CN113272310A - 配体化合物,过渡金属化合物和包含其的催化剂组合物 - Google Patents
配体化合物,过渡金属化合物和包含其的催化剂组合物 Download PDFInfo
- Publication number
- CN113272310A CN113272310A CN202080007606.1A CN202080007606A CN113272310A CN 113272310 A CN113272310 A CN 113272310A CN 202080007606 A CN202080007606 A CN 202080007606A CN 113272310 A CN113272310 A CN 113272310A
- Authority
- CN
- China
- Prior art keywords
- carbon atoms
- group
- formula
- aryl
- transition metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 61
- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 45
- 239000003446 ligand Substances 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 225
- 125000003118 aryl group Chemical group 0.000 claims description 56
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- -1 cationic Lewis acid Chemical class 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 31
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 25
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 24
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 229920000098 polyolefin Polymers 0.000 claims description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000001769 aryl amino group Chemical group 0.000 claims description 3
- 125000005104 aryl silyl group Chemical group 0.000 claims description 3
- 125000005110 aryl thio group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 229940106006 1-eicosene Drugs 0.000 claims description 2
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 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 62
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 54
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 52
- 238000002360 preparation method Methods 0.000 description 47
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 35
- 239000000243 solution Substances 0.000 description 28
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 26
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 24
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 15
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 14
- 239000004711 α-olefin Substances 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 12
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 229910003865 HfCl4 Inorganic materials 0.000 description 10
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 9
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 8
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 8
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- GZRYAEYFIVMKAX-UHFFFAOYSA-N 2-bromo-6-naphthalen-1-ylpyridine Chemical compound BrC1=CC=CC(C=2C3=CC=CC=C3C=CC=2)=N1 GZRYAEYFIVMKAX-UHFFFAOYSA-N 0.000 description 5
- HCIMXTXCDVBLOA-UHFFFAOYSA-N [4-(trifluoromethyl)phenoxy]boronic acid Chemical compound OB(O)OC1=CC=C(C(F)(F)F)C=C1 HCIMXTXCDVBLOA-UHFFFAOYSA-N 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- RFONJRMUUALMBA-UHFFFAOYSA-N 2-methanidylpropane Chemical compound CC(C)[CH2-] RFONJRMUUALMBA-UHFFFAOYSA-N 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 210000000080 chela (arthropods) Anatomy 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002363 hafnium compounds Chemical class 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DQVXWCCLFKMJTQ-UHFFFAOYSA-N (4-methylphenoxy)boronic acid Chemical compound CC1=CC=C(OB(O)O)C=C1 DQVXWCCLFKMJTQ-UHFFFAOYSA-N 0.000 description 3
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000007068 beta-elimination reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000010550 living polymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 3
- 238000002424 x-ray crystallography Methods 0.000 description 3
- DBQOUEWUAIHCNY-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)alumane Chemical compound Fc1c(F)c(F)c([AlH2])c(F)c1F DBQOUEWUAIHCNY-UHFFFAOYSA-N 0.000 description 2
- GWUXLTRGPPIDJA-UHFFFAOYSA-N (4-methylphenyl)alumane Chemical compound CC1=CC=C([AlH2])C=C1 GWUXLTRGPPIDJA-UHFFFAOYSA-N 0.000 description 2
- NRTWALFEFHWMEE-UHFFFAOYSA-N (6-bromopyridin-2-yl)-methyl-diphenylsilane Chemical compound C[Si](C1=CC=CC=C1)(C2=CC=CC=C2)C3=NC(=CC=C3)Br NRTWALFEFHWMEE-UHFFFAOYSA-N 0.000 description 2
- NZCRNCBJOUZGBS-UHFFFAOYSA-N (6-bromopyridin-2-yl)-tri(propan-2-yl)silane Chemical compound CC(C)[Si](C(C)C)(C(C)C)C1=CC=CC(Br)=N1 NZCRNCBJOUZGBS-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- GWKFGTBDSHSZFK-PXLXIMEGSA-N C(=N/c1ccccc1)\c1ccc(s1)-c1cccc2ccccc12 Chemical compound C(=N/c1ccccc1)\c1ccc(s1)-c1cccc2ccccc12 GWKFGTBDSHSZFK-PXLXIMEGSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012711 chain transfer polymerization Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- JHVGQGZQAUEZJZ-UHFFFAOYSA-N (6-bromopyridin-2-yl)-trimethylsilane Chemical compound C[Si](C)(C)C1=CC=CC(Br)=N1 JHVGQGZQAUEZJZ-UHFFFAOYSA-N 0.000 description 1
