CN110386956A - Application of the early transition metal compound and preparation method thereof with intermediate and in olefin polymerization - Google Patents
Application of the early transition metal compound and preparation method thereof with intermediate and in olefin polymerization Download PDFInfo
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- CN110386956A CN110386956A CN201810362109.8A CN201810362109A CN110386956A CN 110386956 A CN110386956 A CN 110386956A CN 201810362109 A CN201810362109 A CN 201810362109A CN 110386956 A CN110386956 A CN 110386956A
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 61
- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 188
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 22
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 118
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 82
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 66
- -1 normal-butyl Chemical group 0.000 claims description 59
- 239000000460 chlorine Substances 0.000 claims description 56
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 56
- 229910052801 chlorine Inorganic materials 0.000 claims description 51
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 48
- 229910052794 bromium Inorganic materials 0.000 claims description 47
- 238000006467 substitution reaction Methods 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 38
- 229910052736 halogen Inorganic materials 0.000 claims description 34
- 150000002367 halogens Chemical class 0.000 claims description 34
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052735 hafnium Inorganic materials 0.000 claims description 18
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 17
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 17
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 17
- 239000012190 activator Substances 0.000 claims description 16
- 150000002790 naphthalenes Chemical class 0.000 claims description 16
- 125000001424 substituent group Chemical group 0.000 claims description 16
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011737 fluorine Substances 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 229910052740 iodine Inorganic materials 0.000 claims description 15
- 239000011630 iodine Substances 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 125000001979 organolithium group Chemical group 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- 150000003624 transition metals Chemical class 0.000 claims description 10
- 239000007818 Grignard reagent Substances 0.000 claims description 9
- CHVJITGCYZJHLR-UHFFFAOYSA-N cyclohepta-1,3,5-triene Chemical class C1C=CC=CC=C1 CHVJITGCYZJHLR-UHFFFAOYSA-N 0.000 claims description 9
- 150000002220 fluorenes Chemical class 0.000 claims description 9
- 150000004795 grignard reagents Chemical class 0.000 claims description 9
- 150000002469 indenes Chemical class 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- 238000003800 Staudinger reaction Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000004306 cyclooctatetraenes Chemical class 0.000 claims description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- HWEQKSVYKBUIIK-UHFFFAOYSA-N cyclobuta-1,3-diene Chemical compound C1=CC=C1 HWEQKSVYKBUIIK-UHFFFAOYSA-N 0.000 claims description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 5
- 229910000765 intermetallic Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 3
- 150000005672 tetraenes Chemical class 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- DFGSACBYSGUJDZ-UHFFFAOYSA-M chloro(dihexyl)alumane Chemical compound [Cl-].CCCCCC[Al+]CCCCCC DFGSACBYSGUJDZ-UHFFFAOYSA-M 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
- 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
- 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
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 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
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical group [Li+].[CH3-] IHLVCKWPAMTVTG-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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 75
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 32
- 239000002904 solvent Substances 0.000 description 27
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000010936 titanium Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 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
- 239000012043 crude product Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 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 5
- 239000007789 gas Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229950005499 carbon tetrachloride Drugs 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 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 2
- 125000004429 atom Chemical group 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
- 238000007334 copolymerization reaction Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 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
- 229910052759 nickel Inorganic materials 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- SEDZOYHHAIAQIW-UHFFFAOYSA-N trimethylsilyl azide Chemical compound C[Si](C)(C)N=[N+]=[N-] SEDZOYHHAIAQIW-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances 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
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical class ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-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
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910003865 HfCl4 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- WYKFBKUNJHMXSA-UHFFFAOYSA-N [N].C[SiH](C)C Chemical compound [N].C[SiH](C)C WYKFBKUNJHMXSA-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 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
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 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
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- ZVQXQPNJHRNGID-UHFFFAOYSA-N tetramethylsuccinonitrile Chemical compound N#CC(C)(C)C(C)(C)C#N ZVQXQPNJHRNGID-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/535—Organo-phosphoranes
- C07F9/5355—Phosphoranes containing the structure P=N-
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to catalyst for olefines polymerizing fields, and in particular, to application of the early transition metal compound and preparation method thereof with intermediate and in olefin polymerization.The early transition metal compound is formula (1) compound represented.Being had using early transition metal compound or its crystal catalyzed alkene of the invention will be indicative high catalytic activity, and excellent catalytic activity be all had under wide in range polymeric reaction condition, and the catalyst is at low cost, be conducive to industrialized production.
Description
Technical field
The present invention relates to catalyst for olefines polymerizing fields, and in particular, to early transition metal compound and its preparation side
Method and intermediate and application in olefin polymerization.
Background technique
Polyolefin is to be widely used and very important a kind of high molecular material, includes ethylene, the homopolymer of alhpa olefin and altogether
Polymers.Polyolefin is with a very important position in synthetic resin industry, can be used as film, tubing, wire and cable and uses.
The progress of olefin polymerization catalysis technology is the direct driving force of polyolefin industry technological progress.From traditional
Single active center's metallocene catalyst that Ziegler-Natta catalyst occurs to late 1980s, then at the end of the 20th century
High activity " cyclopentadienyl after " and late transition metal catalyst, the catalytic polymerization of alkene be always the coke of researcher and production firm's concern
Point.
That there are catalytic activity is low for traditional Ziegler-Natta catalyst, and molecular weight distribution is wide, and polymerisation in solution obtains poly-
Close the disadvantage that remaining catalyst content is high in product.The discovery of 4th race's metallocene catalyst then preferably solves this and asks
Topic, due to single active center, enabling people to obtain expected structure as desired by the structure for changing catalyst
Polymer (W.Kaminsky etc., Adv.Organomet.Chem.1980,18,99；H.H.Brintzinger etc.,
Angew.Chem.Int.Ed.Engl.1995,34,1143).In recent ten years, to be replaced containing the ligand of the coordination atoms such as N, O, P
The metal complex that cyclopentadiene is obtained with transition-metal coordination also flourishes as the research of olefin polymerization catalysis,
This kind of catalyst are collectively referred to as catalyst " after cyclopentadienyl ".
Late transition metal (Fe, Co, Ni, Pd etc.) catalyst can obtain a variety of polyethylene products with catalyzed ethylene polymerization, such as
From the linear polyethylene to highly branched structure of height, from Unimodal Distribution to broad peak or the polyethylene and ethylene of bimodal distribution
With copolymer, the polyolefin block copolymer of polar monomer etc..
US006133387A discloses late transition metal Fe, Co, Ni, Pd being total to for alkene of double phosphinimines containing pyridine
Poly-, structure is as follows, but the activity of the complex-catalyzed vinyl polymerization is only under specific reaction condition (such as high pressure)
What is showed is higher, therefore is unfavorable for the extensive use of the catalyst:
Summary of the invention
The purpose of the present invention is to provide a kind of novel early transition metal compound and preparation method thereof and intermediate with
And application in olefin polymerization, higher urge is shown come catalysis in olefine polymerization using early transition metal compound of the invention
Change activity, high catalytic activity can be all had under wider polymerization pressure.
To achieve the goals above, one aspect of the present invention provides a kind of early transition metal compound, the early transition metal
Conjunction object is formula (1) compound represented:
Formula (1)
Wherein, R1、R2、R3And R4It is each independently selected from H, C1-20Alkyl, C1-20Alkoxy and halogen；
R1And R2It is each independently selected from H, C1-4Alkyl and substituted or unsubstituted C6-12Aryl, the substituted C6-12
Aryl on substituent group be selected from C1-4Alkyl；
R3For-MtXnOr-Mt (X ') Xn, wherein
Mt is group ivb metallic element；
2n X is each independently selected from C1-10Alkyl and halogen, and n=n ' -1, n ' be element M t chemical valence；X ' is
The ligand of metallic element Mt.
Second aspect of the present invention provides the intermediate of above-mentioned early transition metal compound, wherein the early transition metal chemical combination
The intermediate of object is formula (2) compound represented:
Formula (2)
Each R4It is each independently selected from C1-20Alkyl and C1-20Alkoxy.
Third aspect present invention provides the crystal of above-mentioned early transition metal compound, wherein the crystallographic system of the crystal is three oblique
Crystallographic system.
Fourth aspect present invention provides a kind of preparation method of early transition metal compound, this method comprises:
(1) formula (4) compound represented and organolithium reagent are subjected to the first substitution reaction；
(2) product of the first substitution reaction and formula (a) compound represented are subjected to the second substitution reaction, obtain formula (3)
Compound represented；
(3) azide silane class compound shown in formula (3) compound represented and formula (b) is subjected to staudinger reaction,
Obtain formula (2) compound represented；
(4) formula (2) compound represented and formula (c) compound represented are subjected to third substitution reaction, obtain formula (1) institute
The compound shown；
It optionally, should in the case that at least one X is halogen in step (4) resulting formula (1) compound represented
Method further include: (5) formula (1) compound represented and Grignard Reagent or lithium alkylide carry out the 4th substitution reaction, the grignard examination
Agent is formula (d) compound represented, and the lithium alkylide is formula (d ') compound represented；
Formula (1)Formula (2)
Formula (3)Formula (4)
Formula (a)Formula (b)Formula (c) R3- X ",
Formula (d) R5- MgX " ', formula (d ') R5- Li,
Wherein, R1、R2、R3And R4It is each independently selected from H, C1-20Alkyl, C1-20Alkoxy and halogen；
R1And R2It is each independently selected from H, C1-4Alkyl and substituted or unsubstituted C6-12Aryl, the substituted C6-12
Aryl on substituent group be selected from C1-4Alkyl；
Each R4It is each independently selected from C1-20Alkyl and C1-20Alkoxy；
R3For-MtXnOr-Mt (X ') Xn, wherein
Mt is group ivb metallic element；
2n X is each independently selected from C1-10Alkyl and halogen, and n=n ' -1, n ' be element M t chemical valence；X ' is
The ligand of metallic element Mt；
R5Selected from C1-10Alkyl；
X " and X " ' is each independently selected from halogen.
Fifth aspect present invention provides early transition metal compound made from the above method.
Sixth aspect present invention provides the crystal of above-mentioned early transition metal compound or above-mentioned early transition metal compound
Application in the reaction of catalysis ethylene homo and/or ethylene-alpha-olefin copolyreaction.
Seventh aspect present invention provides a kind of carbon monoxide-olefin polymeric suitable for olefinic polymerization, and the composition contains main catalytic
Agent and activator, the major catalyst are the crystal of above-mentioned early transition metal compound or above-mentioned early transition metal compound,
The activator includes one of aluminum contained compound or a variety of and optionally contain organoboron compound.
