more organic solvents selected from the group consisting of toluene, n-hexane, n-pentane, benzene, xylene, dichloromethane, trichloromethane, tetrachloromethane and tetrahydrofuran, which can be used in a wide range, for example in an amount of 10 to 200mL, relative to 10mmol of the compound of formula (3).
According to the present invention, preferably, the conditions of the staudinger reaction include: the temperature is 80-150 ℃ and the time is 5-20 h. More preferably, the conditions of the staudinger reaction include: the temperature is 100 ℃ and 140 ℃, and the time is 8-14 h. In order to extract the compound represented by the formula (2), the solvent may be removed (for example, by rotary evaporation) after the reaction is completed, and the compound represented by the formula (2) may be obtained.
According to the present invention, the compound represented by the formula (2) and the compound represented by the formula (c) are subjected to a third substitution reaction to obtain the compound represented by the formula (1). Preferably, the molar ratio of the compound represented by the formula (2) to the compound represented by the formula (c) is 1: 0.8 to 1.5, preferably 1: 1-1.2. Wherein, the compound shown in the formula (c) can be provided in the form of a solution thereof, and the solvent used can be one or more of toluene, n-hexane, n-pentane, benzene, xylene, dichloromethane, chloroform, tetrachloromethane and tetrahydrofuran, and the concentration thereof can be 0.05 to 1mmol/mL, for example.
According to the invention, the reaction of step (4) can also be carried out in the presence of one or more organic solvents selected from the group consisting of toluene, n-hexane, n-pentane, benzene, xylene, dichloromethane, trichloromethane, tetrachloromethane and tetrahydrofuran, in an amount which can vary within wide limits, for example in an amount of 10 to 500mL, relative to 10mmol of the compound of formula (2).
According to the present invention, preferably, the conditions of the third substitution reaction include: the temperature is 80-150 ℃ and the time is 8-20 h. More preferably, the conditions of the third substitution reaction include: the temperature is 100-140 ℃, and the time is 10-15 h. After the third substitution reaction is completed, the solvent may be removed (for example, by rotary evaporation), washed (for example, with n-pentane), and then dried to obtain the compound represented by formula (1).
According to the invention, the preparation of the compound of formula (1) wherein X is a hydrocarbon group can also be carried out in other ways, for which purpose the process can optionally further comprise: in the case where at least one of n X in the compound represented by formula (1) obtained in step (4) is a halogen, the method further comprises: (5) carrying out a fourth substitution reaction on the compound shown in the formula (1) and a Grignard reagent or alkyl lithium, wherein the Grignard reagent is the compound shown in the formula (d), and the alkyl lithium is the compound shown in the formula (d'); thus, the halogen X in the compound represented by the formula (1) as a reactant can be substituted with a hydrocarbon group.
According to the present invention, in the case of including step (5), the compound represented by formula (1) and the grignard reagent or alkyllithium are used in a molar ratio of 1: 0.8 to 8, preferably 1: 1.5-6. Wherein, the Grignard reagent or alkyl lithium can be provided in the form of a solution thereof, and the solvent generally used can be, for example, one or more of diethyl ether, tetrahydrofuran, n-hexane, n-pentane, etc., and the concentration thereof can be, for example, 0.5 to 5 mmol/mL.
According to the present invention, the fourth substitution reaction is carried out in the presence of an organic solvent, which may be one or more selected from the group consisting of diethyl ether, tetrahydrofuran, n-hexane, n-pentane, etc., in an amount varying over a wide range, for example, 100-2000mL relative to 10mmol of the compound represented by formula (1) as a reactant.
According to the present invention, preferably, the conditions of the fourth substitution reaction include: the temperature is 80-150 ℃ and the time is 8-20 h. More preferably, the conditions of the fourth substitution reaction include: the temperature is 100 ℃ and 140 ℃, and the time is 10-18 h. After the fourth substitution reaction is completed, the solvent may be removed (for example, by rotary evaporation), washed (for example, with n-pentane), and dried to obtain the compound represented by formula (1) as a product.
According to the present invention, in order to obtain a single crystal of the compound represented by formula (1), the crude product of the compound represented by formula (1) obtained by the above-mentioned method may be dissolved in a mixed solvent of dichloromethane/toluene (volume ratio is preferably 1: 0.5-2), the dissolving process is preferably performed in an inert atmosphere (e.g., nitrogen atmosphere, argon atmosphere, etc.), and then the resulting solution is allowed to stand and subjected to a solvent volatilization treatment (preferably performed in a vacuum drier), whereby a single crystal of the compound represented by formula (1) can be obtained.
The fifth aspect of the present invention provides an early transition metal compound obtained by the above-mentioned method.
The early transition metal compound produced by the above-mentioned production method of the present invention may be understood as a crude product of an early transition metal compound, a mixture of a plurality of early transition metal compounds, a single crystal of an early transition metal compound, a mixture of a plurality of single crystals of early transition metal compounds, or the like, and these are within the scope of the present invention.