- GSTUHAGCFGIWDW-UHFFFAOYSA-N 1-(5-bromothiophen-2-yl)-N-[2,6-di(propan-2-yl)phenyl]methanimine Chemical compound BrC1=CC=C(S1)C=NC1=C(C=CC=C1C(C)C)C(C)C GSTUHAGCFGIWDW-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- FEYDZHNIIMENOB-UHFFFAOYSA-N 2,6-dibromopyridine Chemical compound BrC1=CC=CC(Br)=N1 FEYDZHNIIMENOB-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- AGXPNMMYDKKSMT-FSYXRNBESA-N 5-[(e)-2-[(1s,2r)-2-(1h-indol-5-yl)-1,4-dimethylcyclohex-3-en-1-yl]ethenyl]-1h-indole Chemical compound C1=C2NC=CC2=CC(/C=C/[C@@]2(C)[C@H](C=3C=C4C=CNC4=CC=3)C=C(CC2)C)=C1 AGXPNMMYDKKSMT-FSYXRNBESA-N 0.000 description 1
- 241000349731 Afzelia bipindensis Species 0.000 description 1
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- DTZDSNQYNPNCPK-UHFFFAOYSA-N N,N'-bis(diphenylmethyl)ethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)NCCNC(C=1C=CC=CC=1)C1=CC=CC=C1 DTZDSNQYNPNCPK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004636 glovebox technique Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000013537 high throughput screening Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
-
- 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
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61908—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/62003—Refractory metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/62006—Bidentate ligand
- C08F4/6201—Neutral ligand
- C08F4/62013—NN
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/62003—Refractory metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/62006—Bidentate ligand
- C08F4/6201—Neutral ligand
- C08F4/6202—NS
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/62003—Refractory metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/62082—Tridentate ligand
- C08F4/62086—Neutral ligand
- C08F4/62089—NNN
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明涉及具有新颖结构的配体化合物,过渡金属化合物以及包含其的催化剂组合物。
Description
[相关申请的交叉引用]
本申请要求基于在2019年4月26日提交的韩国专利申请第2019-0049172号的优先权的权益,该专利申请的全部内容通过引用并入本文。
技术领域
本发明涉及具有新颖结构的配体化合物,过渡金属化合物以及包含其的催化剂组合物。
背景技术
过渡金属钳形配合物已经广泛应用于有机金属催化剂领域。三齿螯合钳形配体与金属结合而形成以金属为中心的平面结构。配体-金属相互作用是刚性且不可转变的,因此提供了高稳定性。
为了均匀的烯烃聚合,最初的基于Zr的茂金属催化剂已经被引导至基于Ti的半茂金属,最后引导至具有双环戊二烯基配体的后茂金属。在开发的后茂金属中,钳型[C萘基,N吡啶,N氨基]HfMe2配合物是主要的催化剂。该配合物是通过高通量筛选在2000年代初期开发的并进行了深入研究,并且应用于商业过程中。
这样的配合物可以在乙烯/α-烯烃共聚中引入大量的α-烯烃,并且可以控制丙烯聚合的立构规整度用于制备等规聚丙烯。另外,优点是,可以完全阻止β-消除过程,所述β-消除过程是独特的链转移反应,其在用常规的基于Zr的茂金属和基于Ti的半茂金属催化剂进行的烯烃聚合中会不可避免地发生。
由于该特性,通过故意添加过量的二乙基锌(Et2Zn)作为链转移剂,可以从Hf位点生长聚烯烃链,而且可以均匀地生长PO链,后者称为配位链转移聚合(CCTP)。CCTP技术可以很好地用于烯烃嵌段共聚物的商业生产。
另外,在CCTP之后通过在反应中使用配合物的苯乙烯的阴离子聚合可以合成聚烯烃-聚苯乙烯嵌段共聚物。如上所述,包括铪金属的过渡金属化合物可以用作生产烯烃的催化剂,并且正在进行许多研究以通过对其进行改性来改善催化剂性能。
[现有技术文献]
[专利文献]
韩国早期公开专利第10-2018-0055531号
发明内容
技术问题
本发明的目的是提供具有新颖结构的配体化合物,过渡金属化合物以及包含其的催化剂组合物。
技术方案
为了解决上述任务,本发明提供由下式1表示的过渡金属化合物:
[式1]
在式1中,
X为-Si(R1)(R2)(R3);或6至20个碳原子的芳基,其中R1至R3中的任何一个或所述6至20个碳原子的芳基可与Hf结合以形成5元环,
R1至R3各自独立地为1至20个碳原子的烷基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基,
R4和R5各自独立地为氢;1至20个碳原子的烷基;2至20个碳原子的烯基;2至20个碳原子的炔基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基;
R6为氢;1至20个碳原子的烷基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基;其中,当X为6至20个碳原子的芳基时,R6不为6至20个碳原子的芳基或7至20个碳原子的烷基芳基,
每个Y独立地为卤素;1至20个碳原子的烷基;2至20个碳原子的烯基;2至20个碳原子的炔基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;7至20个碳原子的芳基烷基;5至20个碳原子的杂芳基;1至20个碳原子的烷氧基;取代或未取代的5至20个碳原子的芳氧基;1至20个碳原子的烷基氨基;5至20个碳原子的芳基氨基;1至20个碳原子的烷硫基;5至20个碳原子的芳硫基;1至20个碳原子的烷基甲硅烷基;5至20个碳原子的芳基甲硅烷基;羟基;氨基;巯基;甲硅烷基;氰基;或硝基,以及
n为2至4的整数。
有益效果
本发明的新型过渡金属化合物可以用作聚合反应催化剂用于制备具有高分子量的烯烃聚合物。
附图说明
图1示出了配体化合物2-1a的1H NMR图谱和13C NMR图谱。
图2示出了过渡金属化合物1-1a的1H NMR图谱和13C NMR图谱。
图3示出了配体化合物2-1b的1H NMR图谱和13C NMR图谱。
图4示出了过渡金属化合物1-1b的1H NMR图谱和13C NMR图谱。
图5示出了配体化合物2-2a的1H NMR图谱和13C NMR图谱。
图6示出了过渡金属化合物1-2a的1H NMR图谱和13C NMR图谱。
图7示出了配体化合物2-3a的1H NMR图谱和13C NMR图谱。
图8示出了过渡金属化合物1-3a的1H NMR图谱和13C NMR图谱。
图9示出了配体化合物2-3b的1H NMR图谱和13C NMR图谱。
图10示出了过渡金属化合物1-3b的1H NMR图谱和13C NMR图谱。
图11示出了配体化合物2-3c的1H NMR图谱和13C NMR图谱。
图12示出了过渡金属化合物1-3c的1H NMR图谱和13C NMR图谱。
图13示出了配体化合物2-3d的1H NMR图谱和13C NMR图谱。
图14示出了过渡金属化合物1-3d的1H NMR图谱和13C NMR图谱。
具体实施方式
在下文中,将更详细地解释本发明以帮助理解本发明。
应当理解,在说明书和权利要求书中使用的词语或术语不应被解释为在常用词典中定义的含义。将进一步理解的是,基于发明人可以适当地定义词语或术语的含义以最好地解释本发明的原则,这些词语或术语应被解释为具有与本发明的技术思想的含义一致的含义。
本发明提供一种由下式1表示的过渡金属化合物:
[式1]
在式1中,
X为-Si(R1)(R2)(R3);或6至20个碳原子的芳基,其中R1至R3中的任何一个或所述6至20个碳原子的芳基可与Hf结合以形成5元环,
R1至R3各自独立地为1至20个碳原子的烷基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基,