Eighth aspect present invention provides above-mentioned composition in the reaction of catalysis ethylene homo and/or ethylene-alpha-olefin copolyreaction
In application.
Ninth aspect present invention provides a kind of preparation method of olefin polymer, this method comprises: in organic solvent, In
In the presence of catalyst, olefinic monomer is subjected to polymerization reaction；
Wherein, the catalyst is above-mentioned composition.
High catalytic activity will be shown using early transition metal compound or its crystal catalysis in olefine polymerization of the invention,
And excellent catalytic activity is all had under wide in range polymeric reaction condition, and the catalyst is at low cost, be conducive to industrialization
Production.
Detailed description of the invention
Fig. 1 is the complex structure figure that formula (1-Ti-1) compound represented monocrystalline passes through that single crystal diffraction is analyzed to identify
(ORTEP figure) and corresponding atom number.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of early transition metal compound, which is shown in formula (1)
Compound:
Formula (1)
Wherein, R1、R2、R3And R4It is each independently selected from H, C1-20Alkyl, C1-20Alkoxy and halogen；
R1And R2It is each independently selected from H, C1-4Alkyl and substituted or unsubstituted C6-12Aryl, the substituted C6-12
Aryl on substituent group be selected from C1-4Alkyl；
R3For-MtXnOr-Mt (X ') Xn, wherein
Mt is group ivb metallic element；
2n X is each independently selected from C1-10Alkyl and halogen, and n=n ' -1, n ' be element M t chemical valence；X ' is
The ligand of metallic element Mt.
In the present invention, the C1-20Alkyl refer to the total number of carbon atoms be 1-20 alkyl, can be straight chain or branch
Alkyl group can be the alkenyl with unsaturated carbon-carbon double bond of linear chain or branched chain, such as can be C1、C2、C3、C4、C5、C6、
C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19Or C20Alkyl.For example, the C1-20Alkyl can be
C1-20Alkyl or C2-20Alkenyl.For C1-16Alkyl, C1-10Alkyl, C1-8Alkyl, C1-6The explanation of alkyl can also
Using above-mentioned definition, carbon atom number is different, as long as but the specific alkyl in the carbon atom number range can be from above-mentioned tool
It is selected in the suitable carbon atom number alkyl that body is enumerated.
The C1-20Alkoxy refer to that the total number of carbon atoms is the alkoxy of 1-20, such as can be C1、C2、C3、C4、C5、
C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19Or C20Alkoxy.For C1-16Alkoxy, C1-10
Alkoxy, C1-8Alkoxy, C1-6The explanation of alkoxy above-mentioned definition can also be used, carbon atom number is different, but
As long as specific alkoxy in the carbon atom number range can from the above-mentioned suitable carbon atom number alkoxy specifically enumerated into
Row selection.
The C1-4Alkyl refer to that the total number of carbon atoms is the alkyl of 1-4, such as can be C1、C2、C3Or C4Alkyl.Example
It such as can be C1-4Alkyl or C2-4Alkenyl, specific group for example can (can be by for methyl (can be indicated by Me), ethyl
Et is indicated), n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, allyl, acrylic etc..
The unsubstituted C6-16Aryl refer to that the total number of carbon atoms is the aryl of 6-16, can be heteroaryl, can also be with
It is non-heteroaryl, such as can be phenyl (can be indicated by Ph), naphthalene, xenyl, anthryl or phenanthryl.
The substituted C6-16Aryl refer to do not include substituent group carbon atom number under the carbon atom of the aromatic ring always exist
6-16 can be heteroaryl, be also possible to non-heteroaryl, and the H of at least one aromatic ring is by C on the substituted aryl1-4Alkyl
Replace, such as can be by C1-4Alkyl replace phenyl, by C1-4Alkyl replace naphthalene, by C1-4Alkyl replace
Xenyl, by C1-4Alkyl replace anthryl or by C1-4Alkyl replace phenanthryl.
The group ivb metallic element can be Ti, Zr or Hf.
The halogen can be fluorine, chlorine, bromine or iodine.
In the present invention, the group being represented by identical symbol can be selected independently in limited range, can be with
It is identical to can also be different, such as although have the substituent group at two all by R in formula (1)1It indicates, but this R at two1It can be identical
It can also be different, each leisure R1Definition in be selected independently.For example, 2n X also can be the same or different, it
Be all to be selected in the definition of X each independently.
Wherein, n can be 2,3 or 4.
X ' is the ligand of metallic element Mt, and such ligand can be π-ligand, such as X ' replaces or do not take
It is the 1,3- cyclobutadiene in generation, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indenes, substituted or unsubstituted
Fluorenes, substituted or unsubstituted phenyl ring, substituted or unsubstituted 1,3,5- cycloheptatriene or substituted or unsubstituted ring are pungent
Tetraene；It wherein, for example can be C for the substituent group on these ligands1-6Alkyl and one of halogen etc. or a variety of.
In a preferred embodiment of the invention, R1、R2、R3And R4It is each independently selected from H, C1-16Alkyl,
C1-16Alkoxy and halogen；
Mt is Ti, Zr or Hf；
2n X is each independently selected from C1-8Alkyl, fluorine, chlorine, bromine and iodine.
In another preferred embodiment of the invention, R1、R2、R3And R4It is each independently selected from H, C1-10Hydrocarbon
Base, C1-10Alkoxy and halogen；
R1And R2It is each independently selected from H, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, takes
The substituent group of generation or unsubstituted phenyl and substituted or unsubstituted naphthalene, the substituted phenyl and substituted naphthalene is respectively
Independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl and tert-butyl；
Mt is Ti, Zr or Hf；
2n X is each independently selected from methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine and iodine；X ' be replace or
Unsubstituted 1,3- cyclobutadiene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indenes, replace or do not take
The fluorenes in generation, substituted or unsubstituted phenyl ring, substituted or unsubstituted 1,3,5- cycloheptatriene or substituted or unsubstituted
Cyclo-octatetraene.
In a kind of preferred embodiment of the invention, R1、R2、R3And R4It is each independently selected from H, C1-6Hydrocarbon
Base, C1-6Alkoxy and halogen；
R1And R2It is each independently selected from substituted or unsubstituted phenyl and substituted or unsubstituted naphthalene, the substitution
Phenyl and the substituent group of substituted naphthalene be each independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl
And tert-butyl；
Mt is Ti, Zr or Hf；
2n X is each independently selected from methyl, ethyl, fluorine, chlorine, bromine and iodine；X ' is substituted or unsubstituted 1,3- ring
Butadiene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indenes, substituted or unsubstituted fluorenes, replace
Or unsubstituted phenyl ring, substituted or unsubstituted 1,3,5- cycloheptatriene or substituted or unsubstituted cyclo-octatetraene.
According to the present invention, the early transition metal compound is preferably one of compound shown in following formula:
Formula (1-Ti-1): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-Mt (X ') Xn, Mt is
Ti, 2n X are Cl, n=2, X ' it is cyclopentadiene；
Formula (1-Ti-2): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-MtXn, Mt Ti, 2n
A X is Cl, n=3；
Formula (1-Ti-3): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-Mt (X ') Xn, Mt is
Ti, 2n X are methyl, n=2, X ' it is cyclopentadiene；
Formula (1-Ti-4): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-Mt (X ') Xn, Mt is
Ti, 2n X are Br, n=2, X ' it is cyclopentadiene；
Formula (1-Ti-5): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-MtXn, Mt Ti, 2n
A X is Br, n=3；
Formula (1-Ti-6): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-Mt (X ') Xn, Mt is
Ti, 2n X are ethyl, n=2, X ' it is cyclopentadiene；
Formula (1-Ti-7): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-Mt (X ')
Xn, Mt Ti, 2n X are Cl, n=2, X ' and it is cyclopentadiene；
Formula (1-Ti-8): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-MtXn, Mt Ti, n
X is Cl, n=3；
Formula (1-Ti-9): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-Mt (X ')
Xn, Mt Ti, 2n X are methyl, n=2, X ' and it is cyclopentadiene；
Formula (1-Ti-10): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-Mt
(X’)Xn, Mt Ti, 2n X are Br, n=2, X ' and it is cyclopentadiene；
Formula (1-Ti-11): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-MtXn,
Mt is Ti, and 2n X is Br, n=3；
Formula (1-Ti-12): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-Mt
(X’)Xn, Mt Ti, 2n X are ethyl, n=2, X ' and it is cyclopentadiene；
Formula (1-Ti-13): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-Mt (X ') Xn, Mt
It is Cl, n=2, X for Ti, 2n X ' it is cyclopentadiene；
Formula (1-Ti-14): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-MtXn, Mt Ti,
2n X is Cl, n=3；
Formula (1-Ti-15): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-Mt (X ') Xn, Mt
It is methyl, n=2, X for Ti, 2n X ' it is cyclopentadiene；
Formula (1-Ti-16): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-Mt (X ') Xn, Mt
It is Br, n=2, X for Ti, 2n X ' it is cyclopentadiene；
Formula (1-Ti-17): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-MtXn, Mt Ti,
2n X is Br, n=3；
Formula (1-Ti-18): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-Mt (X ') Xn, Mt
It is ethyl, n=2, X for Ti, 2n X ' it is cyclopentadiene；
Formula (1-Ti-19): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-Mt
(X’)Xn, Mt Ti, 2n X are Cl, n=2, X ' and it is cyclopentadiene；
Formula (1-Ti-20): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-
MtXn, Mt Ti, 2n X are Cl, n=3；
Formula (1-Ti-21): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-Mt
(X’)Xn, Mt Ti, 2n X are methyl, n=2, X ' and it is cyclopentadiene；
Formula (1-Ti-22): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-Mt
(X’)Xn, Mt Ti, 2n X are Br, n=2, X ' and it is cyclopentadiene；
Formula (1-Ti-23): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-
MtXn, Mt Ti, 2n X are Br, n=3；
Formula (1-Ti-24): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-Mt
(X’)Xn, Mt Ti, 2n X are ethyl, n=2, X ' and it is cyclopentadiene；
Formula (1-Zr-1): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-Mt (X ') Xn, Mt is
Zr, 2n X are Cl, n=2, X ' it is cyclopentadiene；
Formula (1-Zr-2): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-MtXn, Mt Zr, 2n