In a sixth aspect, the present invention provides use of the above-mentioned early transition metal compound or the above-mentioned crystal of the early transition metal compound for catalyzing ethylene homopolymerization and/or ethylene- α -olefin copolymerization.
The alpha-olefin herein may be an alpha-olefin conventionally used in the art for copolymerization with ethylene, and may be, for example, one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 4-methyl-1-pentene.
In a seventh aspect, the present invention provides a catalyst composition suitable for the polymerisation of olefins, the composition comprising a procatalyst which is a compound of the aforementioned early transition metal or a crystal of a compound of the aforementioned early transition metal and an activator comprising one or more of an aluminium-containing compound and optionally an organoboron compound. It is to be understood that the procatalyst is one or more of the aforementioned early transition metal compounds or one or more of the aforementioned crystals of early transition metal compounds, including of course any combination thereof. Where the activator contains an organoboron compound, it is also understood that the activator contains one or more of organoboron compounds.
According to the invention, in the case where the activator is one or more of aluminum-containing compounds, the composition preferably contains the main catalyst in terms of the metal element Mt and the aluminum-containing compound in terms of the aluminum element in a molar ratio of 1: 50-3000, preferably 1: 100-1000, more preferably 1: 100-500, for example, 1: 100-200, 1: 300-500.
According to the present invention, in the case where the activator is an aluminum-containing compound and an organoboron compound, in the composition, preferably, the main catalyst in terms of a metal element Mt, the aluminum-containing compound in terms of an aluminum element, and the organoboron compound in terms of a boron element are contained in a molar ratio of 1: 0.1-500: 0.5 to 5, preferably 1: 0.2-100: 1-3, for example 1: 0.2-1: 1-2, 1: 2-10: 1-3, 1: 15-30: 1-3, 1: 50-80: 1-3.
According to the present invention, the aluminum-containing compound as an activator may be selected from a wide range and may be one or more of an alkylaluminum compound and an alkylaluminoxane compound, and preferably, the aluminum-containing compound is a mixture of an alkylaluminum compound and an alkylaluminoxane compound or an alkylaluminoxane compound.
Preferably, the alkylaluminoxane compound may be represented by formula (e),
wherein R is31At least one group selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl; t is an integer of 5 to 30. More preferably, in formula (3), R31Is at least one group selected from the group consisting of methyl, ethyl, n-propyl, isopropyl and tert-butyl. Further preferably, in formula (3), R31Is at least one group selected from methyl, ethyl and isobutyl. Particularly preferably, the alkylaluminoxane compound is Methylaluminoxane (MAO) and/or isobutylaluminoxane, i.e., R31Is methyl or isobutyl.
Preferably, the alkylaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride. Particularly preferably, the alkyl aluminum compound is triisobutylaluminum.
According to the invention, preferably, the organoboron compound is selected from tris (pentafluorophenyl) boron (B (C)6F5)3) N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate ([ HNMe)2Ph][B(C6F5)4]) And triphenylcarbenium tetrakis (pentafluorophenyl) borate ([ Ph)3C][B(C6F5)4]) One or more of (a).
The composition of the present invention may also contain other necessary additives as long as these additives do not affect the catalytic effect of the composition. For example, the composition may contain an impurity scavenger.
The eighth aspect of the present invention provides the use of the above composition in the catalysis of ethylene homopolymerization and/or ethylene-alpha olefin copolymerization.
In this application of the present invention, the order of addition and the method of addition of the components forming the catalyst composition suitable for olefin polymerization are not particularly limited, and the procatalyst, the activator and the optionally contained additive may be mixed in advance and then added to the polymerization reaction, or the procatalyst, the activator and the optionally contained additive may be added separately to the polymerization reaction. According to a preferred embodiment: the activator and the additive which is optionally contained are added into the reaction system, then the olefin monomer is introduced, and then the main catalyst is added.
Wherein the alpha olefin is as described above, and the invention is not repeated herein.
The ninth aspect of the present invention provides a process for producing an olefin polymer, which comprises: in an organic solvent, in the presence of a catalyst, carrying out a polymerization reaction on an olefin monomer;
wherein the catalyst is the composition.
According to the present invention, preferably, the polymerization conditions include: the temperature is-50 ℃ to 200 ℃, and the pressure is 0.1MPa to 5 MPa. More preferably, the polymerization conditions include: the temperature is 20-100 deg.C, and the pressure is 0.1-2MPa (such as 0.1-0.5 MPa). The pressure is a gauge pressure.
The polymerization reaction of the present invention may be carried out by solution polymerization or bulk polymerization. The polymerization reaction of the present invention may be a solution polymerization reaction, and it will be apparent to those skilled in the art that the solvent used therein should be liquid under the polymerization conditions and not participate in the polymerization reaction nor react with the polymer obtained by the reaction, i.e., the solvent is inert. Such solvents will be readily apparent to those of ordinary skill in the polymerization art and can be readily selected. Nevertheless, for the present invention, specific examples of the organic solvent may be, for example, one or more of benzene, toluene, ethylbenzene, xylene, n-pentane, n-hexane, n-heptane, n-octane, and cyclohexane, preferably n-hexane, n-octane, or n-heptane, and more preferably n-hexane is used as the solvent in the homopolymerization reaction of the present invention. For the polymerization according to the invention, the solvent is used in such an amount that the concentration of the polymer is in the range from 5 to 30% by weight, preferably from 8 to 10% by weight.