R4和R5各自独立地为氢;1至20个碳原子的烷基;2至20个碳原子的烯基;2至20个碳原子的炔基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基;
R6为氢;1至20个碳原子的烷基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基;其中,当X为6至20个碳原子的芳基时,R6不为6至20个碳原子的芳基或7至20个碳原子的烷基芳基,
每个Y独立地为卤素;1至20个碳原子的烷基;2至20个碳原子的烯基;2至20个碳原子的炔基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;7至20个碳原子的芳基烷基;5至20个碳原子的杂芳基;1至20个碳原子的烷氧基;取代或未取代的5至20个碳原子的芳氧基;1至20个碳原子的烷基氨基;5至20个碳原子的芳基氨基;1至20个碳原子的烷硫基;5至20个碳原子的芳硫基;1至20个碳原子的烷基甲硅烷基;5至20个碳原子的芳基甲硅烷基;羟基;氨基;巯基;甲硅烷基;氰基;或硝基,以及
n为2至4的整数。
当在相对于催化剂过量的链转移剂(例如二乙基锌;(Et)2Zn)的存在下进行聚合反应时,烯烃聚合物链会在锌(Zn)和铪(Hf)之间经历快速的烷基转移以从二烷基锌开始均匀的链增长,来实现活性聚合,这称为配位链转移聚合(CCTP)。常规使用的茂金属催化剂由于β-消除过程而不能进行活性聚合,并且公知的适用于CCTP的少数催化剂仅能够使乙烯均聚,但是通过CCTP使乙烯和α-烯烃共聚非常困难,因此,很难使用普通的过渡金属化合物作为催化剂通过CCTP进行活性聚合来制备嵌段共聚物。
然而,本发明的化合物是钳型的[C硅烷基甲基,N吡啶,N氨基]HfMe2或[C萘基,N吡啶,N烷氨基]HfMe2配合物,并且在乙烯和α-烯烃的聚合反应中显示出优异的α-烯烃混合能力。特别地,烯烃聚合物的分子量和α-烯烃的量根据链转移剂的量而变化,这表明本发明的化合物成功地用于CCTP,并且β-消除过程以可忽略的水平几乎不会发生。即,可以通过使用本发明的铪化合物经CCTP通过活性聚合来进行乙烯和α-烯烃单体的共聚,并且可以成功地制备具有多种嵌段组分的嵌段共聚物。
另外,通过将使用本发明的铪化合物的CCTP转化为阴离子苯乙烯聚合反应,可以进行聚烯烃-聚苯乙烯嵌段共聚物的合成。这样,本发明的铪化合物可用作制备烯烃聚合物的催化剂,并且这是可以通过本发明中新开发的催化剂的新颖结构来实现的独特特征。
特别地,本发明的催化剂是二配位或三配位型新型催化剂,并且具有与常规催化剂不同的结构,并且通过使用铪(Hf)而不是锆(Zr)或钛(Ti)作为过渡金属,可以获得优异的催化剂活性和α-烯烃混合能力。
特别地,为了表现出优异的作为烯烃聚合催化剂的活性,需要在聚合反应期间降低催化剂、单体、烷基铝等的链转移。本发明的催化剂是支链型或大体积的,并引入具有大位阻的取代基以在进行聚合反应期间阻止链转移并提高α-烯烃的混合能力。
在式1中,R1至R3可以各自独立地为1至20个碳原子的烷基;或6至20个碳原子的芳基,R4和R5可以各自独立地为氢;1至20个碳原子的烷基;或6到20个碳原子的芳基,R6可以为1至20个碳原子的烷基;3至20个碳原子的环烷基;或6至20个碳原子的芳基;其中R6可以被1至20个碳原子的烷基取代,每个Y可以独立地为1至20个碳原子的烷基;取代或未取代的3至20个碳原子的环烷基;或取代或未取代的6至20个碳原子的芳基,以及n可以是2或3。
另外,特别地,在式1中,R1至R3可以各自独立地为1至6个碳原子的烷基,或6至12个碳原子的芳基,R4和R5可以各自独立地为氢;或6至12个碳原子的芳基,R6可以为1至12个碳原子的烷基;6至12个碳原子的环烷基;或6至12个碳原子的芳基;其中R6可以被1至6个碳原子的烷基取代,每个Y可以独立地为1至20个碳原子的烷基,以及n可以是2或3。
根据本发明的一个实施方式,在式1中,X可以为-Si(R1)(R2)(R3),其中R1至R3可以各自独立地为1至12个碳原子的烷基,1至6个碳原子的烷基,例如异丙基,R4可以为氢,R5可以为6至12个碳原子的芳基,例如苯基,R6可以为被1至6个碳原子的烷基取代的6至12个碳原子的芳基,例如被异丙基取代的苯基,并且取代基可以为一个或多个。
根据本发明的一个实施方式,在式1中,X可以为-Si(R1)(R2)(R3),其中R1至R3可以各自独立地为1至12个碳原子的烷基或6至20个碳原子的芳基,其中R1至R3中的一个或多个可以为1至12个碳原子的烷基并且与Si相邻的碳可以与Hf结合以形成5元环,R4可以为氢,R5可以为6至12个碳原子的芳基,例如苯基,R6可以为被1至6个碳原子的烷基取代的6至12个碳原子的芳基,例如被异丙基取代的苯基,并且取代基可以为一个或多个。
根据本发明的一个实施方式,在式1中,X可以为6至20个碳原子的芳基,例如萘基,并且同时可以与Hf结合以形成5元环,R4可以为氢,R5可以为6至12个碳原子的芳基,例如苯基,以及R6可以为氢;1至20个碳原子的烷基;3至20个碳原子的环烷基;或7至20个碳原子的烷基芳基,并且在X为6至20个碳原子的芳基的实施方式中,R6不是6至20个碳原子的芳基或7至20个碳原子的烷基芳基。
特别地,由式1表示的过渡金属化合物可以由下式1-1至1-3中的任何一个表示:
[式1-1]
[式1-2]
[式1-3]
在式1-1至1-3中,
R1至R6的定义与上述相同,以及
R7为1至19个碳原子的烷基;6至19个碳原子的芳基;或7至19个碳原子的芳基烷基。
另外,由式1表示的过渡金属化合物可以选自以下化合物:
[式1-1a]
[式1-1b]
[式1-2a]
[式1-3a]
[式1-3b]
[式1-3c]
[式1-3d]
由式1表示的过渡金属化合物可以由下式2表示的配体化合物制备:[式2]
在式2中,
X为-Si(R1)(R2)(R3);或6至20个碳原子的芳基,
R1至R3各自独立地为1至20个碳原子的烷基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基,
R4和R5各自独立地为氢;1至20个碳原子的烷基;2至20个碳原子的烯基;2至20个碳原子的炔基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基;以及
R6为氢;1至20个碳原子的烷基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基;其中,当X为6至20个碳原子的芳基时,R6不为6至20个碳原子的芳基或7至20个碳原子的烷基芳基。
另外,由式2表示的配体化合物可以由以下式2-1或2-2表示:
[式2-1]
[式2-2]
在式2-1和2-2中,
R1至R6的定义与上述相同。
另外,由式2表示的配体化合物可以特别地选自以下化合物:[式2-1a]
[式2-1b]
[式2-2a]
[式2-3a]
[式2-3b]
[式2-3c]
[式2-3d]
本发明的由式1表示的过渡金属化合物可以通过包括使下面由式2表示的配体化合物与下面由式3表示的化合物反应的步骤来制备。
[式2]
[式3]
Hf(Y)4
同时,制备根据由式1表示的过渡金属化合物的最终结构的配体化合物的步骤可以通过下面的反应1或反应2进行:
[反应1]
[反应2]
即,通过使用有机锂化合物和亚胺化合物将氨基烷基基团引入吡啶,然后通过与过渡金属化合物反应而引入过渡金属可以制备式1的过渡金属化合物,并且本领域技术人员可以考虑到最终化合物的结构、实验条件等而适当地改变特定试剂类型、反应温度、压力等。
另外,本发明提供了一种催化剂组合物,其包含由式1表示的过渡金属化合物和助催化剂。在本发明中,术语“组合物”包括在相应组合物中包含的材料的混合物以及由相应组合物的材料形成的反应产物和分解产物。
所述助催化剂可以使用本领域中公知的任何一种,例如,选自下式4至6中的一种或多种:
[式4]
-[Al(Ra)-O]a-
[式5]
D(Ra)3
[式6]
[L-H]+[Z(A)4]-或[L]+[Z(A)4]-
其中,
各Ra独立地为卤素基团;1至20个碳原子的烃基;或卤素取代的1至20个碳原子的烃基,
a是2或更大的整数。
D是铝或硼,
L是中性或阳离子路易斯酸,
Z是第13族中的元素;
各A独立地为6至20个碳原子的芳基或1至20个碳原子的烷基,其中一个或多个氢原子可被取代基取代;以及
A的取代基是卤素基团;1至20个碳原子的烃基;1至20个碳原子的烷氧基;或6至20个碳原子的芳氧基。
由式4表示的化合物没有特别限制,只要其为烷基铝氧烷即可。优选实例可包括甲基铝氧烷、乙基铝氧烷、异丁基铝氧烷、丁基铝氧烷等,特别优选地,甲基铝氧烷。
由式5表示的化合物没有特别限制,其优选实例可以包括三甲基铝、三乙基铝、三异丁基铝、三丙基铝、三丁基铝、二甲基氯化铝、三异丙基铝、三仲丁基铝、三环戊基铝、三戊基铝、三异戊基铝、三己基铝、三辛基铝、乙基二甲基铝、甲基二乙基铝、三苯基铝、三对甲苯基铝、二甲基甲氧基铝、二甲基乙氧基铝、三甲基硼、三乙基硼、三异丁基硼、三丙基硼、三丁基硼等,并且更优选地,选自三甲基铝、三乙基铝和三异丁基铝。
由式6表示的化合物的实例可包括二(十八烷基)甲基铵四(五氟苯基)硼酸盐[(C18H37)2N(H)Me]+[B(C6F5)4]-,三乙基铵四苯基硼酸盐,三丁基铵四苯基硼酸盐,三甲基铵四苯基硼酸盐,三丙基铵四苯基硼酸盐,三甲基铵四(对-甲苯基)硼酸盐,三甲基铵四(邻,对-二甲基苯基)硼酸盐,三丁基铵四(对-三氟甲基苯基)硼酸盐,三甲基铵四(对-三氟甲基苯基)硼酸盐,三丁基铵四(五氟苯基)硼酸盐,N,N-二乙基苯胺四苯基硼酸盐,N,N-二乙基苯胺四苯基硼酸盐,N,N-二乙基苯胺四(五氟苯基)硼酸盐,二乙基铵四(五氟苯基)硼酸盐,三苯基鏻四苯基硼酸盐,三甲基鏻四苯基硼酸盐,三乙基铵四苯基铝,三丁基铵四苯基铝,三甲基铵四苯基铝,三丙基铵四苯基铝,三甲基铵四(对-甲苯基)铝,三丙基铵四(对-甲苯基)铝,三乙基铵四(邻,对-二甲基苯基)铝,三丁基铵四(对-三氟甲基苯基)铝,三甲基铵四(对-三氟甲基苯基)铝,三丁基铵四(五氟苯基)铝,N,N-二乙基苯胺四苯基铝,N,N-二乙基苯胺四苯基铝,N,N-二乙基苯胺四(五氟苯基)铝,二乙基铵四(五氟苯基)铝,三苯基鏻四苯基铝,三甲基鏻四苯基铝,三乙基铵四苯基铝,三丁基铵四苯基铝,三甲基铵四苯基硼酸盐,三丙基铵四苯基硼酸盐,三甲基铵四(对-甲苯基)硼酸盐,三丙基铵四(对-甲苯基)硼酸盐,三乙基铵四(邻,对-二甲基苯基)硼酸盐,三甲基铵四(邻,对-二甲基苯基)硼酸盐,三丁基铵四(对-三氟甲基苯基)硼酸盐,三甲基铵四(对-三氟甲基苯基)硼酸盐,三丁基铵四(五氟苯基)硼酸盐,N,N-二乙基苯胺四苯基硼酸盐,N,N-二乙基苯胺四苯基硼酸盐,N,N-二乙基苯胺四(五氟苯基)硼酸盐,二乙基铵四(五氟苯基)硼酸盐,三苯基鏻四苯基硼酸盐,三苯基碳鎓四(对-三氟甲基苯基)硼酸盐,三苯基碳鎓四(五氟苯基)硼酸盐等。