A X is Cl, n=3；
Formula (1-Zr-3): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-Mt (X ') Xn, Mt is
Zr, 2n X are methyl, n=2, X ' it is cyclopentadiene；
Formula (1-Zr-4): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-Mt (X ') Xn, Mt is
Zr, 2n X are Br, n=2, X ' it is cyclopentadiene；
Formula (1-Zr-5): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-MtXn, Mt Zr, 2n
A X is Br, n=3；
Formula (1-Zr-6): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-Mt (X ') Xn, Mt is
Zr, 2n X are ethyl, n=2, X ' it is cyclopentadiene；
Formula (1-Zr-7): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-Mt (X ')
Xn, Mt Zr, 2n X are Cl, n=2, X ' and it is cyclopentadiene；
Formula (1-Zr-8): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-MtXn, Mt Zr, n
X is Cl, n=3；
Formula (1-Zr-9): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-Mt (X ')
Xn, Mt Zr, 2n X are methyl, n=2, X ' and it is cyclopentadiene；
Formula (1-Zr-10): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-Mt
(X’)Xn, Mt Zr, 2n X are Br, n=2, X ' and it is cyclopentadiene；
Formula (1-Zr-11): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-MtXn,
Mt is Zr, and 2n X is Br, n=3；
Formula (1-Zr-12): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-Mt
(X’)Xn, Mt Zr, 2n X are ethyl, n=2, X ' and it is cyclopentadiene；
Formula (1-Zr-13): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-Mt (X ') Xn, Mt
It is Cl, n=2, X for Zr, 2n X ' it is cyclopentadiene；
Formula (1-Zr-14): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-MtXn, Mt Zr,
2n X is Cl, n=3；
Formula (1-Zr-15): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-Mt (X ') Xn, Mt
It is methyl, n=2, X for Zr, 2n X ' it is cyclopentadiene；
Formula (1-Zr-16): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-Mt (X ') Xn, Mt
It is Br, n=2, X for Zr, 2n X ' it is cyclopentadiene；
Formula (1-Zr-17): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-MtXn, Mt Zr,
2n X is Br, n=3；
Formula (1-Zr-18): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-Mt (X ') Xn, Mt
It is ethyl, n=2, X for Zr, 2n X ' it is cyclopentadiene；
Formula (1-Zr-19): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-Mt
(X’)Xn, Mt Zr, 2n X are Cl, n=2, X ' and it is cyclopentadiene；
Formula (1-Zr-20): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-
MtXn, Mt Zr, 2n X are Cl, n=3；
Formula (1-Zr-21): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-Mt
(X’)Xn, Mt Zr, 2n X are methyl, n=2, X ' and it is cyclopentadiene；
Formula (1-Zr-22): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-Mt
(X’)Xn, Mt Zr, 2n X are Br, n=2, X ' and it is cyclopentadiene；
Formula (1-Zr-23): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-
MtXn, Mt Zr, 2n X are Br, n=3；
Formula (1-Zr-24): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-Mt
(X’)Xn, Mt Zr, 2n X are ethyl, n=2, X ' and it is cyclopentadiene；
Formula (1-Hf-1): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-Mt (X ') Xn, Mt is
Hf, 2n X are Cl, n=2, X ' it is cyclopentadiene；
Formula (1-Hf-2): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-MtXn, Mt Hf, 2n
A X is Cl, n=3；
Formula (1-Hf-3): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-Mt (X ') Xn, Mt is
Hf, 2n X are methyl, n=2, X ' it is cyclopentadiene；
Formula (1-Hf-4): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-Mt (X ') Xn, Mt is
Hf, 2n X are Br, n=2, X ' it is cyclopentadiene；
Formula (1-Hf-5): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-MtXn, Mt Hf, 2n
A X is Br, n=3；
Formula (1-Hf-6): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-Mt (X ') Xn, Mt is
Hf, 2n X are ethyl, n=2, X ' it is cyclopentadiene；
Formula (1-Hf-7): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-Mt (X ')
Xn, Mt Hf, 2n X are Cl, n=2, X ' and it is cyclopentadiene；
Formula (1-Hf-8): in formula (1), R1、R2、R3And R4It is H, R1And R2It is phenyl, R3For-MtXn, Mt Hf, n
X is Cl, n=3；
Formula (1-Hf-9): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-Mt (X ')
Xn, Mt Hf, 2n X are methyl, n=2, X ' and it is cyclopentadiene；
Formula (1-Hf-10): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-Mt
(X’)Xn, Mt Hf, 2n X are Br, n=2, X ' and it is cyclopentadiene；
Formula (1-Hf-11): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-MtXn,
Mt is Hf, and 2n X is Br, n=3；
Formula (1-Hf-12): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is phenyl, R3For-Mt
(X’)Xn, Mt Hf, 2n X are ethyl, n=2, X ' and it is cyclopentadiene；
Formula (1-Hf-13): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-Mt (X ') Xn, Mt
It is Cl, n=2, X for Hf, 2n X ' it is cyclopentadiene；
Formula (1-Hf-14): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-MtXn, Mt Hf,
2n X is Cl, n=3；
Formula (1-Hf-15): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-Mt (X ') Xn, Mt
It is methyl, n=2, X for Hf, 2n X ' it is cyclopentadiene；
Formula (1-Hf-16): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-Mt (X ') Xn, Mt
It is Br, n=2, X for Hf, 2n X ' it is cyclopentadiene；
Formula (1-Hf-17): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-MtXn, Mt Hf,
2n X is Br, n=3；
Formula (1-Hf-18): in formula (1), R1、R2、R3And R4It is H, R1And R2It is tert-butyl, R3For-Mt (X ') Xn, Mt
It is ethyl, n=2, X for Hf, 2n X ' it is cyclopentadiene；
Formula (1-Hf-19): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-Mt
(X’)Xn, Mt Hf, 2n X are Cl, n=2, X ' and it is cyclopentadiene；
Formula (1-Hf-20): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-
MtXn, Mt Hf, 2n X are Cl, n=3；
Formula (1-Hf-21): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-Mt
(X’)Xn, Mt Hf, 2n X are methyl, n=2, X ' and it is cyclopentadiene；
Formula (1-Hf-22): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-Mt
(X’)Xn, Mt Hf, 2n X are Br, n=2, X ' and it is cyclopentadiene；
Formula (1-Hf-23): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-
MtXn, Mt Hf, 2n X are Br, n=3；
Formula (1-Hf-24): in formula (1), R1、R2And R3It is H, R4It is methyl, R1And R2It is tert-butyl, R3For-Mt
(X’)Xn, Mt Hf, 2n X are ethyl, n=2, X ' and it is cyclopentadiene.
In a preferred embodiment of the invention, the early transition metal compound is compound shown in following formula
One of:
Second aspect of the present invention provides the intermediate of above-mentioned early transition metal compound, wherein the early transition metal chemical combination
The intermediate of object is formula (2) compound represented:
Formula (2)
Each R4It is each independently selected from C1-20Alkyl and C1-20Alkoxy.
The selection of other groups in formula (2) will describe to carry out according to the group above for formula (1), and the present invention is herein
It repeats no more.
Preferably, each R4It is each independently selected from C1-16Alkyl and C1-16Alkoxy.
It is highly preferred that each R4It is each independently selected from C1-10Alkyl and C1-10Alkoxy.
It is highly preferred that each R4It is each independently selected from C1-6Alkyl and C1-6Alkoxy.
It is further preferred that each R4It is each independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, secondary
Butyl, tert-butyl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy.
The specific choice of the intermediate of above-mentioned early transition metal compound shown in formula (2) can be according to above-described preceding mistake
The specific example for crossing metallic compound is selected.
In a preferred embodiment of the invention, intermediate shown in formula (2) is in compound shown in following formula
It is a kind of:
Third aspect present invention provides the crystal of above-mentioned early transition metal compound, wherein the crystallographic system of the crystal is
Anorthic system.
Specifically, the monocrystalline of early transition metal compound shown in above-mentioned formula (1-Ti-1), crystallographic system is anorthic system, empty
Between group be P-1, cell parameter:α=86.02 ° (3), β=
89.96 ° (3), γ=61.44 ° (3), Z=2, ρcalc=1.4082g/cm3。
For mixed crystal or the early transition metal compound of on-monocrystalline form, early transition metal chemical combination of the invention
Object monocrystalline will have higher catalytic activity.
Fourth aspect present invention provides a kind of preparation method of early transition metal compound, this method comprises:
(1) formula (4) compound represented and organolithium reagent are subjected to the first substitution reaction；
(2) product of the first substitution reaction and formula (a) compound represented are subjected to the second substitution reaction, obtain formula (3)
Compound represented；
(3) azide silane class compound shown in formula (3) compound represented and formula (b) is subjected to staudinger reaction,
Obtain formula (2) compound represented；
(4) formula (2) compound represented and formula (c) compound represented are subjected to third substitution reaction, obtain formula (1) institute
The compound shown；
It optionally, should in the case that at least one X is halogen in step (4) resulting formula (1) compound represented
Method further include: (5) formula (1) compound represented and Grignard Reagent or lithium alkylide carry out the 4th substitution reaction, the grignard examination
Agent is formula (d) compound represented, and the lithium alkylide is formula (d ') compound represented；
Formula (1)Formula (2)
Formula (3)Formula (4)
Formula (a)Formula (b)Formula (c) R3- X ",
Formula (d) R5- MgX " ', formula (d ') R5- Li,
Wherein, R1、R2、R3And R4It is each independently selected from H, C1-20Alkyl, C1-20Alkoxy and halogen；
R1And R2It is each independently selected from H, C1-4Alkyl and substituted or unsubstituted C6-12Aryl, the substituted C6-12
Aryl on substituent group be selected from C1-4Alkyl；
Each R4It is each independently selected from C1-20Alkyl and C1-20Alkoxy；
R3For-MtXnOr-Mt (X ') Xn, wherein
Mt is group ivb metallic element；
2n X is each independently selected from C1-10Alkyl and halogen, and n=n ' -1, n ' be element M t chemical valence；X ' is
The ligand of metallic element Mt；
R5Selected from C1-10Alkyl；
X " and X " ' is each independently selected from halogen.
According to the present invention, above-mentioned group can be selected according to hereinbefore associated description, and details are not described herein by the present invention.
Preferably, R1、R2、R3And R4It is each independently selected from H, C1-16Alkyl, C1-16Alkoxy and halogen；
Each R4It is each independently selected from C1-16Alkyl and C1-16Alkoxy；
Mt is Ti, Zr or Hf；
2n X is each independently selected from C1-8Alkyl, fluorine, chlorine, bromine and iodine；
R5Selected from C1-8Alkyl.