According to the present invention, the above polymerization process is preferably carried out under protection of an inert atmosphere, for example, one or more of nitrogen, helium, argon, etc. may be used to provide such an inert atmosphere.
In the polymerization reaction of the present invention, a terminator may be used to terminate the polymerization reaction after the completion of the polymerization reaction. The terminating agents used for this step are conventional to those skilled in the art. Commonly used terminating agents include deionized water, alcohols, acids, and the like. In the present invention, the terminator to be preferably used is one or more of isopropyl alcohol, methanol, water and the like.
Preferably, the olefin monomer is one or more of ethylene, an α -olefin and a cyclic olefin. Preferably, the α -olefin is one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 4-methyl-1-pentene, and the cyclic olefin is one or more of cyclopentene, cyclohexene, norbornene, 1-methylnorbornene, 5-methylnorbornene, dicyclopentadiene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene and 5-ethylidene-2-norbornene.
The above catalyst of the present invention is particularly suitable for homopolymerization of ethylene and copolymerization of ethylene-alpha olefin (particularly copolymerization of ethylene-propylene in a molar ratio of 1: 0.5-5).
More specifically, the above-mentioned production process enables to produce an olefin polymer with higher catalytic efficiency, for example, up to 10, using the composition of the present invention as a catalyst6gPolymer and method of making same/molMetalH. The catalyst of the present invention can prepare high density polyethylene with higher molecular weight and higher linearity degree and ethylene-propylene elastomer with high molecular weight under lower pressure.
The present invention will be described in detail below by way of examples.
In the following examples:
the various starting materials used are all commercially available, unless otherwise specified.
The weight average molecular weight of the polymers described below was determined by Waters150 Gel Permeation Chromatography (GPC) and was determined at 135 ℃ with 1,2, 4-trichlorobenzene as the mobile phase.
Catalytic efficiency is the mass of polymer obtained per mole of Mt per unit time, in gPolymer and method of making same/molMetalH represents.
1H NMR spectrometer model Bruker Ascend 400M of Bruker corporation was used
The single crystal diffraction analysis was performed using a Bruker APEX II model X-ray single crystal diffractometer from Bruker.
Example 1
This example is intended to illustrate the early transition metal compound of the present invention, its preparation method, intermediate and single crystal.
Preparation was carried out according to the above reaction formula, specifically:
(1) diluting 9, 9-dimethylxanthene (0.02mol) and Tetramethylethylenediamine (TMEDA) (42mmol) in hexane (50mL), adding n-BuLi (42mmol) in hexane dropwise (after addition within about 5 min) at-78 deg.C, reacting for 1h, then raising to room temperature (about 25 deg.C), and continuing to stir for reaction for 16 h;
(2) then, under the ice-water bath, 15mL of diphenyl phosphine chloride (42mmol) n-hexane solution is dripped into the reaction system in the step (1) (after the addition is completed within about 5 min), and then the stirring reaction is continued at room temperature (about 25 ℃) for 16 h; the solvent was removed by rotary evaporation to give a pale yellow viscous oil, which was washed with acetone and dried in vacuo to give 9.7g of a white powder, i.e., a compound represented by the formula (3-1): the yield is 84 percent,1H NMR(400MHz,C6D6)δ:7.45-7.33(m,8H,o-PPh2),7.08(dd,2H,J=7.7,1.4Hz,PCCHCH),7.05-6.95(m,12H,m-PPh2,p-PPh2),6.84(dd,J=7.5,1.5Hz,2H,CHCHCC),6.76(t,J=7.6Hz,2H,CHCHCH),1.37(s,6H,CH3)ppm。
(3) dissolving a compound (2mmol) shown in a formula (3-1) in 10mL of toluene, dropwise adding trimethylsilyl azide (6mmol) under magnetic stirring (after the addition is completed within about 3 min), and heating to 110 ℃ for refluxing for 10 h; after the reaction was completed, the reaction mixture was rotary evaporated under reduced pressure and then dried by suction to obtain 1.42g of a white solid, i.e., a compound represented by the formula (2-1): the yield thereof was found to be 94%.1H NMR(400MHz,C6D6)δ:8.43(dd,J=14.5,7.5Hz,1H,xanthene),7.90(dd,J=13.0,7.7Hz,4H,o-PPh2),7.10(d,J=7.7Hz,1H,xanthene),6.90(m,14H,m-PPh2,p-PPh2,xanthene),6.75(t,J=6.3Hz,5H,o-PPh2,xanthene),1.17(s,6H,xanthene),0.18(s,9H,SiMe3)ppm.