作为在组合物制备过程中使用的反应溶剂,可以使用烃溶剂,例如戊烷、己烷和庚烷,或芳族溶剂,例如苯和甲苯,但是本发明不限于此,可以使用本技术领域中使用的所有溶剂。
另外,可以以被载体负载的形式使用式1的过渡金属化合物和助催化剂。氧化硅或氧化铝可用作载体。
另外,本发明提供了一种烯烃聚合物的制备方法,包括在所述催化剂组合物的存在下使烯烃单体聚合的步骤。
在本发明中,术语“聚合物”指的是通过聚合相同或不同类型的单体制备的聚合物化合物。这种聚合物的上位术语包括用于指仅由一种单体制备的聚合物的术语均聚物和如下具体说明的术语互聚物。
本公开中使用的术语“互聚物”是指通过聚合至少两种不同种类的单体制备的聚合物。如此,互聚物的上位术语是指由两种不同种类的单体制备的聚合物,并且包括常用的共聚物和由两种或更多种不同种类的单体制备的聚合物。
在本发明中,烯烃单体可以是选自乙烯、丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯、1-十一碳烯、1-十二碳烯、1-十四碳烯、1-十六碳烯和1-二十碳烯中的一种或多种,但不限于此。
特别地,根据烯烃单体的类型,本发明的烯烃聚合物可以是烯烃均聚物或烯烃-α-烯烃共聚物,并且优选可以是乙烯/α-烯烃共聚物。在这种情况下,本领域技术人员可以根据烯烃聚合物的用途、目的等适当选择作为共聚单体的α-烯烃单体的量,并且可以为约1至约99摩尔%。
所述催化剂组合物可以在溶解或稀释于适用于烯烃聚合工艺的5至12个碳原子的脂族烃溶剂(如戊烷、己烷、庚烷、壬烷、癸烷、其异构体),芳族烃溶剂(如甲苯和苯),或被氯原子取代的烃溶剂(如二氯甲烷和氯苯)中之后注入。优选地,使用的溶剂通过用少量的烷基铝处理以除去少量的水或空气(其起催化剂毒物作用)后使用,并且可以通过进一步使用助催化剂来处理。
使用所述催化剂组合物的最优选的制备方法是溶液法,并且如果所述组合物与无机载体(如氧化硅)一起使用,则其也可以应用于淤浆法或气相法。
可通过使用连续淤浆聚合反应器、环管淤浆反应器、气相反应器或溶液反应器中的一种通过均聚一种烯烃单体或共聚两种或更多种烯烃单体来进行聚合。
另外,为了在进行聚合反应期间除去反应器中的水分,可以进一步注入有机铝化合物,并且可以在其存在下进行聚合反应。这种有机铝化合物的特定实例可以包括三烷基铝、二烷基卤化铝、烷基二卤化铝、二烷基氢化铝或烷基倍半卤化铝等,并且其更特定的实例可以包括Al(C2H5)3、Al(C2H5)2H、Al(C3H7)3、Al(C3H7)2H、Al(i-C4H9)2H、Al(C8H17)3、Al(C12H25)3、Al(C2H5)(C12H25)2、Al(i-C4H9)(C12H25)2、Al(i-C4H9)2H、Al(i-C4H9)3、(C2H5)2AlCl、(i-C3H9)2AlCl或(C2H5)3Al2Cl3。这种有机铝化合物可以被连续注入反应器中,或者可以以每1kg注入到反应器中的反应介质约0.1至10mol的比例注入以适当除去水分。
根据本发明的一个实施方式,烯烃聚合物的聚合可以在约60至200℃的温度,特别是约70至150℃的温度,或约80至100℃的温度以及约10至100巴的压力,特别是约15至50巴的压力或约20至40巴的压力的条件下进行约8分钟至2小时。
实施例
在下文中,将参考实施例更详细地说明本发明。但是,这些实施例是为了举例说明本发明,而本发明的范围并不限于这些。
[试剂和实验条件]
所有实验均使用标准手套箱和Schlenk技术在惰性气氛下进行。甲苯、己烷、乙醚、THF和C6D6在从二苯甲酮羰自由基中蒸馏出后使用。聚合反应中使用的甲基环己烷(无水级)购自东京化学工业公司(TCI)并使用Na/K合金纯化。乙烯在通过在50巴的压力下与分子筛和铜接触进行纯化之后使用。
使用ECZ 600仪器(JOEL)记录1H NMR(600MHz)和13C NMR(150MHz)图谱。
通过文献[J.Chem.Soc.,Perkin Trans.1 2002,1858-1868]中公开的方法制备2-溴-6-(三甲基甲硅烷基)吡啶,通过文献[Tetrahedron Lett.1998,39,6151-6154]中公开的方法制备2-溴-6-(三异丙基甲硅烷基)吡啶,通过文献[RSC Adv.2015,5,53073-53085]中公开的方法制备2-溴-6-(萘-1-基)吡啶,通过文献[J.C.U.S.Patent Appl.0220050A1(2004)]中公开的方法制备2-iPrC6H4Li,以及通过文献[Chem.Eur.J.2017,23,10997-11000]中公开的方法制备PhC(H)=NCH(CH3)2。
[过渡金属化合物的合成]
制备例1:式1-1a
(1)配体化合物
[式2-1a]
在-78℃下向2-溴-6-(三甲基甲硅烷基)吡啶(0.735g,3.19mmol)在THF(15mL)中的溶液中,加入在己烷(4mL)中的tBuLi溶液(3.76mL,6.39mmol,在戊烷中,1.7M),然后搅拌2小时。向其中加入PhC(H)=N(2,6-iPr2C6H3)(0.763g,2.87mmol)在THF(15mL)中的溶液。搅拌3小时后,将由此产生的溶液缓慢加热至室温并搅拌过夜。加入水(30mL),并将所得产物用乙酸乙酯(3x 20mL)萃取。收集有机相并在无水MgSO4相上干燥,然后通过旋转蒸发仪除去溶剂。通过使用己烷和甲苯(2:1v/v)的硅胶柱色谱分离获得浅黄色油状物(0.934mg,78%)。结果显示在图1中。
1H NMR(600MHz,C6D6):δ7.50(d,J=7.8Hz,2H),7.15-7.02(m,6H),7.00(t,J=7.8Hz,1H),6.93(t,J=7.8Hz,1H),6.66(d,J=6.6Hz,1H),5.69(br s,1H,NH),5.24(s,1H,NCH),3.44(七重峰,J=6.6Hz,2H,CH(CH3)2),),1.19(d,J=7.2Hz,6H,CH(CH3)2),1.09(d,J=7.2Hz,6H,CH(CH3)2),0.30(s,9H,CH3)ppm.
13C{1H}NMR(150MHz,C6D6):δ-1.76,24.28,28.13,70.17,121.96,123.97,127.07,127.13,128.40,134.42,142.80,143.71,144.39,162.14,167.69ppm.
IR(纯样品):v 3361(N-H)cm-1.
HRMS(EI):m/z计算值([M+]C27H36N2Si)416.2648.实测值:416.2650.
(2)过渡金属化合物
[式1-1a]
在-78℃下向HfCl4(0.230g,0.718mmol)在甲苯(2mL)中的溶液中滴加MeMgBr(1.00mL,2.94mmol,在乙醚中的3.0M溶液)。将所得溶液在-40至-35℃下搅拌1小时以沉淀出白色固体。冷却至-78℃后,逐滴加入配体化合物(0.230g,0.552mmol)在甲苯中的溶液。
将由此获得的混合物在-40至-35℃下搅拌2小时,并缓慢加热至室温。搅拌过夜后,使用真空管线除去所有挥发性材料。加入甲苯(10mL),并将产物萃取,在硅藻土上过滤,并收集。除去溶剂后,将残余物用己烷研磨,得到黄色油状物(0.220g,60%)。
分离后,使由此所得产物与氯甲基-Hf化合物接触,并用甲苯中的MeLi处理,得到铪化合物。1H和13C NMR图谱示于图2中。
1H NMR(600MHz,C6D6):δ7.21-7.11(m,2H),7.06(d,J=7.2Hz,1H),7.00(d,J=7.8Hz,1H),6.98-6.90(m,5H),6.86(t,J=7.2Hz,1H),6.55(d,J=9.0Hz,1H),5.96(s,1H,NCH),3.66(七重峰,J=6.6Hz,1H,CH(CH3)2),3.26(七重峰,J=6.6Hz,1H,CH(CH3)2),1.38(d,J=7.2Hz,3H,CH(CH3)2),1.34(d,J=7.2Hz,3H,CH(CH3)2),1.31(d,J=12.6Hz,1H,SiCH2Hf),1.24(d,J=7.2Hz,3H,CH(CH3)2),0.84(s,3H,SiCH3),0.42(s,3H,HfCH3),0.37(s,3H,SiCH3),0.35(d,J=7.2Hz,3H,CH(CH3)2),0.27(s,3H,HfCH3),0.24(d,J=12.6Hz,1H,SiCH2Hf)ppm.
13C{1H}NMR(150MHz,C6D6):δ11.17,18.70,24.09,24.38,28.00,69.90,121.38,123.77,123.96,126.87,129.14,133.86,142.84,143.84,161.94,164.65ppm.
制备例2:式1-1b
(1)2-溴-6-(甲基二苯基甲硅烷基)吡啶的制备
在-78℃下向2,6-二溴吡啶(1.00g,4.22mmol)在乙醚(20mL)中的溶液中加入nBuLi(1.70mL,4.22mmol,在己烷中的2.5M溶液)。将如此获得的溶液加热至-40℃并搅拌20分钟。冷却至-78℃后,向其中加入在乙醚(5mL)中的Ph2MeSiCl(1.08g,4.64mmol)。搅拌3小时后,将溶液加热至室温,加入水(30mL),然后用乙醚(3x 10mL)萃取产物。将由此收集的有机相在无水MgSO4相上干燥,然后通过旋转蒸发仪除去溶剂。通过使用己烷和乙酸乙酯(50:1v/v)的硅胶柱色谱法分离产物,得到白色固体(1.05g,70%)。
1H NMR(600MHz,C6D6):δ7.58(d,J=7.2Hz,4H),7.20-7.12(m,6H),7.04(d,J=7.2Hz,1H),6.91(d,J=7.8Hz,1H),6.53(t,J=7.2Hz,1H),0.82(s,3H,CH3)ppm.
13C{1H}NMR(150MHz,C6D6):δ-3.92,127.74,128.34,129.98,135.17,135.71,136.54,144.07,167.94ppm.
IR(纯样品):n 478(C-Br)cm-1.
HRMS(FAB):m/z计算值([M+H]+C18H16BrNSi)354.0314.实测值:354.0310.