It is highly preferred that R1、R2、R3And R4It is each independently selected from H, C1-10Alkyl, C1-10Alkoxy and halogen；
R1And R2It is each independently selected from H, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, takes
The substituent group of generation or unsubstituted phenyl and substituted or unsubstituted naphthalene, the substituted phenyl and substituted naphthalene is respectively
Independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl and tert-butyl；
Each R4It is each independently selected from C1-10Alkyl and C1-10Alkoxy；
Mt is Ti, Zr or Hf；
2n X is each independently selected from methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine and iodine；X ' be replace or
Unsubstituted 1,3- cyclobutadiene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indenes, replace or do not take
The fluorenes in generation, substituted or unsubstituted phenyl ring, substituted or unsubstituted 1,3,5- cycloheptatriene or substituted or unsubstituted
Cyclo-octatetraene；
R5Selected from methyl, ethyl, n-propyl or isopropyl.
It is further preferred that R1、R2、R3And R4It is each independently selected from H, C1-6Alkyl, C1-6Alkoxy and halogen
Element；
R1And R2It is each independently selected from substituted or unsubstituted phenyl and substituted or unsubstituted naphthalene, the substitution
Phenyl and the substituent group of substituted naphthalene be each independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl
And tert-butyl；
Each R4It is each independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, methoxy
Base, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy；
Mt is Ti, Zr or Hf；
2n X is each independently selected from methyl, ethyl, fluorine, chlorine, bromine and iodine；X ' is substituted or unsubstituted 1,3- ring
Butadiene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indenes, substituted or unsubstituted fluorenes, replace
Or unsubstituted phenyl ring, substituted or unsubstituted 1,3,5- cycloheptatriene or substituted or unsubstituted cyclo-octatetraene；
R5Selected from methyl or ethyl；
X " and X " ' is each independently selected from fluorine, chlorine, bromine and iodine.
In above-mentioned preparation method, the compound of reaction can be one of above-mentioned formula compound represented or a variety of,
The formula prepared by (1) compound represented can be by one of the formula (1) compound represented or a variety of formulas (1)
The mixture of compound represented, this is within.
Wherein, the specific example of compound shown in formula (3) can be selected from one of compound shown in following formula or a variety of:
Formula (3-1)Formula (3-1)
Formula (3-3)Formula (3-4)
The specific example of compound shown in formula (4) can be selected from one of compound shown in following formula or a variety of:
Formula (4-1)(also referred to as diphenyl ether)；
Formula (4-2)
The specific example of compound shown in formula (a) can be selected from one of compound shown in following formula or a variety of:
Formula (a-1): in formula (a), R1And R2It is phenyl, X3For chlorine (also referred to as diphenyl phosphine chloride)；
Formula (a-2): in formula (a), R1And R2It is tert-butyl, X3For chlorine；
Formula (a-3): in formula (a), R1And R2It is phenyl, X3For H；
Formula (a-4): in formula (a), R1And R2It is tert-butyl, X3For H；
Formula (a-5): in formula (a), R1And R2It is phenyl, X3For bromine；
Formula (a-2): in formula (a), R1And R2It is tert-butyl, X3For bromine.
The specific example of compound shown in formula (b) can be selected from one of compound shown in following formula or a variety of:
Formula (b-1): in formula (b), R4It is methyl (also referred to as azidotrimethylsilane)；
Formula (b-2): in formula (b), R4It is ethyl；
Formula (b-3): in formula (b), R4It is methoxyl group；
Formula (b-2): in formula (b), R4It is ethyoxyl.
The specific example of compound shown in formula (c) can be selected from one of compound shown in following formula or a variety of:
Formula (c-Ti-1): in formula (c), X " is Cl, R3For-Mt (X ') Xn, Mt Ti, n X are Cl, n=2, X ' and it is ring
Pentadiene (also referred to as CpTiCl3)；
Formula (c-Ti-2): in formula (c), X " is Cl, R3For-MtXn, Mt Ti, n X are Cl, and n=3 is (also referred to as
TiCl4)；
Formula (c-Ti-3): in formula (c), X " is Br, R3For-Mt (X ') Xn, Mt Ti, n X are Br, n=2, X ' and it is ring
Pentadiene；
Formula (c-Ti-4): in formula (c), X " is Br, R3For-MtXn, Mt Ti, n X are Br, n=3；
Formula (c-Zr-1): in formula (c), X " is chlorine, R3For-Mt (X ') Xn, Mt Zr, n X are Cl, n=2, X ' and it is ring
Pentadiene (also referred to as CpZrCl3)；
Formula (c-Zr-2): in formula (c), X " is chlorine, R3For-MtXn, Mt Zr, n X are Cl, and n=3 is (also referred to as
ZrCl4)；
Formula (c-Zr-3): in formula (c), X " is Br, R3For-Mt (X ') Xn, Mt Zr, n X are Br, n=2, X ' and it is ring
Pentadiene；
Formula (c-Zr-4): in formula (c), X " is Br, R3For-MtXn, Mt Zr, n X are Br, n=3；
Formula (c-Hf-1): in formula (c), X " is chlorine, R3For-Mt (X ') Xn, Mt Hf, n X are Cl, n=2, X ' and it is ring
Pentadiene (also referred to as CpHfCl3)；
Formula (c-Hf-2): in formula (c), X " is chlorine, R3For-MtXn, Mt Hf, n X are Cl, and n=3 is (also referred to as
HfCl4)；
Formula (c-Hf-3): in formula (c), X " is Br, R3For-Mt (X ') Xn, Mt Hf, n X are Br, n=2, X ' and it is ring
Pentadiene；
Formula (c-Hf-4): in formula (c), X " is Br, R3For-MtXn, Mt Hf, n X are Br, n=3.
The specific example of compound shown in formula (d) can be selected from one of compound shown in following formula or a variety of:
Formula (d-1): in formula (d), R5For methyl, X " ' it is Br (can also be indicated by MeMgBr)；
Formula (d-2): in formula (d), R5For methyl, X " ' it is Cl (can also be indicated by MeMgCl)；
Formula (d-3): in formula (d), R5For ethyl, X " ' it is Br (can also be indicated by EtMgBr)；
Formula (d-4): in formula (d), R5For ethyl, X " ' it is Cl (can also be indicated by EtMgCl).
The specific example of compound shown in formula (d ') can be selected from one of compound shown in following formula or a variety of:
Formula (d ' -1): in formula (d '), R5For methyl；
Formula (d ' -2): in formula (d '), R5For ethyl.
It according to the present invention, will be so that formula (4) compound represented forms lithium salts by the first substitution reaction of step (1)
Form, i.e. the X shown in formula (4)1And X2Lithium salts is formed at group.Wherein, the organolithium reagent can be from a variety of organolithiums
It is selected in compound, it is preferable that the organolithium reagent is formula R6One of-Li compound represented is a variety of,
In, R6For C1-8Alkyl.It is highly preferred that the organolithium reagent is lithium methide, ethyl-lithium, n-propyl lithium, isopropyl lithium, just
One of butyl lithium, s-butyl lithium and tert-butyl lithium are a variety of.
According to the present invention, the dosage of the organolithium reagent can change in a wider range, as long as enabling to formula (4)
Compound represented is adequately formed corresponding lithium salts, it is preferable that formula (4) compound represented and organolithium reagent
Mole dosage ratio be 1:1.8-3, preferably 1:2-2.5.
According to the present invention, the solvent that first substitution reaction uses can be good to have to formula (4) compound represented
The various solvents of good dissolving, such as selected from toluene, n-hexane, pentane, benzene, dimethylbenzene, methylene chloride, chloroform, four
One of chloromethanes and tetrahydrofuran are a variety of.The dosage of the solvent can change in a wider range, such as relative to
Formula (4) compound represented of 10mmol, the dosage of the solvent are 10-200mL.
In the case of, according to the invention it is preferred to, it is -90 DEG C to -50 that the condition of first substitution reaction, which includes: first in temperature,
0.5-2h is reacted at DEG C, then reacts 10-24h at 10-40 DEG C.It is highly preferred that the condition of first substitution reaction includes: elder generation
0.5-1.5h is reacted at being -80 DEG C to -70 DEG C in temperature, then reacts 12-20h at 20-30 DEG C.It can first will be shown in formula (4)
Compound mixed with solvent, then again under -90 DEG C to -50 DEG C (preferably -80 DEG C to -70 DEG C) introduce organolithium reagent (example
Such as using the form being added dropwise), and carry out first substitution reaction.
According to the present invention, formula (3) compound represented will be formed, wherein can by the second substitution reaction in step (2)
The second substitution reaction is carried out with formula (a) compound represented extracting step (1) resulting substitution product, it is preferred that
Not extraction step (1) resulting substitution product, but formula (a) compound represented is directly introduced to the body of the first substitution reaction
The second substitution reaction is carried out in system.Wherein, the dosage of formula (a) compound represented can change in a wider range, as long as energy
Enough obtain formula (3) compound represented, it is preferable that mole of formula (4) compound represented and formula (a) compound represented
Amount ratio is 1:1.8-3, preferably 1:2-2.5.
According to the present invention, formula (a) compound represented can be provided in the form of pure compound, but in order to promote
Second substitution reaction substantially more carries out, and formula (a) compound represented is provided in the form of its solution, used molten
Agent for example can be toluene, n-hexane, pentane, benzene, dimethylbenzene, methylene chloride, chloroform, tetrachloromethane and tetrahydrofuran
One of or it is a variety of, dosage can for example make formula (a) compound represented solution concentration be 0.5-10mmol/mL.
In the case of, according to the invention it is preferred to, the condition of second substitution reaction includes: that temperature is 10-40 DEG C, and the time is
10-24h.It is highly preferred that it is 20-30 DEG C that the condition of second substitution reaction, which includes: temperature, time 12-20h.Wherein, should
The operating process of step (2) may include: that formula (a) compound represented solution is introduced to the first substitution under condition of ice bath
(for example, by using the mode of dropwise addition) in the system of reaction, then reacted under conditions of the second substitution reaction again.
According to the present invention, in order to extract formula (3) compound represented, can terminate in second substitution reaction
Solvent (for example, by using the mode of rotary evaporation) is removed afterwards, and is washed (such as with acetone washing), is then dried, i.e.,
It can get formula (3) compound represented.
According to the present invention, the staudinger reaction by step (3) can make formula (3) compound represented and formula (b)
Shown in azide silane class compound react be made formula (2) compound represented.Wherein, formula (3) compound represented and formula (b)
Shown in the consumption proportion of azide silane class compound can change in a wider range, in order to enable chemical combination shown in formula (3)
Object can substantially more react, it is preferable that azide silane class compound shown in formula (3) compound represented and formula (b)
Mole dosage ratio is 1:1.8-5, preferably 1:2-4.