(4) The compound of formula (2-1) (1mmol) was dissolved in 10mL of toluene and 5mL of CpTiCl was added dropwise with magnetic stirring3(1mmol) of a toluene solution, and then heating to 110 ℃ for refluxing for 12 h; after the reaction is finished, the solvent toluene is removed by reduced pressure rotary evaporation to obtain a light yellow crude productThe crude product was washed 3 times with n-pentane and dried in vacuo to give 0.72g of a yellow solid, i.e., a compound represented by the formula (1-Ti-1): the yield thereof was found to be 93%.1H NMR(400MHz,CD2Cl2)δ:8.49(ddd,J=15.1,7.7,1.4Hz,1H,xanthene),7.83(ddd,J=14.7,7.9,6.8Hz,4H,o-PPh2),7.76-7.70(m,1H,xanthene),7.40(dd,J=7.8,1.6Hz,1H),7.25-7.10(m,12H),7.00-6.94(m,1H,xanthene),6.91(t,J=7.6Hz,1H,xanthene),6.77(ddd,J=7.0,5.8,1.4Hz,4H,o-PPh2),6.56-6.49(m,1H,xanthene),5.94(s,4H,Cp),1.58(s,6H)ppm.
Preparing a single crystal: dissolving the compound (about 0.1mmol) of the formula (1-Ti-1) obtained in the step (4) in 5mL of dichloromethane/toluene mixed solvent (volume ratio is 1: 1) under the protection of nitrogen, placing the mixture in a vacuum drier for slow volatilization of the solvent to obtain a corresponding compound single crystal of the formula (1-Ti-1), and analyzing by single crystal diffraction to confirm that the structure is shown in figure 1, the crystal system is orthorhombic and the space group is Pna21The unit cell parameters are as follows:α=90°,β=90°,γ=90°,Z=4,ρcalc=1.332g/cm3。
example 2
This example is intended to illustrate the early transition metal compound of the present invention, its preparation method, intermediate and single crystal.
The method of embodiment 1, except that in step (4): the compound represented by the formula (2-1) (1mmol) was dissolved in 10mL of toluene, and 5mL of TiCl was added dropwise with magnetic stirring4(1mmol) of a toluene solution, and then heating to 110 ℃ for refluxing for 12 h; after the reaction is finished, the solvent toluene is removed by reduced pressure rotary evaporation, the crude product is washed for 3 times by pentane, and the product is obtained by vacuum drying1The compound represented by the formula (1-Ti-2) was identified by H NMR.
Example 3
This example is intended to illustrate the early transition metal compound of the present invention, its preparation method, intermediate and single crystal.
The method according to example 1, differentThat is, an equimolar amount of CpZrCl is used in step (4)3In place of CpTiCl3To give the corresponding product, via1The compound represented by the formula (1-Zr-1) was identified by H NMR.
Example 4
This example is intended to illustrate the early transition metal compound of the present invention, its preparation method, intermediate and single crystal.
The method of example 1, except that an equimolar amount of CpHfCl was used in step (4)3In place of CpTiCl3To give the corresponding product, via1The compound represented by the formula (1-Hf-1) was identified by H NMR.
Example 5
This example is intended to illustrate the early transition metal compound of the present invention, its preparation method, intermediate and single crystal.
The method of embodiment 1, except that the example further comprises:
(5) dissolving a compound (0.3mmol) shown in a formula (1-Ti-1) in 25mL of diethyl ether, dropwise adding 1.5mmol of MeMgBr in diethyl ether (0.5mL) under magnetic stirring (after the addition is finished within about 5 min), and then heating to 110 ℃ for refluxing for 15 h; after the reaction is finished, removing the solvent by rotary evaporation, washing the crude product with pentane, drying in vacuum to obtain a corresponding product, and purifying by vacuum distillation1The compound represented by the formula (1-Ti-3) was identified by H NMR.
Example 6
This example is intended to illustrate the early transition metal compound of the present invention, its preparation method, intermediate and single crystal.
The method of example 5, except that an equimolar amount of CpZrCl was used in step (4)3In place of CpTiCl3Thus obtaining the corresponding product after step (5) by1The compound represented by the formula (1-Zr-3) was identified by H NMR.
Comparative example 1
Preparation was carried out according to the above reaction formula, specifically:
(1) to a stirred solution of diphenylphosphine (PHPh) in THF (100mL) at-78 deg.C2) (0.02mol) was added n-BuLi (12.5mL of 1.6M n-hexane solution) to give a deep red solution, which was stirred at 25 ℃ for 8 h;
(2) then, 20mL of a THF solution of 2, 6-dibromopyridine (0.01mol) was added dropwise to the above solution, and the mixture was stirred for 8 hours, followed by removal of the solvent by vacuum suction to obtain a ligand represented by the formula (B1).
The yield is 78 percent;1H NMR(400MHz,C6D6)δ:7.44(m,8H,o-PPh2),7.02(m,12H,m-PPh2,p-PPh2),6.94(d,J=8.4Hz,2H,py),6.73(m,1H,py)。
(3) reacting trimethyl azide silane N3SiMe3(0.02mol) was slowly added to a solution of the ligand represented by the formula (B1) (0.01mol) and 20mL of toluene, and the reaction mixture was heated under reflux for 12 h. When the vacuum is applied to remove the solvent and the excess TMSN3Then, a white solid, i.e., the ligand represented by formula (B2), was obtained.