(2)配体化合物
[式2-1b]
使用tBuLi(1.66mL,2.82mmol,在戊烷中,1.7M)、2-溴-6-(甲基二苯基甲硅烷基)吡啶(0.500g,1.41mmol)和PhC(H)=N(2,6-iPr2C6H3)(0.337g,1.27mmol)进行用于制备[式2-1a]的相同方法。
通过使用己烷和甲苯(2:1v/v)的硅胶色谱法分离,获得白色玻璃状固体(0.186g,27%)。结果显示在图3中。
1H NMR(600MHz,C6D6):δ7.63(t,J=7.8Hz,4H),7.46(d,J=7.2Hz,2H),7.22-7.00(m,13H),6.86(t,J=7.2Hz,1H),6.66(d,J=7.2Hz,1H),5.52-5.40(br,1H,NH),5.32-5.20(br,1H,NCH),3.31(七重峰,J=6.0Hz,2H,CH(CH3)2),1.35(d,J=6.6Hz,6H,CH(CH3)2),1.09(d,J=6.6Hz,6H,CH(CH3)2),0.87(s,3H,CH3)ppm.
13C{1H}NMR(150MHz,C6D6):δ-3.83,24.20,24.45,28.13,122.14,123.94,127.11,128.26,128.42,129.31,129.76,129.81,134.66,135.79,142.72,143.43,144.14,162.61,164.85ppm.
IR(纯样品):v 3361(N-H)cm-1.
HRMS(EI):m/z计算值([M+]C37H40N2Si)540.2961.实测值:540.2964.
(3)过渡金属化合物
[式1-1b]
通过使用HfCl4(0.155g,0.483mmol)、MeMgBr(0.70mL,2.0mmol,在乙醚中的3.0M溶液)和[式2-1b]化合物(0.174g,0.322mmol),并进行用于制备[式1-1a]的相同方法,获得橙色玻璃状固体(0.169g,84%)。1H和13C NMR图谱示于图4中。
1H NMR(600MHz,C6D6):δ7.66(d,J=5.4Hz,2H),7.61-7.52(m,2H),7.27-7.11(m,9H),7.04(d,J=7.8Hz,1H),6.95-6.86(m,5H),6.79(t,J=7.2Hz,1H),6.53(d,J=8.4Hz,1H),5.95(s,1H,NCH),3.64(七重峰,J=6.6Hz,1H,CH(CH3)2),3.29(七重峰,J=6.6Hz,1H,CH(CH3)2),1.69(d,J=13.2Hz,1H,SiCH2Hf),1.36(d,J=7.2Hz,3H,CH(CH3)2),1.32(d,J=7.2Hz,3H,CH(CH3)2),1.28(d,J=7.2Hz,3H,CH(CH3)2),0.79(d,J=13.2Hz,3H,SiCH2Hf),0.53(s,3H,HfCH3),0.40(s,3H,HfCH3),0.31(d,J=7.2Hz,3H,CH(CH3)2)ppm.
13C{1H}NMR(150MHz,C6D6):δ24.22,25.19,26.45,26.59,28.04,28.64,54.40,62.43,64.65,83.14,127.82,128.28,128.40,128.83,129.43,129.62,129.77,131.11,135.49,135.52,136.58,137.46,139.82,144.12,145.66,146.34,146.82,170.02,172.44ppm.分析计算值(C39H44N2SiHf):C,62.68;H,5.93;N,3.75%.实测值:C,62.73;H,5.97;N,3.80%.
制备例3:式1-2a
(1)配体化合物
[式2-2a]
使用tBuLi(0.56mL,0.954mmol,在戊烷中,1.7M)、2-溴-6-(三异丙基甲硅烷基)吡啶(0.150g,0.477mmol)和PhC(H)=N(2,6-iPr2C6H3)(0.114g,0.429mmol)进行用于制备[式2-1a]的相同方法。
通过使用己烷和甲苯(2:1v/v)的硅胶色谱法分离,获得浅黄色油状物(0.161g,75%)。1H和13C NMR图谱示于图5中。
1H NMR(600MHz,C6D6):δ7.40(d,J=7.2Hz,2H),7.15-7.05(m,6H),7.22-7.00(m,2H),6.70(d,J=8.4Hz,1H),5.34-5.21(br,2H,NH,NCH),3.35(七重峰,J=7.2Hz,2H,CH(CH3)2),1.47(七重峰,J=7.2Hz,3H,SiCH(CH3)2),1.20-1.10(m,30H,CH(CH3)2,SiCH(CH3)2)ppm.
13C{1H}NMR(150MHz,C6D6):δ11.17,18.70,24.09,24.38,28.00,69.90,121.38,123.77,123.96,126.87,129.14,133.86,142.84,143.84,161.94,164.65ppm.
IR(纯样品):v 3366(N-H)cm-1.
HRMS(EI):m/z计算值([M+]C33H48N2Si)500.3587.实测值:500.3589.
(2)过渡金属化合物
[式1-2a]
通过使用HfCl4(0.071g,0.22mmol)、MeMgBr(0.30mL,0.91mmol,在乙醚中的3.0M溶液)和[式2-2a]化合物(0.074g,0.15mmol),并进行用于制备[式1-1a]的相同方法,获得黄色油状物(0.097g,91%)。1H和13C NMR图谱示于图6中。
1H NMR(600MHz,C6D6):δ7.32(d,J=7.8Hz,2H),7.19(d,J=7.8Hz,1H),7.14(t,J=7.8Hz,1H),7.10(d,J=7.8Hz,1H),7.05(d,J=7.2Hz,1H),7.00(t,J=7.2Hz,2H),6.92(t,J=7.2Hz,1H),6.79(t,J=7.2Hz,1H),6.10(d,J=7.8Hz,1H),5.56(s,1H,NCH),3.82(七重峰,J=6.6Hz,1H,CH(CH3)2),3.63(七重峰,J=6.6Hz,1H,CH(CH3)2),1.76(七重峰,J=7.2Hz,3H,SiCH(CH3)2),1.43(d,J=7.2Hz,3H,CH(CH3)2),1.42(d,J=6.6Hz,3H,CH(CH3)2),1.36(d,J=6.6Hz,3H,CH(CH3)2),1.15(d,J=7.8Hz,9H,SiCH(CH3)2),1.12(d,J=7.2Hz,9H,SiCH(CH3)2),0.52(s,9H,Hf(CH3)3),0.43(d,J=7.8Hz,3H,CH(CH3)2)ppm.
13C{1H}NMR(150MHz,C6D6):δ12.90,19.25,19.56,24.86,25.45,25.73,26.24,28.38,28.41,61.07,81.25,123.02,124.64,125.02,126.54,127.98,128.86,129.18,131.71,135.31,143.56,144.00,146.32,147.25ppm.
制备例4:式1-3a
(1)配体化合物
[式2-3a]
使用tBuLi(0.79mL,1.34mmol,在戊烷中,1.7M)、2-溴-6-(萘-1-基)吡啶(0.190g,0.669mmol)和PhC(H)=NCH(CH3)2(0.108g,0.736mmol)进行用于制备[式2-1a]的相同方法。
通过使用己烷和三乙胺(100:1v/v)的硅胶色谱法分离,获得无色油状物(0.150g,64%)。1H和13C NMR图谱示于图7中。
1H NMR(600MHz,C6D6):δ8.32(d,J=8.4Hz,1H),7.68(d,J=7.8Hz,1H),7.65(d,J=7.8Hz,1H),7.59(d,J=7.2Hz,2H),7.52(d,J=6.0Hz,1H),7.34-7.24(m,3H),7.24-7.11(m,4H),7.11-7.04(m,2H),5.23(s,1H,NCH),2.81(七重峰,J=6.0Hz,1H,CH(CH3)2),0.11-0.09(m,6H,CH(CH3)2ppm.
13C{1H}NMR(150MHz,C6D6):δ23.17,23.57,46.43,66.16,120.30,123.12,125.49,126.10,126.46,126.77,127.30,127.85,128.28,128.63,128.72,129.09,132.01,134.58,136.88,139.35,144.40,159.02,163.50ppm.
IR(纯样品):v 3311(N-H)cm-1.
HRMS(FAB):m/z计算值([M+H]+C25H24N2)353.2018.实测值:353.2015.
(2)过渡金属化合物
[式1-3a]
通过使用HfCl4(0.171g,0.534mmol)、MeMgBr(0.80mL,2.2mmol,在乙醚中的3.0M溶液)和[式2-3a]化合物(0.126g,0.356mmol),并进行用于制备[式1-1a]的相同方法,获得黄色固体(0.164g,82%)。通过在-30℃下在甲苯和己烷中重结晶,获得了适合于X射线晶体学的单晶。1H和13C NMR图谱示于图8中。
1H NMR(600MHz,C6D6):δ8.64(d,J=7.2Hz,1H),8.27(d,J=8.4Hz,1H),7.85(d,J=7.2Hz,1H),7.73(d,J=8.4Hz,1H),7.43(d,J=7.2Hz,1H),7.33(t,J=7.8Hz,1H),7.28(t,J=7.2Hz,1H),7.20(d,J=7.2Hz,2H),7.09(t,J=7.2Hz,2H),7.05(t,J=7.8Hz,1H),6.73(t,J=7.8Hz,1H),6.39(d,J=7.8Hz,1H),5.85(s,1H,NCH),3.98(七重峰,J=6.6Hz,1H,CH(CH3)2),1.53(d,J=3.3Hz,3H,CH(CH3)2),1.02(d,J=6.0Hz,3H,CH(CH3)2),0.81(s,3H,HfCH3),0.77(s,3H,HfCH3)ppm.