According to the present invention, which can be selected from toluene, n-hexane, pentane, benzene, dimethylbenzene, methylene chloride, three chloromethanes
It is carried out in the presence of one of alkane, tetrachloromethane and tetrahydrofuran or a variety of organic solvents, the dosage of the organic solvent can be with
It changes in a wider range, such as relative to formula (3) compound represented of 10mmol, the dosage of the organic solvent is 10-
200mL。
In the case of, according to the invention it is preferred to, the condition of the staudinger reaction includes: that temperature is 80-150 DEG C, the time
For 5-20h.It is highly preferred that it is 100-140 DEG C that the condition of the staudinger reaction, which includes: temperature, time 8-14h.Wherein,
In order to extract formula (2) compound represented, solvent can be removed after the completion of reaction (for example, by using the side of rotary evaporation
Formula), it can be obtained formula (2) compound represented.
According to the present invention, formula (2) compound represented and formula (c) compound represented carry out third substitution reaction
Obtain formula (1) compound represented.Preferably, the mole dosage ratio of formula (2) compound represented and formula (c) compound represented
For 1:1.8-4, preferably 1:2-3.Wherein, formula (c) compound represented can be provided in the form of its solution, use
Solvent for example can be toluene, n-hexane, pentane, benzene, dimethylbenzene, methylene chloride, chloroform, tetrachloromethane and tetrahydro furan
It one of mutters or a variety of, concentration for example can be 0.05-1mmol/mL.
According to the present invention, the reaction of the step (4) can also be selected from toluene, n-hexane, pentane, benzene, dimethylbenzene, two
It is carried out in the presence of one of chloromethanes, chloroform, tetrachloromethane and tetrahydrofuran or a variety of organic solvents, this is organic molten
The dosage of agent can change in a wider range, such as relative to formula (2) compound represented of 10mmol, the organic solvent
Dosage is 10-500mL.
In the case of, according to the invention it is preferred to, the condition of the third substitution reaction includes: that temperature is 80-150 DEG C, the time
For 8-20h.It is highly preferred that it is 100-140 DEG C that the condition of the third substitution reaction, which includes: temperature, time 10-15h.Its
In, after third substitution reaction, it can remove solvent (for example, by using the mode of rotary evaporation), and washed (such as adopt
Washed with pentane), then drying can be obtained formula (1) compound represented.
According to the present invention, for the preparation of formula (1) compound represented that X is alkyl, other modes can also be taken
Carry out, thus optionally, this method can also include: in step (4) resulting formula (1) compound represented at least one
In the case that X is halogen, this method further include: (5) formula (1) compound represented and Grignard Reagent or lithium alkylide progress the 4th take
Generation reaction, the Grignard Reagent are formula (d) compound represented, and the lithium alkylide is formula (d ') compound represented；Thus just
Alkyl can will be substituted by as the halogen X in the formula of reactant (1) compound represented.
According to the present invention, in the case where including step (5), formula (1) compound represented and Grignard Reagent or lithium alkylide
Mole dosage ratio be 1:1.8-8, preferably 1:2-6.Wherein, the Grignard Reagent or lithium alkylide can be in the form of its solution
It provides, the solvent generallyd use for example can be one of ether, tetrahydrofuran, n-hexane, pentane etc. or a variety of, dense
Degree for example can be 0.5-5mmol/mL.
According to the present invention, the 4th substitution reaction carries out in the presence of an organic, which can be selected from second
One of ether, tetrahydrofuran, n-hexane, pentane etc. are a variety of, and dosage can change in a wider range, such as relatively
In formula (1) compound represented of 10mmol as reactant, the dosage of the organic solvent is 100-2000mL.
In accordance with the present invention it is preferred that it is 80-150 DEG C that the condition of the 4th substitution reaction, which includes: temperature, time 8-
20h.It is highly preferred that it is 100-140 DEG C that the condition of the 4th substitution reaction, which includes: temperature, time 10-18h.Wherein,
After four substitution reactions, solvent (for example, by using the mode of rotary evaporation) can remove, and washed (for example, by using positive penta
Alkane is washed), then drying can be obtained formula (1) compound represented as product.
It according to the present invention, can be by formula made from the above method (1) in order to obtain the monocrystalline of formula (1) compound represented
Compound represented crude product is dissolved in methylene chloride/toluene mixed solvent (volume ratio is preferably 1:0.5-2), the dissolution
Process preferably carries out in inert atmosphere (such as nitrogen atmosphere, argon atmosphere etc.), is then stood resulting solution simultaneously
Solvent flashing handles (carrying out preferably in vacuum desiccator), so that the monocrystalline of formula (1) compound represented can be obtained.
Fifth aspect present invention provides early transition metal compound made from the above method.
Early transition metal compound made from above-mentioned preparation method of the invention can be understood as early transition metal chemical combination
The crude product of object, the mixture of a variety of early transition metal compounds, the monocrystalline of early transition metal compound or a variety of preceding transition
The mixture etc. of metallic compound monocrystalline, these are within.
Sixth aspect present invention provides the crystal of above-mentioned early transition metal compound or above-mentioned early transition metal compound
Application in the reaction of catalysis ethylene homo and/or ethylene-alpha-olefin copolyreaction.
Here alhpa olefin can be this field conventionally used for the alhpa olefin that is copolymerized with ethylene, for example, can for propylene,
One of 1- butylene, 1- amylene, 1- hexene, 1- octene and 4-methyl-1-pentene are a variety of.
Seventh aspect present invention provides a kind of carbon monoxide-olefin polymeric suitable for olefinic polymerization, and the composition contains main catalytic
Agent and activator, the major catalyst are the crystal of above-mentioned early transition metal compound or above-mentioned early transition metal compound,
The activator includes one of aluminum contained compound or a variety of and optionally contain organoboron compound.It should be understood that institute
State the crystal that major catalyst is one of above-mentioned early transition metal compound or a variety of or above-mentioned early transition metal compound
One of or it is a variety of, certainly also include that they arbitrary are combined.When the activator contains organoboron compound, it should also
It is interpreted as the activator and contains one of organoboron compound or a variety of.
According to the present invention, in the case where the activator is one of aluminum contained compound or is a variety of, the composition
In, it is preferable that the content mole of the major catalyst in terms of metallic element Mt and the aluminum contained compound in terms of aluminium element
Than for 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 aluminum contained compound and organoboron compound, the composition
In, it is preferable that the major catalyst in terms of metallic element Mt, the aluminum contained compound in terms of aluminium element and in terms of boron element
The organoboron compound content molar ratio be 1:0.1-500:0.5-5, 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, it can be selected in a wider range as the aluminum contained compound of activator, can be alkyl aluminum
Close one of object and alkyl aluminum compound or a variety of, it is preferable that the aluminum contained compound is alkyl aluminum compound and alkane
The mixture or alkyl aluminum compound of base aluminium alkoxide compound.
Preferably, the alkyl aluminum compound can be indicated by formula (e),
Wherein, R31For selected from methyl, ethyl, n-propyl, isopropyl, positive fourth
At least one of base, sec-butyl and tert-butyl group；T is the integer of 5-30.It is highly preferred that in formula (3), R31For selected from first
At least one of base, ethyl, n-propyl, isopropyl and tert-butyl group.It is further preferred that in formula (3), R31For selected from
At least one of methyl, ethyl and isobutyl group group.It is particularly preferred that the alkyl aluminum compound is methylaluminoxane
(MAO) and/or isobutyl aluminium alkoxide, that is, R31For methyl or isobutyl group.
Preferably, the alkyl aluminum compound be selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three oneself
Base aluminium, dimethylaluminum chloride, diethyl aluminum chloride, dipropyl aluminium chloride, diisobutyl aluminum chloride, dihexylaluminum chloride, methyl
Al dichloride, ethylaluminum dichloride, propyl al dichloride, isobutyl aluminium dichloride, hexyl al dichloride, dimethyl hydrogenated aluminium,
At least one of diethylaluminum hydride, dipropyl aluminum hydride, diisobutyl aluminium hydride and dihexyl aluminum hydride.Particularly preferably
Ground, the alkyl aluminum compound are triisobutyl aluminium.
In accordance with the present invention it is preferred that the organoboron compound is selected from three (pentafluorophenyl group) boron (B (C6F5)3), N, N- bis-
(pentafluorophenyl group) borate of methyl puratized agricultural spray four ([HNMe2Ph][B(C6F5)4]) and triphen carbon four (pentafluorophenyl group) borate
([Ph3C][B(C6F5)4]) one of or it is a variety of.
In composition of the invention can also contain other necessary additives, as long as these additives will not influence it is described
The catalytic effect of composition.For example, the composition can contain impurity scavenger.
Eighth aspect present invention provides above-mentioned composition in the reaction of catalysis ethylene homo and/or ethylene-alpha-olefin copolyreaction
In application.
In the application of the invention, to the formation each component suitable for the carbon monoxide-olefin polymeric of olefinic polymerization
There is no particular limitation for addition sequence and Adding Way, major catalyst, activator and the optionally additive that contains can be shifted to an earlier date
It is added in polymerization reaction after mixing, major catalyst, activator and the optionally additive that contains can also be added separately to gather
It closes in reaction.According to a kind of preferred embodiment: the additive first contained by activator and optionally is added to reactant
In system, then it is passed through olefinic monomer, then adds major catalyst.
Wherein, the alhpa olefin is as described above, and details are not described herein the present invention.
Ninth aspect present invention provides a kind of preparation method of olefin polymer, this method comprises: in organic solvent, In
In the presence of catalyst, olefinic monomer is subjected to polymerization reaction；
Wherein, the catalyst is above-mentioned composition.
In the case of, according to the invention it is preferred to, the condition of the polymerization reaction includes: that temperature is -50 DEG C to 200 DEG C, pressure
For 0.1-5MPa.It is highly preferred that the condition of the polymerization reaction include: temperature be 20-100 DEG C, pressure be 0.1-2MPa (such as
For 0.1-0.5MPa).The pressure is gauge pressure.
The polymerization reaction of the invention can be carried out using polymerisation in solution or bulk polymerization mode.Polymerization of the invention is anti-
It should be able to be solution polymerization, those skilled in the art are it will of course be appreciated that solvent is in polymeric reaction condition used in it
Under should be in a liquid state, and cannot participate in polymerization reaction, will not react with the polymer reacted, i.e., the solvent is
It is inert.This kind of solvent is it will be apparent that and can be easy to carry out for the those of ordinary skill of polymerization field
Selection.Nevertheless, for the purpose of the present invention, the specific example of the organic solvent for example can be benzene, toluene, ethylbenzene, diformazan
One of benzene, pentane, n-hexane, normal heptane, normal octane and hexamethylene are a variety of, preferably n-hexane, normal octane or just
Heptane more preferably uses n-hexane as the solvent in homopolymerization of the invention.For polymerization reaction of the invention, institute
The dosage for stating solvent makes the concentration of polymer be 5-30 weight %, preferably in the range of 8-10 weight %.