The yield is 86%;1H NMR(400MHz,CDCl3)δ:8.45-8.37(m,2H,py),8.05-7.97(m,1H,py),7.51–7.43(m,12H,m-PPh2,p-PPh2),7.27–7.22(m,8H,o-PPh2),0.01(s,18H,-SiMe3).
(4) dissolving the ligand (5mmol) shown in the formula (B2) in 10mL of toluene, stirring uniformly, adding 5mL of toluene solution containing cyclopentadienyl titanium trichloride (10mmol), heating to 110 ℃, reacting for 12h, cooling to 25 ℃, and removing the solvent to obtain the product, namely the compound shown in the formula (1B).
Polymerization example 1
This example illustrates the preparation of an ethylene homopolymer according to the invention.
2mL of MAO in toluene (purchased from Albemarle, the same shall apply hereinafter) was added to 200mL of toluene under nitrogen protection at 50 ℃ so that the Al content was 10mmol, and ethylene gas (volume flow rate: 50L/h) was continuously introduced while maintaining a gauge pressure of 0.1MPa, and then the compound represented by the formula (1-Ti-1) (0.02mmol) obtained in step (4) of example 1 was added and polymerization was carried out for 15min, and the supply of monomers was stopped. The reaction was terminated with isopropanol, the resulting polymer was freed of solvent and oven dried.
The results are shown in table 1.
Polymerization example 2
This example illustrates the preparation of an ethylene homopolymer according to the invention.
According to the method described in polymerization example 1, except that the compound represented by the formula (1-Ti-1) was used in an amount of 0.03mmol, the corresponding polymer was obtained, and the results are shown in Table 1.
Polymerization examples 3 to 8
This example illustrates the preparation of an ethylene homopolymer according to the invention.
The process of polymerization example 1, except that:
polymerization example 3 in which the compound represented by the formula (1-Ti-1) obtained in step (4) of example 1 was replaced with an equimolar amount of single crystal of the compound represented by the formula (1-Ti-1) gave the corresponding polymer, and the results are shown in Table 1.
Polymerization example 4 in place of the compound represented by the formula (1-Ti-1) obtained in the step (4) of example 1, an equimolar amount of the compound represented by the formula (1-Ti-2) obtained in the step (4) of example 2 was used to obtain a corresponding polymer, and the results are shown in Table 1.
Polymerization example 5 in which the compound represented by the formula (1-Zr-1) obtained in the step (4) of example 3 was used in an equimolar amount instead of the compound represented by the formula (1-Ti-1) obtained in the step (4) of example 1, the corresponding polymer was obtained, and the results are shown in Table 1.
Polymerization example 6 was conducted using an equimolar amount of the compound represented by the formula (1-Hf-1) obtained in the step (4) of example 4 in place of the compound represented by the formula (1-Ti-1) obtained in the step (4) of example 1 to obtain a corresponding polymer, and the results are shown in Table 1.
Polymerization example 7 in which the compound represented by the formula (1-Ti-1) obtained in step (4) of example 1 was replaced with an equimolar amount of the compound represented by the formula (1-Ti-3) obtained in step (5) of example 5, the corresponding polymer was obtained, and the results are shown in Table 1.
Polymerization example 8 in which the compound represented by the formula (1-Zr-3) obtained in the step (5) of example 6 was used in an equimolar amount instead of the compound represented by the formula (1-Ti-1) obtained in the step (4) of example 1, the corresponding polymer was obtained, and the results are shown in Table 1.
Polymerization example 9
This example illustrates the preparation of an ethylene homopolymer according to the invention.
0.5mL of MAO in toluene was added to 200mL of toluene under nitrogen protection at 50 deg.C (so that the Al content was 10mmol), and ethylene gas was continuously introduced (volume flow: 50L/h) while maintaining a gauge pressure of 0.5MPa, [ CPh ] was added3][B(C6F5)4]A toluene solution of an organoboron compound (used in such an amount that the molar ratio B/Mt is 1/1) was added, and then a compound represented by the formula (1-Ti-3) (0.02mmol) was subjected to polymerization for 15min, and the supply of the monomer was stopped. The reaction was terminated with isopropanol, the resulting polymer was freed of solvent and oven dried.
The results are shown in table 1.
Polymerization example 10
This example illustrates the preparation of an ethylene homopolymer according to the invention.
According to the method described in polymerization example 9, except that the compound represented by the formula (1-Ti-3) was replaced with an equimolar amount of the compound represented by the formula (1-Zr-3), the corresponding polymer was obtained, and the results are shown in Table 1.
Polymerization example 11
This example is intended to illustrate the preparation of the ethylene-propylene copolymer of the present invention.