13C{1H}NMR(150MHz,C6D6):δ22.13,24.04,46.31,59.38,60.35,75.52,119.82,120.11,124.11,125.35,126.86,129.09,129.77,130.01,130.62,133.95,135.70,140.23,144.18,146.38,164.45,170.90,204.71ppm.分析计算值(C27H28N2Hf):C,58.01;H,5.05;N,5.01%.实测值:C,58.10;H,5.16;N,5.09%.
制备例5:式1-3b
(1)配体化合物
[式2-3b]
使用tBuLi(0.79mL,1.34mmol,在戊烷中,1.7M)、2-溴-6-(萘-1-基)吡啶(0.190g,0.669mmol)和PhC(H)=NCH(CH3)2(0.119g,0.736mmol)进行用于制备[式2-1a]的相同方法。
通过使用己烷和三乙胺(100:1v/v)的硅胶色谱法分离,获得无色油状物(0.187g,76%)。1H和13C NMR图谱示于图9中。
1H NMR(600MHz,C6D6):δ8.34(d,J=8.4Hz,1H),7.68(d,J=7.2Hz,1H),7.64(d,J=7.8Hz,1H),7.59(d,J=7.8Hz,2H),7.52(d,J=7.8Hz,1H),7.33-7.24(m,3H),7.24-7.12(m,4H),7.11-7.03(m,2H),5.27(s,1H,NCH),1.07(s,9H,C(CH3)3)ppm.
13C{1H}NMR(150MHz,C6D6):δ30.25,51.64,63.24,120.46,122.83,125.49,126.42,126.76,127.01,128.69,129.10,132.00,134.61,136.79,139.32,146.89,158.66,165.02ppm.
IR(纯样品):v 3302(N-H)cm-1.
HRMS(EI):m/z计算值([M+]C26H26N2)366.2096.实测值:366.2098.
(2)过渡金属化合物
[式1-3b]
通过使用HfCl4(0.131g,0.409mmol)、MeMgBr(0.60mL,1.7mmol,在乙醚中的3.0M溶液)和[式2-3a]化合物(0.100g,0.272mmol),并进行用于制备[式1-1a]的相同方法,获得亮棕色固体(0.120g,79%)。1H和13C NMR图谱示于图10中。
1H NMR(600MHz,C6D6):δ8.65(d,J=7.2Hz,1H),8.27(d,J=8.4Hz,1H),7.86(d,J=7.8Hz,1H),7.74(d,J=8.4Hz,1H),7.42(d,J=7.8Hz,1H),7.33(t,J=7.2Hz,1H),7.28(t,J=7.2Hz,1H),7.25(d,J=7.2Hz,2H),7.11(t,J=7.2Hz,2H),7.03(t,J=7.2Hz,1H),6.74(t,J=7.2Hz,1H),6.41(d,J=8.4Hz,1H),5.93(s,1H,NCH),3.56(tt,J=8.4,3.6Hz,1H,C6H11),2.17(d,J=11.4Hz,1H,C6H11),2.06(qd,1H,J=12,3.6Hz,C6H11),1.93(d,1H,J=12.6Hz,C6H11),1.81(d,1H,J=13.8Hz,C6H11),1.61(d,1H,J=12Hz,C6H11),1.50(d,1H,J=13.2Hz,C6H11),1.25(qt,1H,J=12,3.6Hz,C6H11),1.20-0.97(m,3H,C6H11),0.84(s,3H,HfCH3),0.80(s,3H,HfCH3)ppm.
13C{1H}NMR(150MHz,C6D6):δ26.45,27.08,27.49,33.61,35.43,55.83,59.25,60.41,75.78,119.82,120.10,124.12,125.35,126.85,129.08,129.07,130.00,130.61,134.00,135.70,140.22,144.23,146.53,164.46,170.99,204.72ppm.分析计算值(C30H32N2Hf):C,60.15;H,5.38;N,4.68%.实测值:C,60.32;H,5.51;N,4.83%.
制备例6:式1-3c
(1)配体化合物
[式2-3c]
使用tBuLi(1.04mL,1.76mmol,在戊烷中,1.7M)、2-溴-6-(萘-1-基)吡啶(0.250g,0.880mmol)和PhC(H)=NC6H11(0.181g,0.968mmol)进行用于制备[式2-1a]的相同方法。
通过使用己烷和三乙胺(100:1v/v)的硅胶色谱法分离,获得无色油状物(0.238g,69%)。1H和13C NMR图谱示于图11中。
1H NMR(600MHz,C6D6):δ8.34(d,J=7.8Hz,1H),7.68(d,J=7.2Hz,1H),7.64(d,J=8.4Hz,1H),7.61(d,J=7.2Hz,2H),7.52(d,J=6.6Hz,1H),7.36-7.23(m,3H),7.23-7.15(m,2H),7.10-7.04(m,2H),5.32(s,1H,NCH),2.56(tt,J=9.6,3.0Hz,1H,C6H11),1.94(d,J=12Hz,2H,C6H11),1.90(d,J=12.6Hz,2H,C6H11),1.59(s,2H,C6H11),1.41(s,1H,C6H11),1.19-0.98(m,5H,C6H11)ppm.
13C{1H}NMR(150MHz,C6D6):δ25.20,26.62,33.92,34.29,54.33,65.61,120.30,123.12,125.49,126.10,126.44,126.80,127.32,128.63,128.74,129.10,132.02,134.60,136.92,139.36,144.65ppm.
IR(纯样品):v 3310(N-H)cm-1.
HRMS(FAB):m/z计算值([M+H]+C28H28N2)393.2096.实测值:393.2329.
(2)过渡金属化合物
[式1-3c]
通过使用HfCl4(0.216g,0.675mmol)、MeMgBr(1.00mL,2.77mmol,在乙醚中的3.0M溶液)和[式2-3c]化合物(0.165g,0.450mmol),并进行用于制备[式1-1a]的相同方法,获得黄色固体(0.209g,81%)。通过在-30℃下在甲苯和己烷中重结晶,获得了适合于X射线晶体学的单晶。1H和13C NMR图谱示于图12中。
1H NMR(600MHz,C6D6):δ8.65(d,J=7.8Hz,1H),8.18(d,J=8.4Hz,1H),7.83(d,J=7.2Hz,1H),7.71(d,J=7.8Hz,1H),7.33-7.24(m,4H),7.05(t,J=7.2Hz,3H),6.94(t,J=7.2Hz,1H),6.70(t,J=7.2Hz,1H),6.47(d,J=7.8Hz,1H),5.88(s,1H,NCH),1.43(s,9H,C(CH3)3),1.03(s,3H,HfCH3),0.80(s,3H,HfCH3)ppm.
13C{1H}NMR(150MHz,C6D6):δ31.10,55.17,60.66,63.223,75.73,119.26,119.42,124.02,125.22,126.78,127.30,127.42,129.15,129.77,129.97,130.55,134.49,135.42ppm.分析计算值(C28H30N2Hf):C,58.69;H,5.28;N,4.89%.实测值:C,58.81;H,5.38;N,4.97%.
制备例7:式1-3d
(1)配体化合物
[式2-3d]
使用tBuLi(1.04mL,1.76mmol,在戊烷中,1.7M)、2-溴-6-(萘-1-基)吡啶(0.250g,0.880mmol)和PhC(H)=NC10H16(0.232g,0.968mmol)进行用于制备[式2-1a]的相同方法。
通过使用己烷和三乙胺(100:1v/v)的硅胶色谱法分离,获得白色玻璃状固体(0.260g,74%)。1H和13C NMR图谱示于图13中。
1H NMR(600MHz,C6D6):δ8.38(d,J=7.8Hz,1H),7.68(d,J=8.4Hz,1H),7.66-7.59(m,4H),7.53(d,J=7.2Hz,2H),7.37-7.25(m,4H),7.25-7.18(m,3H),7.12-7.05(m,2H),5.45(s,1H,NCH),2.56(s,1H,C10H16),1.90(s,3H,C10H16),1.67(t,6H,J=15Hz,C10H16),1.51(dd,6H,J=19.8,12Hz,C10H16)ppm.
13C{1H}NMR(150MHz,C6D6):δ30.15,37.03,44.20,51.93,61.16,120.49,122.80,125.49,126.08,126.40,126.87,126.97,127.98,128.39,128.63,128.67,129.10,132.02,134.63,136.79,139.35ppm.
IR(纯样品):v 3293(N-H)cm-1.
HRMS(EI):m/z计算值([M+]C32H32N2)444.2565.实测值:444.2563.