According to the present invention, above-mentioned polymerization process preferably carries out under inert atmosphere protection, such as can use nitrogen, helium
One of gas, argon gas etc. a variety of provide such inert atmosphere.
In polymerization reaction of the invention, terminator can be used after completion of the polymerization reaction and terminate polymerization reaction.For
The terminator of this step is conventional to those skilled in the art.The terminator that usually can be used includes deionization
Water, alcohol, acid etc..In the present invention, it is preferred to which the terminator used is one of isopropanol, methanol, water etc. or a variety of.
Preferably, the olefinic monomer is one of ethylene, alpha-olefin and cycloolefin or a variety of.Preferably, the α-
Alkene is one of propylene, 1- butylene, 1- amylene, 1- hexene, 1- octene and 4-methyl-1-pentene or a variety of, the cyclenes
Hydrocarbon is cyclopentene, cyclohexene, norbornene, 1- methyinorbornene, 5- methyinorbornene, dicyclopentadiene, 5- methylene-
One of 2- norbornene, 5- vinyl -2- norbornene and 5- ethylidene -2- norbornene are a variety of.
Above-mentioned catalyst of the invention (especially rubs especially suitable for the homopolymerization of ethylene and the copolymerization of ethylene-alpha-olefin
The copolymerization for the ethylene-propylene that your ratio is 1:0.5-5).
More specifically, above-mentioned preparation method using composition of the invention as catalyst in the case where, can be with more
Olefin polymer is made in high catalytic efficiency, such as catalytic efficiency can achieve 106gPolymer/molMetal·h.Using of the invention
The high density polyethylene (HDPE) of higher molecular weight and more High Linear degree can be made in catalyst at lower pressures, and has height
The ethylene-propylene elastomeric of molecular weight.
The present invention will be described in detail by way of examples below.
In following example:
In case of no particular description, the various raw materials used are all from commercially available.
The weight average molecular weight of polymer as described below is measured using Waters150 gel permeation chromatography (GPC), and 135
At DEG C, it is measured with 1,2,4- trichloro-benzenes for mobile phase.
Catalytic efficiency refers to the quality of every mole in the unit time of the resulting polymer of Mt, with unit gPolymer/molMetal·
H is indicated.
1The nuclear magnetic resonance spectrometer of the Bruker Ascend 400M model for the Bruker company that H NMR is used
Single crystal diffraction analyzes the X-ray single crystal diffraction of the Bruker APEX II model using Bruker company
Instrument.
Embodiment 1
The present embodiment is for illustrating early transition metal compound of the invention and preparation method thereof and intermediate and monocrystalline.
It is prepared according to above-mentioned reaction equation, specifically:
(1) by diphenyl ether (0.02mol), n-BuLi (42mmol) is added dropwise at -78 DEG C in the dilution in hexane (50mL)
Hexane solution (finishes) in about 5min, reacts 1h, is then warmed to room temperature (about 25 DEG C), and continue to be stirred to react 16h；
(2) hexane solution of 15mL diphenyl phosphine chloride (42mmol) is then added dropwise to step (1) under ice-water bath
Reaction system in (finished in about 5min), then continue to be stirred to react 16h under room temperature (about 25 DEG C)；It is removed by rotary evaporation
Solvent is removed, faint yellow viscous oily matter is obtained, with being dried in vacuo after acetone washing, obtains 9.4g white powder, as formula (3-1)
Compound represented: yield 87%,1H NMR(400MHz,C6D6)δ:7.41-7.26(m,8H,o-PPh2),7.08-6.93
(m,14H,m-PPh2,p-PPh2, phenylate), 6.91-6.87 (t, J=8Hz, 2H, phenylate), 6.72-6.66 (m,
4H,phenylate)ppm。
(3) formula (3-1) compound represented (2mmol) is dissolved in 10mL toluene, is then added dropwise under magnetic stirring folded
Nitrogen trimethyl silane (6mmol) (finishes) in about 3min, is then heated to 110 DEG C of reflux 10h；After reaction, decompression rotation
Evaporation is drained, and white solid 1.38g, i.e. formula (2-1) compound represented: yield 97%. are obtained1H NMR(400MHz,
C6D6) δ: 8.22 (ddd, J=14.3,7.6,1.4Hz, 2H, phenylate), 7.57 (ddd, J=24.2,12.8,7.1Hz,
8H,o-PPh2),7.05–6.81(m,14H,m-PPh2,p-PPh2, phenylate), 6.73 (t, J=7.5Hz, 2H,
), phenylate 5.80 (dd, J=7.9,5.2Hz, 2H, phenylate), 0.31 (s, 18H, SiMe3)ppm.
(4) formula (2-1) compound represented (1mmol) is dissolved in 10mL toluene, and 5mL is added dropwise under magnetic stirring
CpTiCl3(2mmol) toluene solution is then heated to 110 DEG C of reflux 12h；After reaction, decompression rotary evaporation removes solvent
Toluene obtains faint yellow crude product, and crude product is washed 3 times with pentane, is dried in vacuo to obtain product 0.86g, i.e. formula (1-Ti-
1) compound represented: yield 92%.1H NMR(400MHz,CD2Cl2) δ: 8.16 (ddd, J=14.5,7.4,1.8Hz,
2H,phenylate),7.68–7.56(m,2H,phenylate),7.54–7.40(m,14H,m-PPh2,p-PPh2,
), phenylate 7.38 (dd, J=16.6,9.3Hz, 2H, phenylate), 7.28-7.15 (m, 8H, o-PPh2),6.08(s,
8H, cp), 5.87 (t, J=6.9Hz, 2H, phenylate) ppm.
Single crystal preparation: under nitrogen protection by step (4) resulting formula (1-Ti-1) compound represented (about 0.1mmol)
It is dissolved in methylene chloride/toluene mixed solvent (volume ratio 1:1) of 5mL, is placed in vacuum desiccator and slowly waves
Solvent is sent out, corresponding formula (1-Ti-1) compound represented monocrystalline is obtained, is analyzed by single crystal diffraction, the structure of confirmation such as Fig. 1
It is shown, crystallographic system be anorthic system, space group P-1, cell parameter:
α=86.02 ° (3), β=89.96 ° (3), γ=61.44 ° (3), Z=2, ρcalc=1.4082g/cm3。
Embodiment 2
The present embodiment is for illustrating early transition metal compound of the invention and preparation method thereof and intermediate.
According to method described in embodiment 1, the difference is that, in step (4): by formula (2-1) compound represented (1mmol)
It is dissolved in 10mL toluene, and 5mL TiCl is added dropwise under magnetic stirring4(2mmol) toluene solution is then heated to 110 DEG C of reflux
12h；After reaction, decompression rotary evaporation removes solvent toluene, and crude product is washed 3 times with pentane, and vacuum drying is produced
Object, warp1What H NMR was identified is formula (1-Ti-2) compound represented.
Embodiment 3
The present embodiment is for illustrating early transition metal compound of the invention and preparation method thereof and intermediate.
According to method described in embodiment 1, the difference is that, using the CpZrCl of equimolar amounts in step (4)3Instead of
CpTiCl3, to obtain corresponding product, pass through1What H NMR was identified is formula (1-Zr-1) compound represented.
Embodiment 4
The present embodiment is for illustrating early transition metal compound of the invention and preparation method thereof and intermediate.
According to method described in embodiment 1, the difference is that, using the CpHfCl of equimolar amounts in step (4)3Instead of
CpTiCl3, to obtain corresponding product, pass through1What H NMR was identified is formula (1-Hf-1) compound represented.
Embodiment 5
The present embodiment is for illustrating early transition metal compound of the invention and preparation method thereof and intermediate.
According to method described in embodiment 1, the difference is that, the example further include:
(5) formula (1-Ti-1) compound represented (0.3mmol) is dissolved in 25mL ether, is added dropwise under magnetic stirring
The diethyl ether solution (0.5mL) (finishing in about 5min) of the MeMgBr of 1.5mmol then heats to 110 DEG C of reflux 15h；Reaction knot
Shu Hou removes solvent using rotary evaporation, crude product is washed with pentane, and vacuum drying obtains corresponding product, passes through1H NMR mirror
Surely what is obtained is formula (1-Ti-3) compound represented.
Embodiment 6
The present embodiment is for illustrating early transition metal compound of the invention and preparation method thereof and intermediate.
According to method described in embodiment 5, the difference is that, using the CpZrCl of equimolar amounts in step (4)3Instead of
CpTiCl3, to obtain corresponding product after step (5), pass through1What H NMR was identified is formula (1-Zr-3) compound represented.
Comparative example 1
It is prepared according to above-mentioned reaction equation, specifically:
(1) at -78 DEG C, to the diphenylphosphine (PHPh of the THF (100mL) of stirring2) (0.02mol) middle addition n-BuLi
(hexane solution of 12.5mL, 1.6M), obtains dark red solution, stirs 8h at 25 DEG C；
(2) THF solution that 2, the 6- dibromo pyridine (0.01mol) of 20mL is added dropwise in solution is stated then up, by mixture
After stirring 8h, removing solvent is vacuumized, ligand shown in formula (B1) is obtained.
Yield 78%；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) by trimethyl azide silane N3SiMe3(0.02mol) is slowly added into ligand (0.01mol) shown in formula (B1)
In the solution of 20mL toluene, reaction mixture is heated to reflux 12h.Solvent and excessive TMSN are removed when vacuumizing3When, it obtains
To white solid, i.e. ligand shown in formula (B2).
Yield 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) ligand (5mmol) shown in formula (B2) is dissolved in 10mL toluene, is stirred evenly, and contains ring penta to 5mL is added
The toluene solution of diene titanium trichloride (10mmol) is heated to 110 DEG C, reacts 12h, is subsequently cooled to 25 DEG C, removes solvent institute
Obtaining product is formula (1B) compound represented.
Polymerization Example 1
The present embodiment is used to illustrate the preparation method of Alathon of the invention.