0.4mL of MAO in toluene was added to 200mL of toluene under nitrogen protection at 50 deg.C (so that the Al content was 2mmol), and an ethylene/propylene/hydrogen mixture (molar ratio 1: 2: 0.01, volume flow rate 50L/h) was continuously introduced while maintaining the gauge pressure at 0.5MPa, and [ CPh ] was added3][B(C6F5)4]A toluene solution of an organoboron compound (used in such an amount that the molar ratio B/Mt is 1/1), followed by addition of a compound represented by the formula (1-Ti-3) (0.02mmol), and polymerization reaction 15min, stopping the monomer supply. The reaction was terminated with isopropanol and an antioxidant lrganox 1520 (from BASF, same below; used in such an amount that the content of the antioxidant in the polymer was 0.2% by weight) was added. The resulting polymer was freed of the solvent and oven dried.
The results are shown in table 1.
Polymerization comparative example 1
According to the method described in polymerization example 1, except that this comparative example employed an equimolar amount of ZrCp2Cl2The complexes were substituted for the compound represented by the formula (1-Ti-1), and the remainder was the same as in polymerization example 1, to give corresponding polymers, the results of which are shown in Table 1.
Polymerization comparative example 2
According to the procedure described in polymerization example 11, except that this comparative example employed an equimolar amount of ZrCp2Me2The complex was substituted for the compound represented by the formula (1-Ti-3), and the remainder was the same as in polymerization example 11, to obtain a corresponding polymer, the results of which are shown in Table 1.
Polymerization comparative example 3
According to the method described in polymerization example 1, except that this comparative example uses an equimolar amount of C2H4{Ph2PNTiCl2Cp*}2The complexes were substituted for the compound represented by the formula (1-Ti-1), and the remainder was the same as in polymerization example 1, to give corresponding polymers, the results of which are shown in Table 1.
Comparative example 4 polymerization
The same procedure as in polymerization example 1 was conducted except that this comparative example used an equimolar amount of the compound represented by the formula (1B) obtained in comparative example 1 in place of the compound represented by the formula (1-Ti-1) to obtain the corresponding polymer, and the results are shown in Table 1.
TABLE 1
As can be seen from the data of Table 1, the olefin catalyzed by the early transition metal compound or the crystal thereof of the present invention has high catalytic activity as will be shown, and has excellent catalytic activity under a wide range of polymerization reaction conditions; in particular, the single crystal catalytic activity of the early transition metal compound of the present invention is higher.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (47)
1. An early transition metal compound, characterized in that the early transition metal compound is a compound represented by the formula (1):
Wherein R is1、R2、R3And R4Each independently selected from H, C1-20A hydrocarbon group of1-20Alkoxy and halogen of (a);
R1and R2Each independently selected from H, C1-4And substituted or unsubstituted C6-16Aryl of (a), the substituted C6-16The substituents on the aryl group of (A) are selected from C1-4A hydrocarbon group of (a);
R3is-MtXnor-Mt (X') Xn-1Wherein, in the step (A),
mt is a group IVB metal element;
n or n-1X are each independently selected from C1-10And halogen, and n ═ n '-1, n' is the valence of the element Mt; x' is a ligand of a metal element Mt and is selected from substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene and substituted or unsubstituted fluorene, and a substituent on the substituted cyclopentadiene, the substituted indene and the substituted fluorene is C1-6In the hydrocarbon radical and halogenOne or more of (a).
2. The early transition metal compound of claim 1, wherein R1、R2、R3And R4Each independently selected from H, C1-16A hydrocarbon group of1-16Alkoxy and halogen of (a);
mt is Ti, Zr or Hf;
n or n-1X are each independently selected from C1-8Linear or branched alkyl, fluorine, chlorine, bromine and iodine.
3. The early transition metal compound of claim 2, wherein R1、R2、R3And R4Each independently selected from H, C1-10A hydrocarbon group of1-10Alkoxy and halogen of (a);
R1and R2Each independently selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;
mt is Ti, Zr or Hf;
n or n-1X are each independently selected from methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo and iodo.
4. The early transition metal compound of claim 3, wherein R1、R2、R3And R4Each independently selected from H, C1-6A hydrocarbon group of1-6Alkoxy and halogen of (a);
R1and R2Each independently selected from substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;
mt is Ti, Zr or Hf;
n or n-1X are each independently selected from methyl, ethyl, fluorine, chlorine, bromine and iodine.
6. the intermediate of a transition metal compound according to any one of claims 1 to 5, wherein the intermediate of a transition metal compound is a compound represented by formula (2):
Each R is4Each independently selected from C1-20And C is a hydrocarbon group1-20And the other substituents are as defined in any one of claims 1 to 5.
7. An intermediate according to claim 6, wherein each R is4Each independently selected from C1-16And C is a hydrocarbon group1-16Alkoxy group of (2).
8. An intermediate according to claim 7, wherein each R is4Each independently selected from C1-10And C is a hydrocarbon group1-10Alkoxy group of (2).
9. An intermediate according to claim 8, wherein each R is4Each independently selected from C1-6And C is a hydrocarbon group1-6Alkoxy group of (2).