(2)过渡金属化合物
[式1-3d]
通过使用HfCl4(0.256g,0.800mmol)、MeMgBr(1.10mL,3.28mmol,在乙醚中的3.0M溶液)和[式2-3d]化合物(0.237g,0.533mmol),并进行用于制备[式1-1a]的相同方法,获得黄色固体(0.288g,83%)。通过在-30℃下在甲苯/己烷共溶剂中重结晶,获得了适合于X射线晶体学的单晶。1H和13C NMR图谱示于图14中。
1H NMR(600MHz,C6D6):δ8.68(d,J=7.8Hz,1H),8.17(d,J=8.4Hz,1H),7.85(d,J=7.8Hz,1H),7.72(d,J=8.4Hz,1H),7.38(d,J=8.4Hz,2H),7.34(d,J=8.4Hz,1H),7.33-7.25(m,2H),7.08(t,J=7.8Hz,2H),6.94(t,J=7.8Hz,1H),6.73(t,J=7.8Hz,1H),6.54(d,J=7.8Hz,1H),6.05(s,1H,NCH),2.33(d,3H,J=11.4Hz,C10H16),2.10(d,3H,J=10.8Hz,C10H16),2.02(s,3H,C10H16),1.62(d,3H,J=12Hz,C10H16),1.56(d,3H,J=11.4Hz,C10H16),1.10(s,3H,HfCH3),0.86(s,3H,HfCH3)ppm.
13C{1H}NMR(150MHz,C6D6):δ30.30,36.98,44.25,56.72,61.04,63.92,73.91,119.18,119.44,124.04,125.20,126.76,127.16,127.35,127.98,129.11,129.73,129.95,130.55,134.67,135.42,140.80,143.10,149.16,164.91,170.90,204.57ppm.分析计算值(C34H36N2Hf):C,62.71;H,5.57;N,4.30%.实测值:C,62.59;H,5.44;N,4.18%.
比较制备例1
(1)配体化合物
使用tBuLi(0.79mL,1.34mmol,在戊烷中,1.7M)、2-溴-6-(萘-1-基)吡啶(0.190g,0.669mmol)和(Z)-N-(2-异丙基亚苄基)苯胺(0.165g,0.740mmol)进行用于制备[式2-1a]的相同方法。
使用HfCl4(0.256g,0.800mmol)、MeMgBr(1.10mL,3.28mmol,在乙醚中的3.0M溶液)和所述配体化合物(0.237g,0.533mmol)进行用于制备[式1-1a]的相同方法。
(2)过渡金属化合物
使用HfCl4(0.256g,0.800mmol)、MeMgBr(1.10mL,3.28mmol,在乙醚中的3.0M溶液)和所述配体化合物(0.237g,0.533mmol)进行用于制备[式1-1a]的相同方法。
比较制备例2
(1)配体化合物
进行文献[Organometallics 2011,30,6028-6033]中公开的方法。
(2)过渡金属化合物
使用HfCl4(0.158g,0.492mmol)、MeMgBr(0.700mL,2.08mmol,在乙醚中的3.0M溶液)、所述配体化合物(0.150g,0.328mmol)和甲苯(6mL)进行用于制备[式1-1a]的相同方法。
比较制备例3
(1)配体化合物
在N2气氛下向Schlenk烧瓶中加入(5-溴噻吩-2-基)-N-(2,6-二异丙基苯基)甲亚胺(1.00g,2.86mmol)、1-萘基硼酸(0.491g,2.86mmol)、Na2CO3(0.759g,7.17mmol)和甲苯(3mL)。向其中加入(Ph3P)4Pd(9.0mg,0.0080mmol)在经脱气的H2O/EtOH(2mL,1:1v/v)和甲苯(1mL)中的溶液。将如此获得的两相溶液加热至70℃并剧烈搅拌过夜。冷却至室温后,收集有机相并用H2O(5mL)洗涤。收集的有机相在无水MgSO4相上干燥,然后通过旋转蒸发仪除去溶剂。通过在-30℃下在甲醇中的重结晶进行分离,得到黄色固体状的(E)-N-((5-(萘-1-基)噻吩-2-基)亚甲基)苯胺(0.738g,65%)。
将nBuLi(0.90mL,1.4mmol,在己烷中的1.61M溶液)逐滴添加到(E)-N-((5-(萘-1-基)噻吩-2-基)亚甲基)苯胺(0.500g,1.26mmol)在甲苯(10mL)中的溶液中。搅拌1小时后,添加水(10mL),然后将所得产物用甲苯(3x 5mL)萃取。将合并的有机相在无水MgSO4相上干燥,然后通过旋转蒸发仪除去溶剂。通过1H和13C NMR图谱分析,确认由此获得的粗油状物是纯的,并且没有进行额外分离就用于下一步骤(0.573g,100%)。
(2)过渡金属化合物
使用HfCl4(0.229g,0.716mmol)、MeMgBr(1.00mL,2.94mmol,在乙醚中的3.0M溶液)和所述配体化合物(0.251g,0.551mmol)进行用于制备[式1-1a]的相同方法。
烯烃聚合物的制备
实施例1
将弹式反应器(125mL)在60℃下真空处理1小时。在将大气压力的乙烯气体充入弹式反应器后,将Me3Al(28.8mg,200μmol-Al)在甲基环己烷(15.5g)中的溶液加入到反应器中。使用加热套将由此获得的混合物在100℃下搅拌1小时,然后使用套管除去溶液。再次排空反应器以除去残留的溶剂,并在大气压力下用乙烯气体再填充。进行该过程是为了清除催化剂毒物。
向反应器中充入含MMAO(AkzoNobel,在庚烷中,6.7wt%-Al,20mg,50μmol-Al)的甲基环己烷(15.5g),并将温度设定为80℃。使制备例1的过渡金属化合物与助催化剂[(C18H37)2N(H)Me]+[B(C6F5)4]-(1.0当量)反应以进行活化,并注入含有经活化的催化剂(2.0μmol-Hf)的甲基环己烷溶液(0.30g)。
从储罐向反应器中充入30巴的乙烯/丙烯混合气体(15巴/15巴,总计30巴),然后在80-90℃下进行聚合50分钟。排出乙烯/丙烯混合气体,并将反应器冷却至75℃。收集由此产生的聚合物,并在160℃的真空烘箱中干燥过夜。
实施例2至7和比较例1至3
除了如下表1中改变催化剂的类型之外,以与实施例1相同的方法制备烯烃聚合物。
[表1]
催化剂 | |
实施例1 | 制备例1 |
实施例2 | 制备例2 |
实施例3 | 制备例3 |
实施例4 | 制备例4 |
实施例5 | 制备例5 |
实施例6 | 制备例6 |
实施例7 | 制备例7 |
比较例1 | 比较制备例1 |
比较例2 | 比较制备例2 |
比较例3 | 比较制备例3 |
实验例1
通过以下方法分析烯烃聚合物的聚合结果。
(1)熔融温度(Tm,℃)
使用差示扫描量热计(DSC,装置名称:DSC 2920,制造商:TA仪器)测量聚合物的熔融温度。特别地,将聚合物加热至150℃,将该温度保持5分钟,将温度降低至-100℃,并再次升高温度。在这种情况下,将温度的升高速率和降低速率分别控制为10℃/min。将熔融温度设定为在温度的第二上升区间中测得的吸收峰的最大点。
(2)数均分子量(Mn)和分子量分布(MWD)
在通过使用PL-SP260在160℃下溶解于含有0.0125%的BHT的1,2,4-三氯苯中进行预处理3小时后,使用PL-GPC220在160℃的测量温度下分别测量重均分子量(Mw)和数均分子量(Mn)。在这种情况下,通过使用聚苯乙烯的标准化来测量各个分子量。通过使用如此测量的Mw和Mn,通过将Mw值除以Mn值来计算MWD。
[表2]
如上表2所示,根据本发明的化合物可用作乙烯和丙烯的共聚反应中的催化剂,并且能够成功地获得乙烯/丙烯共聚物。
相反,比较制备例2和比较制备例3的化合物没有显示出作为催化剂的活性,聚合反应没有适当地进行,几乎没有得到乙烯/丙烯共聚物。
另外,比较例1使用比较制备例1的化合物,其中X是6至20个碳原子的芳基,并且该芳基位于R6,与本发明的化合物不同,证实了当与制备例7的化合物相比时,收率和α-烯烃的混合能力显著降低,并且不能制备具有高数均分子量的共聚物。
Claims (10)
1.一种由下式1表示的过渡金属化合物:
[式1]
在式1中,
X为-Si(R1)(R2)(R3);或6至20个碳原子的芳基,其中R1至R3中的任何一个或所述6至20个碳原子的芳基可与Hf结合以形成5元环,
R1至R3各自独立地为1至20个碳原子的烷基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基,
R4和R5各自独立地为氢;1至20个碳原子的烷基;2至20个碳原子的烯基;2至20个碳原子的炔基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基;
R6为氢;1至20个碳原子的烷基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基;其中,当X为6至20个碳原子的芳基时,R6不为6至20个碳原子的芳基或7至20个碳原子的烷基芳基,
每个Y独立地为卤素;1至20个碳原子的烷基;2至20个碳原子的烯基;2至20个碳原子的炔基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;7至20个碳原子的芳基烷基;5至20个碳原子的杂芳基;1至20个碳原子的烷氧基;取代或未取代的5至20个碳原子的芳氧基;1至20个碳原子的烷基氨基;5至20个碳原子的芳基氨基;1至20个碳原子的烷硫基;5至20个碳原子的芳硫基;1至20个碳原子的烷基甲硅烷基;5至20个碳原子的芳基甲硅烷基;羟基;氨基;巯基;甲硅烷基;氰基;或硝基,以及
n为2至4的整数。
2.根据权利要求1所述的过渡金属化合物,其中
R1至R3各自独立地为1至20个碳原子的烷基;或6至20个碳原子的芳基,
R4和R5各自独立地为氢;1至20个碳原子的烷基;或6至20个碳原子的芳基,
R6为1至20个碳原子的烷基;取代或未取代的3至20个碳原子的环烷基;或取代或未取代的6至20个碳原子的芳基,
每个Y独立地为1至20个碳原子的烷基;取代或未取代的3至20个碳原子的环烷基;或取代或未取代的6至20个碳原子的芳基,以及
n为2或3。
5.一种由下式2表示的配体化合物:
[式2]
在式2中,
X为-Si(R1)(R2)(R3);或6至20个碳原子的芳基,
R1至R3各自独立地为1至20个碳原子的烷基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基,
R4和R5各自独立地为氢;1至20个碳原子的烷基;2至20个碳原子的烯基;2至20个碳原子的炔基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基;以及
R6为氢;1至20个碳原子的烷基;3至20个碳原子的环烷基;6至20个碳原子的芳基;7至20个碳原子的烷基芳基;或7至20个碳原子的芳基烷基;其中,当X为6至20个碳原子的芳基时,R6不为6至20个碳原子的芳基或7至20个碳原子的烷基芳基。