Under nitrogen protection and at 50 DEG C, the toluene solution (being purchased from Albemarle company, similarly hereinafter) of the MAO of 2mL is added
Enter into the toluene of 200mL (so that the content of Al be 10mmol), and be continuously passed through ethylene gas (volume flow 50L/h) and
Holding gauge pressure is 0.1MPa, and 1 step of embodiment (4) resulting formula (1-Ti-1) compound represented is then added
(0.02mmol), and polymerization reaction 15min is carried out, stop supply monomer.It is terminated and is reacted using isopropanol, the polymer that will be obtained
Remove solvent, oven drying.
As a result as shown in table 1.
Polymerization Example 2
The present embodiment is used to illustrate the preparation method of Alathon of the invention.
According to method described in Polymerization Example 1, the difference is that, the dosage of formula (1-Ti-1) compound represented is
0.03mmol obtains corresponding polymer, as a result as shown in table 1.
Polymerization Example 3-8
The present embodiment is used to illustrate the preparation method of Alathon of the invention.
According to method described in Polymerization Example 1, the difference is that:
In Polymerization Example 3,1 step of embodiment is replaced using the monocrystalline of formula (1-Ti-1) compound represented of equimolar amounts
Suddenly (4) resulting formula (1-Ti-1) compound represented, obtains corresponding polymer, as a result as shown in table 1.
In Polymerization Example 4, using 2 step of equimolar amounts embodiment (4) resulting formula (1-Ti-2) compound represented
Instead of 1 step of embodiment (4) resulting formula (1-Ti-1) compound represented, corresponding polymer is obtained, as a result such as institute in table 1
Show.
In Polymerization Example 5, using 3 step of equimolar amounts embodiment (4) resulting formula (1-Zr-1) compound represented
Instead of 1 step of embodiment (4) resulting formula (1-Ti-1) compound represented, corresponding polymer is obtained, as a result such as institute in table 1
Show.
In Polymerization Example 6, using 4 step of equimolar amounts embodiment (4) resulting formula (1-Hf-1) compound represented
Instead of 1 step of embodiment (4) resulting formula (1-Ti-1) compound represented, corresponding polymer is obtained, as a result such as institute in table 1
Show.
In Polymerization Example 7, using 5 step of equimolar amounts embodiment (5) resulting formula (1-Ti-3) compound represented
Instead of 1 step of embodiment (4) resulting formula (1-Ti-1) compound represented, corresponding polymer is obtained, as a result such as institute in table 1
Show.
In Polymerization Example 8, using 6 step of equimolar amounts embodiment (5) resulting formula (1-Zr-3) compound represented
Instead of 1 step of embodiment (4) resulting formula (1-Ti-1) compound represented, corresponding polymer is obtained, as a result such as institute in table 1
Show.
Polymerization Example 9
The present embodiment is used to illustrate the preparation method of ethylene-propylene copolymer of the invention.
Under nitrogen protection and at 50 DEG C, the toluene solution of the MAO of 2mL is added into the toluene of 200mL (so that Al
Content be 10mmol), and be continuously passed through ethylene/propene/hydrogen mixed gas (molar ratio 1:2:0.05, volume flow be
It 50L/h) and keeps gauge pressure for 0.5MPa, 1 step of embodiment (4) resulting formula (1-Ti-1) compound represented is then added
(0.02mmol), and polymerization reaction 15min is carried out, stop supply monomer.It is terminated and is reacted using isopropanol, and anti-aging agent is added
Lrganox 1520 (is purchased from BASF AG, similarly hereinafter；Dosage makes the content of anti-aging agent in polymer be 0.2 weight %).Will
The polymer arrived removes solvent, oven drying.
As a result as shown in table 1.
Polymerization Example 10
The present embodiment is used to illustrate the preparation method of ethylene-propylene copolymer of the invention.
According to method described in Polymerization Example 9, the difference is that, using 3 step of equimolar amounts embodiment (4) resulting formula
(1-Zr-1) compound represented replaces 1 step of embodiment (4) resulting formula (1-Ti-1) compound represented, obtains corresponding
Polymer, as a result as shown in table 1.
Polymerization Example 11
The present embodiment is used to illustrate the preparation method of ethylene-propylene copolymer of the invention.
Under nitrogen protection and at 70 DEG C, the toluene solution of the MAO of 0.4mL is added into the toluene of 200mL (so that
The content of Al is 2mmol), and be continuously passed through ethylene/propene/hydrogen mixed gas (molar ratio 1:2:0.01, volume flow are
It 50L/h) and keeps gauge pressure for 0.5MPa, [CPh is added3][B(C6F5)4] (its dosage makes for the toluene solution of organoboron compound
Molar ratio B/Mt=1/1), formula (1-Ti-3) compound represented (0.02mmol) is then added, and carry out polymerization reaction
15min stops supply monomer.Terminated and reacted using isopropanol, and be added anti-aging agent lrganox 1520 (purchased from BASF AG,
Similarly hereinafter；Dosage makes the content of anti-aging agent in polymer be 0.2 weight %).Obtained polymer is removed into solvent, baking oven is dry
It is dry.
As a result as shown in table 1.
Polymerization Example 12
The present embodiment is used to illustrate the preparation method of ethylene-propylene copolymer of the invention.
According to method described in Polymerization Example 11, the difference is that, it is resulting using 6 step of equimolar amounts embodiment (5)
Formula (1-Zr-3) compound represented replaces 1 step of embodiment (4) resulting formula (1-Ti-1) compound represented, obtains corresponding
Polymer, as a result as shown in table 1.
It polymerize comparative example 1
According to method described in Polymerization Example 1, the difference is that, using the ZrCp of 0.04mmol2Cl2Complex alternate form
(1-Ti-1) compound represented, remaining is identical with Polymerization Example 1, obtains corresponding polymer, as a result such as institute in table 1
Show.
It polymerize comparative example 2
According to method described in Polymerization Example 11, the difference is that, using the ZrCp of 0.04mmol2Me2Complex alternate form
(1-Ti-3) compound represented, remaining is identical with Polymerization Example 11, obtains corresponding polymer, as a result as in table 1
It is shown.
It polymerize comparative example 3
According to method described in Polymerization Example 1, the difference is that, this comparative example uses the C of equimolar amounts2H4
{Ph2PNTiCl2Cp*}2Complex alternate form (1-Ti-1) compound represented, remaining is identical with Polymerization Example 1, obtains
To corresponding polymer, as a result as shown in table 1.
It polymerize comparative example 4
According to method described in Polymerization Example 1, the difference is that, obtained by comparative example 1 of this comparative example using equimolar amounts
Formula (1B) compound represented alternate form (1-Ti-1) compound represented, remaining is identical with Polymerization Example 1, obtains
Corresponding polymer, as a result as shown in table 1.
Table 1
It can be seen that by the data of table 1 and had using early transition metal compound of the invention or its crystal catalyzed alkene
Have and will be indicative high catalytic activity, and all has excellent catalytic activity under wide in range polymeric reaction condition；Especially
The monocrystalline catalytic activity of early transition metal compound of the invention is higher.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (20)
1. a kind of early transition metal compound, which is characterized in that the early transition metal compound is formula (1) compound represented:
Formula (1)
Wherein, R1、R2、R3And R4It is each independently selected from H, C1-20Alkyl, C1-20Alkoxy and halogen；
R1And R2It is each independently selected from H, C1-4Alkyl and substituted or unsubstituted C6-12Aryl, the substituted C6-12Virtue
Substituent group on base is selected from C1-4Alkyl；
R3For-MtXnOr-Mt (X ') Xn, wherein
Mt is group ivb metallic element；
2n X is each independently selected from C1-10Alkyl and halogen, and n=n ' -1, n ' be element M t chemical valence；X ' is metal
The ligand of element M t.
2. early transition metal compound according to claim 1, wherein R1、R2、R3And R4It is each independently selected from H, C1-16
Alkyl, C1-16Alkoxy and halogen；
Mt is Ti, Zr or Hf；
2n X is each independently selected from C1-8Alkyl, fluorine, chlorine, bromine and iodine；
Preferably, R1、R2、R3And R4It is each independently selected from H, C1-10Alkyl, C1-10Alkoxy and halogen；
R1And R2It is each independently selected from H, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, substituted
Or unsubstituted phenyl and substituted or unsubstituted naphthalene, the substituent group of the substituted phenyl and substituted naphthalene are respectively independent
Ground is selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl and tert-butyl；
Mt is Ti, Zr or Hf；
2n X is each independently selected from methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine and iodine；X ' replaces or does not take
It is the 1,3- cyclobutadiene in generation, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indenes, substituted or unsubstituted
Fluorenes, substituted or unsubstituted phenyl ring, substituted or unsubstituted 1,3,5- cycloheptatriene or substituted or unsubstituted ring are pungent
Tetraene；
It is highly preferred that R1、R2、R3And R4It is each independently selected from H, C1-6Alkyl, C1-6Alkoxy and halogen；
R1And R2It is each independently selected from substituted or unsubstituted phenyl and substituted or unsubstituted naphthalene, the substituted benzene
The substituent group of base and substituted naphthalene is each independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl and uncle
Butyl；
Mt is Ti, Zr or Hf；
2n X is each independently selected from methyl, ethyl, fluorine, chlorine, bromine and iodine；X ' is substituted or unsubstituted 1,3- ring fourth two
Alkene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indenes, substituted or unsubstituted fluorenes, replace or not
Substituted phenyl ring, substituted or unsubstituted 1,3,5- cycloheptatriene or substituted or unsubstituted cyclo-octatetraene.
3. early transition metal compound according to claim 1 or 2, wherein the early transition metal compound is following formula
One of compound represented；
4. the intermediate of early transition metal compound described in any one of claim 1-3, wherein the early transition metal
The intermediate for closing object is formula (2) compound represented:
Formula (2)
Each R4It is each independently selected from C1-20Alkyl and C1-20Alkoxy.
5. intermediate as claimed in claim 4, wherein each R4It is each independently selected from C1-16Alkyl and C1-16Alkoxy；
Preferably, each R4It is each independently selected from C1-10Alkyl and C1-10Alkoxy；
It is highly preferred that each R4It is each independently selected from C1-6Alkyl and C1-6Alkoxy；
It is further preferred that each R4Be each independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl,
Tert-butyl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy.
6. the crystal of early transition metal compound described in any one of claim 1-3, wherein the crystallographic system of the crystal is three
Oblique system.
7. a kind of preparation method of early transition metal compound, which is characterized in that this method comprises:
(1) formula (4) compound represented and organolithium reagent are subjected to the first substitution reaction；
(2) product of the first substitution reaction and formula (a) compound represented are subjected to the second substitution reaction, obtained shown in formula (3)
Compound；
(3) azide silane class compound shown in formula (3) compound represented and formula (b) is subjected to staudinger reaction, obtained
Formula (2) compound represented；
(4) formula (2) compound represented and formula (c) compound represented are subjected to third substitution reaction, obtained shown in formula (1)
Compound；
Optionally, in the case that at least one X is halogen in step (4) resulting formula (1) compound represented, this method
Further include: 5) formula (1) compound represented and Grignard Reagent or lithium alkylide carry out the 4th substitution reaction, and the Grignard Reagent is formula
(d) compound represented, the lithium alkylide are formula (d ') compound represented；
Formula (1)Formula (2)
Formula (3)Formula (4)
Formula (a)Formula (b)Formula (c) R3- X ",
Formula (d) R5- MgX " ', formula (d ') R5- Li,
Wherein, R1、R2、R3And R4It is each independently selected from H, C1-20Alkyl, C1-20Alkoxy and halogen；
R1And R2It is each independently selected from H, C1-4Alkyl and substituted or unsubstituted C6-12Aryl, the substituted C6-12Virtue
Substituent group on base is selected from C1-4Alkyl；
Each R4It is each independently selected from C1-20Alkyl and C1-20Alkoxy；
R3For-MtXnOr-Mt (X ') Xn, wherein
Mt is group ivb metallic element；
2n X is each independently selected from C1-10Alkyl and halogen, and n=n ' -1, n ' be element M t chemical valence；X ' is metal
The ligand of element M t；
R5Selected from C1-10Alkyl；
X " and X " ' is each independently selected from halogen.
8. according to the method described in claim 7, wherein, R1、R2、R3And R4It is each independently selected from H, C1-16Alkyl, C1-16
Alkoxy and halogen；
Each R4It is each independently selected from C1-16Alkyl and C1-16Alkoxy；
Mt is Ti, Zr or Hf；
2n X is each independently selected from C1-8Alkyl, fluorine, chlorine, bromine and iodine；
R5Selected from C1-8Alkyl；
Preferably, R1、R2、R3And R4It is each independently selected from H, C1-10Alkyl, C1-10Alkoxy and halogen；
R1And R2It is each independently selected from H, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, substituted
Or unsubstituted phenyl and substituted or unsubstituted naphthalene, the substituent group of the substituted phenyl and substituted naphthalene are respectively independent
Ground is selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl and tert-butyl；
Each R4It is each independently selected from C1-10Alkyl and C1-10Alkoxy；
Mt is Ti, Zr or Hf；
2n X is each independently selected from methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine and iodine；X ' replaces or does not take
It is the 1,3- cyclobutadiene in generation, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indenes, substituted or unsubstituted
Fluorenes, substituted or unsubstituted phenyl ring, substituted or unsubstituted 1,3,5- cycloheptatriene or substituted or unsubstituted ring are pungent
Tetraene；
R5Selected from methyl, ethyl, n-propyl or isopropyl；
It is highly preferred that R1、R2、R3And R4It is each independently selected from H, C1-6Alkyl, C1-6Alkoxy and halogen；
R1And R2It is each independently selected from substituted or unsubstituted phenyl and substituted or unsubstituted naphthalene, the substituted benzene
The substituent group of base and substituted naphthalene is each independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl and uncle
Butyl；
Each R4It is each independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, methoxyl group, second
Oxygroup, positive propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy；
Mt is Ti, Zr or Hf；
2n X is each independently selected from methyl, ethyl, fluorine, chlorine, bromine and iodine；X ' is substituted or unsubstituted 1,3- ring fourth two
Alkene, substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indenes, substituted or unsubstituted fluorenes, replace or not
Substituted phenyl ring, substituted or unsubstituted 1,3,5- cycloheptatriene or substituted or unsubstituted cyclo-octatetraene；
R5Selected from methyl or ethyl；
X " and X " ' is each independently selected from fluorine, chlorine, bromine and iodine.
9. method according to claim 7 or 8, wherein the organolithium reagent is formula R6In-Li compound represented
It is one or more, wherein R6For the alkyl of C1-C8；
Preferably, the organolithium reagent is lithium methide, ethyl-lithium, n-propyl lithium, isopropyl lithium, n-BuLi, s-butyl lithium
With one of tert-butyl lithium or a variety of；
Preferably, the mole dosage ratio of formula (4) compound represented and organolithium reagent is 1:1.8-3, preferably 1:2-
2.5。
10. the method according to any one of claim 7-9, wherein shown in formula (4) compound represented and formula (a)
Compound mole dosage ratio be 1:1.8-3, preferably 1:2-2.5；
Preferably, the mole dosage ratio of azide silane class compound shown in formula (3) compound represented and formula (b) is 1:1.8-
5, preferably 1:2-4；
Preferably, the mole dosage ratio of formula (2) compound represented and formula (c) compound represented be 1:1.8-4, preferably 1:
2-3。
11. method according to any one of claims of claim 7-10, wherein the condition of first substitution reaction includes:
0.5-2h is reacted at being first -90 DEG C to -50 DEG C in temperature, then reacts 10-24h at 10-40 DEG C；
Preferably, it is 10-40 DEG C that the condition of second substitution reaction, which includes: temperature, time 10-24h；
Preferably, it is 80-150 DEG C that the condition of the staudinger reaction, which includes: temperature, time 5-20h；
Preferably, it is 80-150 DEG C that the condition of the third substitution reaction, which includes: temperature, time 8-20h.
12. the method according to any one of claim 7-11, wherein in the case where including step (5), formula (1)
Compound represented and the mole dosage of grignard reagent or lithium alkylide ratio are 1:1.8-8, preferably 1:2-6；
Preferably, it is 80-150 DEG C that the condition of the 4th substitution reaction, which includes: temperature, time 8-20h.
13. early transition metal compound made from the method as described in any one of claim 7-12.
14. early transition metal compound described in any one of claim 1-3 and 13 or preceding mistake as claimed in claim 6
Cross application of the crystal of metallic compound in the reaction of catalysis ethylene homo and/or ethylene-alpha-olefin copolyreaction.
15. a kind of carbon monoxide-olefin polymeric suitable for olefinic polymerization, the composition contains major catalyst and activator, the main reminder
Agent is early transition metal compound or preceding mistake as claimed in claim 6 described in any one of claim 1-3 and 13
Cross the crystal of metallic compound, the activator includes one of aluminum contained compound or a variety of and optionally contain organic boron chemical combination
Object.
16. composition according to claim 15, wherein in the activator be one of aluminum contained compound or a variety of
In the case where, in the composition, the major catalyst in terms of metallic element Mt and in terms of aluminium element described in closed containing calorize
The content molar ratio of object is 1:50-3000, preferably 1:100-1000, more preferably 1:100-500；
In the case where the activator is aluminum contained compound and organoboron compound, in the composition, with metallic element Mt
The major catalyst, the aluminum contained compound in terms of aluminium element and the organoboron compound in terms of boron element counted contain
Amount molar ratio is 1:0.1-500:0.5-5, preferably 1:0.2-100:1-3.
17. composition according to claim 15 or 16, wherein the aluminum contained compound is alkyl aluminum compound and alkyl
The mixture or alkyl aluminum compound of aluminium alkoxide compound,
Preferably, the alkyl aluminum compound is methylaluminoxane and/or isobutyl aluminium alkoxide, the alkyl aluminum compound
Selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three hexyl aluminium, dimethylaluminum chloride, diethyl aluminum chloride,
Dipropyl aluminium chloride, diisobutyl aluminum chloride, dihexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propyl dichloride
Aluminium, isobutyl aluminium dichloride, hexyl al dichloride, dimethyl hydrogenated aluminium, diethylaluminum hydride, dipropyl aluminum hydride, two isobutyls
One of base aluminum hydride and dihexyl aluminum hydride are a variety of；
Preferably, the organoboron compound is selected from three (pentafluorophenyl group) boron, N, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) boric acid
One of salt and triphen carbon four (pentafluorophenyl group) borate are a variety of.
18. composition described in any one of claim 15-17 is total in the reaction of catalysis ethylene homo and/or ethylene-alpha-olefin
Application in poly- reaction.
19. a kind of preparation method of olefin polymer, this method comprises: in organic solvent, in the presence of a catalyst, by alkene
Monomer carries out polymerization reaction；
Wherein, the catalyst is composition described in any one of claim 15-17.
20. preparation method according to claim 19, wherein the condition of the polymerization reaction include: temperature be -50 DEG C extremely
200 DEG C, pressure 0.1-5MPa.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321161A (en) * | 1998-07-21 | 2001-11-07 | 诺瓦化学品公司 | Bis-phosphinimine catalyst |
| US20030109730A1 (en) * | 1999-10-05 | 2003-06-12 | Masaaki Nabika | Transition metal compound, addition polymerization catalyst component, addition polymerization catalyst and process for production of olefin polymer |
| KR100533925B1 (en) * | 1998-07-21 | 2005-12-07 | 노바 케미컬즈 (인터내셔널) 소시에테 아노님 | Cyclopentadienyl/phosphinimine catalyst with one and only one activatable ligand |
| CN107793510A (en) * | 2016-09-06 | 2018-03-13 | 中国石油化工股份有限公司 | Non-metallocene compound and ethylene styrene copolymer and preparation method and catalyst for olefines polymerizing composition and its application |
-
2018
- 2018-04-20 CN CN201810362109.8A patent/CN110386956B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321161A (en) * | 1998-07-21 | 2001-11-07 | 诺瓦化学品公司 | Bis-phosphinimine catalyst |
| KR100533925B1 (en) * | 1998-07-21 | 2005-12-07 | 노바 케미컬즈 (인터내셔널) 소시에테 아노님 | Cyclopentadienyl/phosphinimine catalyst with one and only one activatable ligand |
| US20030109730A1 (en) * | 1999-10-05 | 2003-06-12 | Masaaki Nabika | Transition metal compound, addition polymerization catalyst component, addition polymerization catalyst and process for production of olefin polymer |
| CN107793510A (en) * | 2016-09-06 | 2018-03-13 | 中国石油化工股份有限公司 | Non-metallocene compound and ethylene styrene copolymer and preparation method and catalyst for olefines polymerizing composition and its application |
Non-Patent Citations (2)
| Title |
|---|
| 陈建军等: "单茂膦亚胺钛配合物催化乙丙共聚及其共聚物在改善润滑油黏度指数中的应用 ", 《石油化工》 * |
| 陈建军等: "膦亚胺半茂钛催化体系合成无规聚丙烯弹性体的研究", 《高分子学报》 * |
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