10. An intermediate according to claim 9, wherein each R is4Each is independentSelected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy.
11. The crystal of an early transition metal compound according to any one of claims 1 to 5, wherein the crystal system of the crystal is an orthorhombic system.
12. A process for preparing an early transition metal compound according to any of claims 1 to 5, which comprises:
(1) carrying out a first substitution reaction on a compound shown as a formula (4) and an organic lithium reagent;
(2) carrying out a second substitution reaction on the product of the first substitution reaction and the compound shown in the formula (a) to obtain a compound shown in a formula (3);
(3) carrying out a Staudinger reaction on a compound shown in a formula (3) and an azidosilane compound shown in a formula (b) to obtain a compound shown in a formula (2);
(4) carrying out a third substitution reaction on the compound shown in the formula (2) and the compound shown in the formula (c) to obtain a compound shown in the formula (1);
optionally, in the case that at least one of n X in the compound represented by formula (1) obtained in step (4) is halogen, the method further comprises: (5) performing a fourth substitution reaction on the compound shown in the formula (1) and a Grignard reagent or alkyl lithium, wherein the Grignard reagent is the compound shown in the formula (d), and the alkyl lithium is the compound shown in the formula (d');
Formula (d) R5-MgX '", formula (d') R5-Li,
Wherein R is1、R2、R3And R4Each independently selected from H, C1-20A hydrocarbon group of1-20Alkoxy and halogen of (a);
R1and R2Each independently selected from H, C1-4And substituted or unsubstituted C6-16Aryl of (a), the substituted C6-16The substituents on the aryl group of (A) are selected from C1-4A hydrocarbon group of (a);
each R is4Each independently selected from C1-20And C is a hydrocarbon group1-20Alkoxy group of (a);
R3is-MtXnor-Mt (X') Xn-1Wherein, in the step (A),
mt is a group IVB metal element;
n or n-1X are each independently selected from C1-10And halogen, and n ═ n '-1, n' is the valence of the element Mt; x' is a ligand of a metal element Mt and is selected from substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene and substituted or unsubstituted fluorene, and a substituent on the substituted cyclopentadiene, the substituted indene and the substituted fluorene is C1-6One or more of hydrocarbyl and halogen;
R5is selected from C1-10A hydrocarbon group of (a);
x "and X'" are each independently selected from halogen;
X1and X2Is H, X3Is H, ClOr Br.
13. The method of claim 12, wherein R1、R2、R3And R4Each independently selected from H, C1-16A hydrocarbon group of1-16Alkoxy and halogen of (a);
each R is4Each independently selected from C1-16And C is a hydrocarbon group1-16Alkoxy group of (a);
mt is Ti, Zr or Hf;
n or n-1X are each independently selected from C1-8Linear or branched alkyl groups of (a), fluorine, chlorine, bromine and iodine;
R5is selected from C1-8A hydrocarbon group of (1).
14. The method of claim 13, wherein R1、R2、R3And R4Each independently selected from H, C1-10A hydrocarbon group of1-10Alkoxy and halogen of (a);
R1and R2Each independently selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;
each R is4Each independently selected from C1-10And C is a hydrocarbon group1-10Alkoxy group of (a);
mt is Ti, Zr or Hf;
n or n-1X are each independently selected from methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, and iodo;
R5selected from methyl, ethyl, n-propyl or isopropyl.
15. The method of claim 14, wherein R1、R2、R3And R4Each independently selected from H, C1-6A hydrocarbon group of1-6Alkoxy and halogen of (a);
R1and R2Each independently selected from substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, the substituents of the substituted phenyl and substituted naphthyl each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl;
each R is4Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy;
mt is Ti, Zr or Hf;
n or n-1X are each independently selected from methyl, ethyl, fluoro, chloro, bromo and iodo;
R5selected from methyl or ethyl;
x "and X'" are each independently selected from the group consisting of fluorine, chlorine, bromine, and iodine.
16. The process of any one of claims 12-15, wherein the organolithium reagent is of formula R6-one or more of the compounds represented by Li, wherein R6Is C1-8Alkyl group of (1).
17. The process of claim 16, wherein the organolithium reagent is one or more of methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium.
18. The method of claim 16, wherein the compound of formula (4) and the organolithium reagent are used in a molar ratio of 1: 1.8-3.
19. The method of claim 18, wherein the compound of formula (4) and the organolithium reagent are used in a molar ratio of 1: 2-2.5.
20. The method of claim 16, wherein the first substitution reaction is carried out in the presence of a coordinating additive that is one or more of N, N' -Tetramethylethylenediamine (TMEDA), hexamethylphosphoric triamide (HMPA), and N, N-Dimethylpropylurea (DMPU).
21. The method of claim 20, wherein the complexing additive and organolithium reagent are present in a molar ratio of 0.5-2: 1.
22. the method of claim 21, wherein the complexing additive and organolithium reagent are present in a molar ratio of 0.8 to 1.5: 1.
23. the process according to any one of claims 12 to 15, wherein the compound of formula (4) and the compound of formula (a) are used in a molar ratio of 1: 1.8-3.
24. The method of claim 23, wherein the compound of formula (4) and the compound of formula (a) are used in a molar ratio of 1: 2-2.5.
25. The method according to claim 24, wherein the molar ratio of the compound represented by formula (3) to the azidosilane compound represented by formula (b) is 1: 1-5.
26. The method according to claim 25, wherein the molar ratio of the compound represented by formula (3) to the azidosilane compound represented by formula (b) is 1: 2-4.
27. The method according to claim 23, wherein the compound of formula (2) and the compound of formula (c) are used in a molar ratio of 1: 0.8-1.5.
28. The method of claim 27, wherein the compound of formula (2) and the compound of formula (c) are used in a molar ratio of 1: 1-1.2.
29. The method of any one of claims 12-15, wherein the conditions of the first substitution reaction comprise: the reaction is carried out for 0.5 to 2 hours at the temperature of between 90 ℃ below zero and 50 ℃ below zero, and then for 10 to 24 hours at the temperature of between 10 and 40 ℃.
30. The method of claim 29, wherein the conditions of the second substitution reaction comprise: the temperature is 10-40 ℃ and the time is 10-24 h.
31. The method of claim 30, wherein the conditions of the staudinger reaction comprise: the temperature is 80-150 ℃ and the time is 5-20 h.
32. The method of claim 30, wherein the conditions of the third substitution reaction comprise: the temperature is 80-150 ℃ and the time is 8-20 h.
33. The method according to any one of claims 12 to 15, wherein the compound represented by formula (1) and the grignard reagent or the alkyllithium are used in a molar ratio of 1: 0.8-8.
34. The method according to claim 33, wherein, in the case where step (5) is included, the compound represented by formula (1) and the grignard reagent or the alkyllithium are used in a molar ratio of 1: 1.5-6.
35. The method of claim 33, wherein the conditions of the fourth substitution reaction comprise: the temperature is 80-150 ℃ and the time is 8-20 h.
36. An early transition metal compound produced by the process of any one of claims 12 to 35.
37. Use of the early transition metal compound according to any one of claims 1 to 5 and 36 or the crystal of the early transition metal compound according to claim 11 for catalyzing ethylene homopolymerization and/or ethylene-alpha olefin copolymerization.
38. A catalyst composition for the polymerisation of olefins comprising a procatalyst which is an early transition metal compound according to any one of claims 1 to 5 and 36 or a crystal of an early transition metal compound according to claim 11 and an activator comprising one or more of an aluminium-containing compound and optionally an organoboron compound.
39. The composition according to claim 38, wherein, in the case where the activator is one or more of aluminum-containing compounds, the molar ratio of the contents of the main catalyst in terms of metal element Mt and the aluminum-containing compound in terms of aluminum element in the composition is 1: 50-3000 parts of;
in the case where the activator is an aluminum-containing compound and an organoboron compound, the composition contains the main catalyst in terms of metal element Mt, the aluminum-containing compound in terms of aluminum element, and the organoboron compound in terms of boron element in a molar ratio of 1: 0.1-500: 0.5-5.
40. The composition according to claim 39, wherein, in the case where the activator is one or more of aluminum-containing compounds, the molar ratio of the contents of the main catalyst in terms of metal element Mt and the aluminum-containing compound in terms of aluminum element in the composition is 1: 100-;
in the case where the activator is an aluminum-containing compound and an organoboron compound, the composition contains the main catalyst in terms of metal element Mt, the aluminum-containing compound in terms of aluminum element, and the organoboron compound in terms of boron element in a molar ratio of 1: 0.2-100: 1-3.
41. The composition according to claim 40, wherein, in the case where the activator is one or more of aluminum-containing compounds, the molar ratio of the contents of the main catalyst in terms of metal element Mt and the aluminum-containing compound in terms of aluminum element in the composition is 1: 100-500.
42. The composition of any of claims 38-41, wherein the aluminum-containing compound is a mixture of an alkylaluminum compound and an alkylaluminoxane compound or an alkylaluminoxane compound.
43. The composition according to claim 42, wherein the alkylaluminoxane compound is methylaluminoxane and/or isobutylaluminoxane and the alkylaluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride.
44. A composition as claimed in claim 42 wherein the organoboron compound is selected from one or more of tris (pentafluorophenyl) boron, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and triphenylcarbenium tetrakis (pentafluorophenyl) borate.
45. Use of a composition according to any one of claims 38 to 44 for catalysing ethylene homopolymerisation and/or ethylene-alpha olefin copolymerisation.
46. A process for producing an olefin polymer, the process comprising: in an organic solvent, in the presence of a catalyst, carrying out a polymerization reaction on an olefin monomer;
wherein the catalyst is the composition of any one of claims 38-44.
47. The method of claim 46, wherein the polymerization conditions comprise: the temperature is-50 ℃ to 200 ℃, and the pressure is 0.1MPa to 5 MPa.
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