7.一种催化剂组合物,其包含根据权利要求1至4任一项所述的过渡金属化合物和助催化剂。
8.根据权利要求7所述的催化剂组合物,其中,所述助催化剂包含选自下式4至6中的一种或多种:
[式4]
-[Al(Ra)-O]a-
[式5]
D(Ra)3
[式6]
[L-H]+[Z(A)4]-或[L]+[Z(A)4]-
其中,
各Ra独立地为卤素基团;1至20个碳原子的烃基;或卤素取代的1至20个碳原子的烃基,
a是2或更大的整数。
D是铝或硼,
L是中性或阳离子路易斯酸,
Z是第13族中的元素,
各A独立地为6至20个碳原子的芳基或1至20个碳原子的烷基,其中一个或多个氢原子可被取代基取代,以及
A的取代基是卤素基团;1至20个碳原子的烃基;1至20个碳原子的烷氧基;或6至20个碳原子的芳氧基。
9.一种制备烯烃聚合物的方法,所述方法包括:在根据权利要求7所述的催化剂组合物的存在下聚合烯烃单体的步骤。
10.根据权利要求9所述的制备烯烃聚合物的方法,其中,所述烯烃单体是选自乙烯、丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯、1-十一碳烯、1-十二碳烯、1-十四碳烯、1-十六碳烯和1-二十碳烯中的一种或多种。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2019-0049172 | 2019-04-26 | ||
KR20190049172 | 2019-04-26 | ||
PCT/KR2020/005437 WO2020218874A1 (ko) | 2019-04-26 | 2020-04-24 | 리간드 화합물, 전이금속 화합물 및 이를 포함하는 촉매 조성물 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113272310A true CN113272310A (zh) | 2021-08-17 |
CN113272310B CN113272310B (zh) | 2024-07-12 |
Family
ID=
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024051442A1 (zh) * | 2022-09-08 | 2024-03-14 | 中国石油天然气股份有限公司 | 一种用于制备聚(4-甲基-1-戊烯)的主催化剂及其应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002038628A2 (en) * | 2000-11-07 | 2002-05-16 | Symyx Technologies, Inc. | Substituted pyridyl amine ligands, complexes and catalysts therefrom; processes for producing polyolefins therewith |
WO2006096881A1 (en) * | 2005-03-09 | 2006-09-14 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins |
WO2013012897A1 (en) * | 2011-07-19 | 2013-01-24 | Dow Corning Corporation | Copper containing complex, condensation reaction compositions containing the complex, and methods for the preparation and use of the compositions |
CN105849116A (zh) * | 2013-11-26 | 2016-08-10 | 庄信万丰股份有限公司 | 用于制备包含p和n供体配体的钌或锇络合物的方法 |
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002038628A2 (en) * | 2000-11-07 | 2002-05-16 | Symyx Technologies, Inc. | Substituted pyridyl amine ligands, complexes and catalysts therefrom; processes for producing polyolefins therewith |
WO2006096881A1 (en) * | 2005-03-09 | 2006-09-14 | Exxonmobil Chemical Patents Inc. | Methods for oligomerizing olefins |
WO2013012897A1 (en) * | 2011-07-19 | 2013-01-24 | Dow Corning Corporation | Copper containing complex, condensation reaction compositions containing the complex, and methods for the preparation and use of the compositions |
CN105849116A (zh) * | 2013-11-26 | 2016-08-10 | 庄信万丰股份有限公司 | 用于制备包含p和n供体配体的钌或锇络合物的方法 |
Non-Patent Citations (7)
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024051442A1 (zh) * | 2022-09-08 | 2024-03-14 | 中国石油天然气股份有限公司 | 一种用于制备聚(4-甲基-1-戊烯)的主催化剂及其应用 |
Also Published As
Publication number | Publication date |
---|---|
WO2020218874A1 (ko) | 2020-10-29 |
TW202110859A (zh) | 2021-03-16 |
KR102564410B1 (ko) | 2023-08-08 |
JP7309256B2 (ja) | 2023-07-18 |
JP2022515668A (ja) | 2022-02-21 |
US20220049031A1 (en) | 2022-02-17 |
EP3892624A1 (en) | 2021-10-13 |
KR20200125518A (ko) | 2020-11-04 |
EP3892624A4 (en) | 2022-03-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6858558B2 (en) | Olefin polymerization catalyst component and catalyst system and polymerization process using such a catalyst system | |
JP5302219B2 (ja) | 新規なシクロペンタジエニルリガンドを有する第4族遷移金属化合物、その製造方法、およびそれを用いたオレフィン系重合体の製造方法 | |
JP2018502819A (ja) | リガンド化合物、遷移金属化合物及びこれを含む触媒組成物 | |
KR20150058054A (ko) | 메탈로센 담지 촉매 및 이를 이용하는 폴리올레핀의 제조방법 | |
CN107075008B (zh) | 金属茂化合物、负载金属茂的催化剂以及使用该负载金属茂的催化剂制备聚烯烃的方法 | |
EP3184556B1 (en) | Metallocene-supported catalyst and method of preparing polyolefin using the same | |
AU4112000A (en) | Method for polymerising olefins | |
KR20150062004A (ko) | 혼성 담지 메탈로센 촉매의 제조방법 | |
US20120071615A1 (en) | Bi-Nuclear Metallocene Compound and the Preparation Method of Polyolefin Using the Same | |
JP7214300B2 (ja) | 遷移金属化合物、触媒組成物およびそれを用いたポリプロピレンの製造方法 | |
CN107001394B (zh) | 新颖的第4族过渡金属化合物及其用途 | |
KR101734427B1 (ko) | 담지 촉매 및 이를 이용하는 올레핀계 중합체의 제조방법 | |
CN113272310A (zh) | 配体化合物,过渡金属化合物和包含其的催化剂组合物 | |
EP3330296B1 (en) | Method for preparing supported metallocene catalyst | |
CN113272310B (zh) | 配体化合物,过渡金属化合物和包含其的催化剂组合物 | |
EP4050013A1 (en) | Ligand compound, transition metal compound, and catalyst composition comprising same | |
CN107406538B (zh) | 金属茂负载型催化剂及使用其制备聚烯烃的方法 | |
TWI837350B (zh) | 配位基化合物、過渡金屬化合物、及含彼之觸媒組成物 | |
KR102065163B1 (ko) | 전이금속 화합물 및 이를 포함하는 촉매 조성물 | |
CN112745414B (zh) | 非对称桥联二茂茚基过渡金属催化剂、制备方法及应用 | |
KR20190023926A (ko) | 에틸렌 올리고머화용 전이금속 화합물을 포함하는 촉매 시스템 및 이를 이용한 선형 알파 올레핀의 제조방법 | |
KR100548614B1 (ko) | 폴리에틸렌 제조용 메탈로센 촉매 및 이를 이용한 폴리에틸렌의제조방법 | |
KR102092271B1 (ko) | 전이금속 화합물 및 이를 포함하는 촉매 조성물 | |
CN111875630B (zh) | 吡啶基二氨基过渡金属络合物,其的生产和用途 | |
EP3696184A1 (en) | Polyolefin catalyst and method for preparing polyolefin using same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant |