CN1060176C - 有机金属芴基化合物其制备和应用 - Google Patents
有机金属芴基化合物其制备和应用 Download PDFInfo
- Publication number
- CN1060176C CN1060176C CN94118160A CN94118160A CN1060176C CN 1060176 C CN1060176 C CN 1060176C CN 94118160 A CN94118160 A CN 94118160A CN 94118160 A CN94118160 A CN 94118160A CN 1060176 C CN1060176 C CN 1060176C
- Authority
- CN
- China
- Prior art keywords
- fluorenyl
- dichloride
- cyclopentadienyl
- metallocenes
- zirconium
- 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.)
- Expired - Lifetime
Links
- 238000002360 preparation method Methods 0.000 title description 21
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 93
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 229910052726 zirconium Inorganic materials 0.000 claims description 153
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 150
- -1 tetrahydro indenyl Chemical group 0.000 claims description 142
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 84
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 48
- 238000006116 polymerization reaction Methods 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 229910052735 hafnium Inorganic materials 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 23
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 17
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 6
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- QVRBGKYLLCLCHL-UHFFFAOYSA-N 5-methylcyclopenta-1,3-diene Chemical compound CC1C=CC=C1 QVRBGKYLLCLCHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- DTNMLFOXJUUMQV-UHFFFAOYSA-N 1-ethyl-9h-fluorene Chemical compound C1C2=CC=CC=C2C2=C1C(CC)=CC=C2 DTNMLFOXJUUMQV-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims 20
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 20
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- GQFDBTYBFCGPNW-UHFFFAOYSA-N CCC1=C(C=C(C2=C1CC3=C2C=CC(=C3)C(C)(C)C)C)C(C)(C)C Chemical compound CCC1=C(C=C(C2=C1CC3=C2C=CC(=C3)C(C)(C)C)C)C(C)(C)C GQFDBTYBFCGPNW-UHFFFAOYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 229920013639 polyalphaolefin Polymers 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- 239000000126 substance Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- 150000001721 carbon Chemical group 0.000 description 17
- 229910007926 ZrCl Inorganic materials 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 239000004411 aluminium Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000003446 ligand Substances 0.000 description 11
- 150000002736 metal compounds Chemical class 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 229910052723 transition metal Inorganic materials 0.000 description 9
- 150000003624 transition metals Chemical class 0.000 description 9
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- BFWHKZGBJPYOPJ-UHFFFAOYSA-N 2-tert-butyl-1-ethyl-9H-fluorene Chemical compound C(C)(C)(C)C1=C(C=2CC3=CC=CC=C3C=2C=C1)CC BFWHKZGBJPYOPJ-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- MUYPYDXTPSWUKZ-UHFFFAOYSA-N 1-ethyl-4-methyl-9H-fluorene Chemical compound CC1=CC=C(C=2CC3=CC=CC=C3C12)CC MUYPYDXTPSWUKZ-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- CGSHGJCXYTZXAP-UHFFFAOYSA-N 2-ethyl-1-methyl-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(CC)C(C)=C3CC2=C1 CGSHGJCXYTZXAP-UHFFFAOYSA-N 0.000 description 3
- 102000040350 B family Human genes 0.000 description 3
- 108091072128 B family Proteins 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000027455 binding Effects 0.000 description 3
- 238000009739 binding Methods 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052752 metalloid Inorganic materials 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- MNHSTWRXCNIKFM-UHFFFAOYSA-N 1,2-diethyl-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(CC)C(CC)=C3CC2=C1 MNHSTWRXCNIKFM-UHFFFAOYSA-N 0.000 description 2
- QZNJRVQSDQIRCQ-UHFFFAOYSA-N 1-(2-bromoethyl)-9h-fluorene Chemical compound C1C2=CC=CC=C2C2=C1C(CCBr)=CC=C2 QZNJRVQSDQIRCQ-UHFFFAOYSA-N 0.000 description 2
- CLRIMWMVEVYXAK-UHFFFAOYSA-N 5-ethylcyclopenta-1,3-diene Chemical compound CCC1C=CC=C1 CLRIMWMVEVYXAK-UHFFFAOYSA-N 0.000 description 2
- CVIGYQZQDNHNTC-UHFFFAOYSA-N 5-propan-2-ylcyclopenta-1,3-diene Chemical compound CC(C)C1C=CC=C1 CVIGYQZQDNHNTC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
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- 230000002776 aggregation Effects 0.000 description 2
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
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- 239000012965 benzophenone Substances 0.000 description 2
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
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- FDAFQMKZQJTHEK-UHFFFAOYSA-N (7-benzoyl-9h-fluoren-2-yl)-phenylmethanone Chemical class C=1C=C(C2=CC=C(C=C2C2)C(=O)C=3C=CC=CC=3)C2=CC=1C(=O)C1=CC=CC=C1 FDAFQMKZQJTHEK-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- NMEQHHYHRUXYEN-UHFFFAOYSA-N 1,2-diiodo-9h-fluorene Chemical class C1=CC=C2CC3=C(I)C(I)=CC=C3C2=C1 NMEQHHYHRUXYEN-UHFFFAOYSA-N 0.000 description 1
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 1
- FWYDVUVWJDWWQH-UHFFFAOYSA-N 1-(1-acetyl-9h-fluoren-2-yl)ethanone Chemical class C1=CC=C2C3=CC=C(C(=O)C)C(C(C)=O)=C3CC2=C1 FWYDVUVWJDWWQH-UHFFFAOYSA-N 0.000 description 1
- WSCPBPGDAIVEBL-UHFFFAOYSA-N 1-(2-bromopropyl)-9h-fluorene Chemical compound C1C2=CC=CC=C2C2=C1C(CC(Br)C)=CC=C2 WSCPBPGDAIVEBL-UHFFFAOYSA-N 0.000 description 1
- JDDQUCYOIWBQIL-UHFFFAOYSA-N 1-[2-(3-methylcyclopenta-2,4-dien-1-yl)ethyl]-9H-fluorene Chemical compound C1(=CC=CC=2C3=CC=CC=C3CC1=2)CCC1C=C(C=C1)C JDDQUCYOIWBQIL-UHFFFAOYSA-N 0.000 description 1
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- GAKILTKGUQTOBF-UHFFFAOYSA-N 1-ethyl-2-methyl-9H-fluorene Chemical compound CC1=C(C=2CC3=CC=CC=C3C=2C=C1)CC GAKILTKGUQTOBF-UHFFFAOYSA-N 0.000 description 1
- JNTPESLCFLAUMV-UHFFFAOYSA-N 1-naphthalen-1-yl-9h-fluorene Chemical class C1=CC=C2C(C=3C=CC=C4C5=CC=CC=C5CC=34)=CC=CC2=C1 JNTPESLCFLAUMV-UHFFFAOYSA-N 0.000 description 1
- WNWQTRNYOODDCV-UHFFFAOYSA-N 1-tert-butyl-2-ethyl-9H-fluorene Chemical compound C(C)C1=C(C=2CC3=CC=CC=C3C=2C=C1)C(C)(C)C WNWQTRNYOODDCV-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZRUORDUHAYISIU-UHFFFAOYSA-N 2,7-di(propan-2-yl)-9h-fluorene Chemical class CC(C)C1=CC=C2C3=CC=C(C(C)C)C=C3CC2=C1 ZRUORDUHAYISIU-UHFFFAOYSA-N 0.000 description 1
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical class BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 description 1
- BERZFFGKIZFGLB-UHFFFAOYSA-N 2,7-dicyclohexyl-9h-fluorene Chemical class C1=C2CC3=CC(C4CCCCC4)=CC=C3C2=CC=C1C1CCCCC1 BERZFFGKIZFGLB-UHFFFAOYSA-N 0.000 description 1
- AYSWCWQPPPZQFM-UHFFFAOYSA-N 2,7-diethyl-9h-fluorene Chemical class CCC1=CC=C2C3=CC=C(CC)C=C3CC2=C1 AYSWCWQPPPZQFM-UHFFFAOYSA-N 0.000 description 1
- TYZBYRNPCRCLDA-UHFFFAOYSA-N 2,7-ditert-butyl-1-[2-(9h-fluoren-1-yl)ethyl]-9h-fluorene Chemical compound C1C2=CC=CC=C2C2=C1C(CCC1=C(C=CC3=C1CC=1C3=CC=C(C=1)C(C)(C)C)C(C)(C)C)=CC=C2 TYZBYRNPCRCLDA-UHFFFAOYSA-N 0.000 description 1
- DFZYPLLGAQIQTD-UHFFFAOYSA-N 2,7-ditert-butyl-9h-fluorene Chemical compound CC(C)(C)C1=CC=C2C3=CC=C(C(C)(C)C)C=C3CC2=C1 DFZYPLLGAQIQTD-UHFFFAOYSA-N 0.000 description 1
- OWWRMMIWAOBBFK-UHFFFAOYSA-N 3,4-dimethylhex-1-ene Chemical compound CCC(C)C(C)C=C OWWRMMIWAOBBFK-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical class C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- FMIDFXCVRGPJHZ-UHFFFAOYSA-N 4,4-diethylhex-1-ene Chemical compound CCC(CC)(CC)CC=C FMIDFXCVRGPJHZ-UHFFFAOYSA-N 0.000 description 1
- HVQLOZLIRFSRPU-UHFFFAOYSA-N 4-tert-butyl-1-ethyl-9H-fluorene Chemical compound C1C2=CC=CC=C2C2=C1C(CC)=CC=C2C(C)(C)C HVQLOZLIRFSRPU-UHFFFAOYSA-N 0.000 description 1
- DGDAVTPQCQXLGU-UHFFFAOYSA-N 5437-38-7 Chemical compound CC1=CC=CC(C(O)=O)=C1[N+]([O-])=O DGDAVTPQCQXLGU-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZZQGRHDFPHLPFH-UHFFFAOYSA-N C1(=CC=CC=2C3=CC=CC=C3CC12)C1=CC=C(CN)C=C1 Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)C1=CC=C(CN)C=C1 ZZQGRHDFPHLPFH-UHFFFAOYSA-N 0.000 description 1
- JZMQTTMEACDUMH-UHFFFAOYSA-N C1(=CCCCC1)C1=CC=CC=2C3=CC=CC=C3CC1=2 Chemical class C1(=CCCCC1)C1=CC=CC=2C3=CC=CC=C3CC1=2 JZMQTTMEACDUMH-UHFFFAOYSA-N 0.000 description 1
- PYUCPHXJBDFVMO-UHFFFAOYSA-N C1(C=CC=C1)CCC1=CC=CC=2C3=CC=CC=C3CC1=2 Chemical compound C1(C=CC=C1)CCC1=CC=CC=2C3=CC=CC=C3CC1=2 PYUCPHXJBDFVMO-UHFFFAOYSA-N 0.000 description 1
- LAFLRXFSXWXQJT-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3CC12.[I] Chemical class C1=CC=CC=2C3=CC=CC=C3CC12.[I] LAFLRXFSXWXQJT-UHFFFAOYSA-N 0.000 description 1
- MFQKHGLBNFGNQQ-UHFFFAOYSA-N C1C(C2=CC=CC3=C2CC2=CC=CC=C32)=CC=C1.Cl.Cl Chemical compound C1C(C2=CC=CC3=C2CC2=CC=CC=C32)=CC=C1.Cl.Cl MFQKHGLBNFGNQQ-UHFFFAOYSA-N 0.000 description 1
- USFMDNKRRAPFHC-UHFFFAOYSA-N CC(C)(C)BrC1=CC=CC=C1 Chemical compound CC(C)(C)BrC1=CC=CC=C1 USFMDNKRRAPFHC-UHFFFAOYSA-N 0.000 description 1
- CXBUWYDCUCYOSH-UHFFFAOYSA-N CC(C1=C(C=CC2=C1CC3=C2C=CC(=C3)C(C)(C)C)C(C)(C)C)Br Chemical compound CC(C1=C(C=CC2=C1CC3=C2C=CC(=C3)C(C)(C)C)C(C)(C)C)Br CXBUWYDCUCYOSH-UHFFFAOYSA-N 0.000 description 1
- TZYQADPFBSMPOR-UHFFFAOYSA-N CC1(C=CC=C1)[Zr] Chemical compound CC1(C=CC=C1)[Zr] TZYQADPFBSMPOR-UHFFFAOYSA-N 0.000 description 1
- YRYSAQCKKXGZGJ-UHFFFAOYSA-N CC1=CC=C(C=2CC3=CC=CC=C3C12)[Zr] Chemical compound CC1=CC=C(C=2CC3=CC=CC=C3C12)[Zr] YRYSAQCKKXGZGJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- RJNJGYJBMIOKMX-UHFFFAOYSA-N FC1=CC=C(C=C1)C1=CC=CC=2C3=CC=CC=C3CC1=2 Chemical class FC1=CC=C(C=C1)C1=CC=CC=2C3=CC=CC=C3CC1=2 RJNJGYJBMIOKMX-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- 235000005764 Theobroma cacao ssp. cacao Nutrition 0.000 description 1
- 235000005767 Theobroma cacao ssp. sphaerocarpum Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 1
- JFWBIRAGFWPMTI-UHFFFAOYSA-N [Zr].[CH]1C=CC=C1 Chemical compound [Zr].[CH]1C=CC=C1 JFWBIRAGFWPMTI-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910000091 aluminium hydride Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001499 aryl bromides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000001046 cacaotero Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- PWAPCRSSMCLZHG-UHFFFAOYSA-N cyclopentylidene Chemical group [C]1CCCC1 PWAPCRSSMCLZHG-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 150000002234 fulvenes Chemical class 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 1
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- DBKDYYFPDRPMPE-UHFFFAOYSA-N lithium;cyclopenta-1,3-diene Chemical compound [Li+].C=1C=C[CH-]C=1 DBKDYYFPDRPMPE-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- CXIRWLOIAQYBLZ-UHFFFAOYSA-N nickel(2+);5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Ni+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 CXIRWLOIAQYBLZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000006209 tert-butylation Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
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Abstract
本发明公开了含芴基金属茂及其制备方法。也公开了使用金属茂作为聚合催化剂及由这类聚合制得的聚合物。
Description
本申请是申请日为1991年7月23日的美国专利申请序列号07/734,853的部分继续申请,而序列号07/734 853是申请日为1991年5月9日的美国专利申请序列号07/697,363(现在的美国专利第5,191,132号)的部分继续申请。本申请也是申请日为1993年1月7日的美国专利申请序列号08/003,221(它是申请日为1991年5月9日的美国专利申请序列号07/697,363的继续申请)的部分继续申请。本申请也是申请日为1993年5月20日的美国专利申请序列号08/064/630(它是上述的申请日为1991年7月23日的美国专利申请序列号07/734,853的部分继续申请)的部分继续申请。本申请还是申请日为1992年11月30日的美国专利申请序列号07/984,054(它是上述的申请日为1991年5月9日的美国专利申请序列号07/6967,363的部分继续申请)的部分继续申请。上述申请披露的内容作为文献并入本文。
本发明涉及有机金属化合物。更具体地说,本发明涉及含至少一个芴基配位体的有机化合物。另一个方面,本发明涉及含有机金属芴基化合物的催化剂体系。第三个方面,本发明涉及使用这类有机金属芴基化合物聚合稀烃的方法及由这类聚合制得的聚合物。
用于本文中的“环戊二烯型化合物”指含环戊二烯结构化合物。例子包括未取代的环戊二烯,未取代的茚,未取代的芴和这类化合物的取代衍生物。该术语也包括四氢茚。多环环戊二烯化合物也包括在该术语中。
许多环戊二烯型金属茂被发现在烯烃聚合催化剂体系中是有用的。本领域注意到这类环戊二烯型金属茂化学结构的变化对金属茂用作聚合催化剂的适宜性有重大影响。例如人们发现在环戊二烯型配位体上的取代基类型和大小影响催化剂的活性,催化剂的立体选择性,催化剂的稳定性和所得聚合物的其它性能,然而各种取代基的效果在很大程度上仍然是经验性的,就是说为确定具体的变化将对环戊二烯基型金属茂具体的效果必须进行实验。一些环戊二烯基型金属茂的一些例子公开在U.S.Patent Nos、4,530,914;4,808,561;和4,892,851,它们公开的内容作为文献并入本文。
虽然先有技术许多文献设相了含芴基的金属茂,但在本发明以前仅有很有限的含芴基金属茂被制备。The journal of Orgenometallicchemistry,vol,113,331-339(1976)(其公开的内容作为文献并入本文)公开了制备二氯化二-芴基合锆和二-芴基二甲基合锆。美国专利4,982,851和Vew Journal of Chemistry,Vol,14,第499-503页(1990)(其公开的内容作为文献并入本文)都公开了由配位体1-(环戊二烯基)-1-(芴基)-1,1-二甲基亚甲基制备金属茂。The New Journal of Chemistry文章也公开了制备类似的化合物,其中环戊二烯基在3位有甲基取代基。除非另有说明,用于本文中的术语芴基指9-芴基。
本发明的目的是提供新的含芴基的金属茂。本发明的第二个目的是提供制备新的芴基类金属茂的方法。本发明的第三个目的是提供使用芴基类金属茂的聚合催化剂。本发明的第四个目的是提供使用芴基类金属茂催化体系聚合烯烃的方法。本发明的第五个目的是提供使用这类含芴基金属茂的催化剂制得的聚合物。
本发明提供式Rx”(F1Rn)(CpRm)MeQK的新金属茂,其中F1是芴基,Cp是环戊二烯基,茚基,四氢茚基或芴基,每个R可相或不同为卤根或有1到20个碳原子的有机基团,R”是连结(F1Rn)和(CpRm)的结构桥联基,Me是选自周期表ⅣB,ⅤB和ⅥB族的金属,每个Q相同或不同,选自有1到20个碳原子的烃基或烃基氧基和卤素,X是1或0,K是足以添满Me余下价的数字,n是0到7的数,m是0到7的数,其附加特征在于如果(CpRm)是未取代的芴基和x是0,那么n是1至7,和如果(CpRm)是未取代的环戊二烯基或3-甲基环戊二烯基和R”是1,1-二甲基-亚甲基,则n是1到7。
按本发明第二个方面,提供一种形成含芴基金属茂的方法,包括在与过渡金属化合物不配位的用于芴基盐的非卤化的溶剂存芴下,将选择的芴基化合物的碱金属盐与式MeQk表示的过渡金属化合物反应。
按照本发明的第三个方面,提供一种烯烃的聚合方法,包括在适宜的反应条件下将所述烯烃与催化剂体系接触,所述催化剂体系包括如上所述的含芴基金属茂和适宜的有机铝助催化剂。
按照本发明第四个方面,提供由这类聚合所获得的聚合物产品。
本发明提供的新的金属茂分成两大类。一类涉及其中取代或未取代的芴基通过桥结构R”联到另一个环戊二烯型基团上的金属茂(bridged metallocenes)。这些金属茂在本文中称为桥联金属茂。另一类为未桥联金属茂即芴基配位体和另一环戊二烯基型配位体联到金属上但彼此不相联。这些金属茂被称作未桥联金属茂。制备能用于制备金属茂的含芴基的环戊二烯型化合物的方法公开在上述美国专利申请序列号697,363中。
金属Me选自周期表Ⅳ,ⅤB或ⅥB族金属。优选的金属包括钛,锆,铪,锆和钒。R”能选自任何适宜的桥结构。通常包括有1到20个碳原子,特别是2到20个碳原子的烃基和含杂原子的亚烷基;锗;硅;磷;硼;铝;锡;氧;氮;等。桥联基团甚至可以是环烃基团。一些例子包括亚环戊基,亚金刚烷基,亚环己烯基,亚环己基,亚茚基等。桥联基团R”为烃基时,可以有芳基性质如苯基取代的亚烷基;但优选使用脂肪亚烷基。最优选的桥联基团是有1至6个碳原子的烃基或含杂原子的亚烷基。在一特别优选的实施方案中k等于Me的化合价减2。
取代基R能从一系列取代基中选择。在优选的实施方案中,取代基R各自独立地选自卤根或有1到20个碳原子的烃基。在一特别优选的实施方案中,烃基R是烷基,芳基或芳烷基。更优选的烷基R有1到5个碳原子。
每个Q是烃基如芳基,烷基,链烯基,芳烷基或有1到20个碳原子的芳烷基,有1到20个碳原子的烃基氧基,或卤素。示例性的Q烃基包括甲基,乙基,丙基,丁基,戊基,异戊基,己基,异丁基,庚基,辛基,壬基,癸基,十六烷基,2-乙基己基,苯基等。示例性卤素原子包括氯,溴,氟和碘,在这些卤原子中,氯是优选的。示例性的烃氧基包括甲氧基,乙氧基,丙氧基,丁氧基,戊氧基等。
在上述结构式范围内的未桥联金属茂的说明性而非限制性的例子包括二氯化二(1-甲基芴基)合锆,二(1-甲基芴基)·二甲基合锆,二氯化二(1-甲基芴基)合铪,二氯化二(1-叔丁基芴基)合锆,二氯化二(2-乙基芴基)合锆,二氯化二(4-甲基芴基)合锆,二氯化二(4-甲基芴基)合铪,二氯化二(2-叔丁基芴基)合锆,二氯化二(4-叔丁基芴基)合锆,二氯化(2,7-二叔丁基芴基)合锆,二氯代二(2,7-二叔丁基-4-甲基芴基)合锆等。
含桥联芴基配位体的金属茂的说明而非限定性例子包括例如二氯化(1,1-二芴基甲烷)合锆,二氯化(1,2-二芴基乙烷)合锆,二氯化(1,3-二芴基丙烷)合锆,二氯化(1,2-二芴基乙烷)合铪,二氯化(1,3-二芴基丙烷)合铪,二氯化(1-芴基-2-甲基-2-芴基乙烷)合锆,二氯化(二甲基甲硅烷基二芴基)合锆,二氯化(1,2-二(1-甲基)芴基乙烷)合锆,二氯化(1,2-二(1-甲基芴基)乙烷)合铪,二氯化(1,2-二(2-乙基芴基)乙烷)合锆,二氯化(1,2-二(2-叔丁基芴基)乙烷)合锆,二氯化(1,2-二(2-叔丁基芴基)乙烷)合铪,二氯化(1,2-二(2-叔丁基芴基)乙烷)合锆,二氯化(1,2-二(2-叔丁基芴基)乙烷)合锆,二氯化(1,2-二(4-甲基芴基)乙烷)合锆,二氯化(1,2-二(4-甲基芴基)乙烷)合铪,二氯化(1,2-二(4-甲基芴基)乙烷)合锆,二氯化(1-(芴基)-1-(环戊二烯基)甲烷)合锆,二氯化(1-芴基-1-环戊二烯基甲烷)合铪,二氯化(1-(2,7-二叔丁基芴基)-1-(环戊二烯基)乙烷)合铬,二氧化(1-芴基)-2-(环戊二烯基)乙烷)合锆,二氯化(1-芴基-2-茚基乙烷)合锆,二氯化(1-芴基-2-(3-甲基环戊二烯基)乙烷)合锆,二氧化(1-芴基-2-茚基乙烷)合铪,二氯化(1-芴基-2-甲基-2-茚基乙烷)合锆,二氯化(1-芴基-2-甲基-2-茚基乙烷)合铪,二氯化(1-芴基-2-甲基-2-茚基乙烷)合锆,二氯化(1-芴基-2-甲基-2-茚基乙烷)合铪,二氯化(二-芴基乙烷)合钒,二氯化(1,2-二芴基乙烷)合钒,三氯化(1-芴基-1-环戊二烯基甲烷)合锆,二氯化(1-芴基-2-甲基-2-(3-甲基环戊二烯基)乙烷)合锆,二氯化(1-(1-甲基芴基)-2-(4-甲基芴基)乙烷)合锆,二氯化(1-(2,7-二叔丁基芴基)-2-(芴基)乙烷)合锆,二氯化(1,2-二(2,7-二叔丁基-4-甲基芴基)乙烷)合锆,二氯化(1-(2,7-二甲基乙烯基芴基)-1-(环戊二烯)-1,1-二甲基甲烷)合铬(它也可称为二氯化(1-(2,7-二异丙烯基芴基)-1-(环戊二烯基)-1,1-二甲基甲烷)合锆),二氯化(1-(2,7-二
基芴基)-1-(环戊二烯基)-1,1-二甲基甲烷)合铬,二氧化(1-(2,7-二甲氧基芴基)-1-(环戊二烯基)-1,1-二苯基甲烷)合锆,二氯化(1-(2,7-二甲氧基芴基)-1-(环戊二烯基)-1,1-二甲基甲烷)合锆,二氯化(1-(2,7-二苯基芴基)-1-(环戊二烯基)-1-苯基甲烷)合锆,二氯化(1-(2,7-二溴芴基)-1-(环戊二烯基)-1-甲基甲烷)合锆,二氯化(1-(2,7-二
基芴基)-1-(环戊二烯基)环戊烷)合锆,二氯化(1-(2,7-二甲基芴基)-1-(环戊二烯基)甲烷)合锆,二氯化(1-(2,7-二苯基芴基)-1-(环戊二烯基)2,3-二氢化茚)合锆,二氯化(1-(2,7-二叔丁基芴基)-1-(环戊二烯基)环戊烷)合锆,二氯化(1-(2,7-二溴芴基)-1-(环戊二烯基)甲烷)合锆,二氯化(1-(2,7-二甲基芴基)-1-(环戊二烯基)-1,1-二甲基甲烷)合锆和二氯(1-(2,7-二(二甲基苯基二价碳基)芴基)-1-(环戊二烯基)二苯基甲烷)合锆等。
特别优选的金属茂包括含至少一个取代的芴基即有至少一个F1Rn。基团其中n是1至7的桥联和未桥联金属茂。在一优别优选的实施方案中,使用式(F1(Rn)R”(CpRm)所示的桥联芴基化合物其中F1,R,R”和m定义同上,n是1到7。优选1到4,特别是2。
另一类特别优选的金属茂是含至少一个对称取代的芴基基团的桥联金属茂。用于本文中的术语、对称取代的”是指在芴基基团相对位置上有取代基的芴基,如2,7-二烷基芴基;2,7-二环烯基芴基;3,6-二烷基芴基,2,7-二卤代芴基;2,7-二芳基芴基;1,8-二烷基芴基;4,5-二烷基芴基;2,7-二芳烷基芴基等。最优选在芴基上的取代基是相同的。优选的烷基取代基有1到20个碳原子,更好为1到6个碳原子,最好为1到4相碳原子。最优选在芴基上的取代基是相同。优选的烷基取代基有1到20个碳原子,更好为1到6个碳原子,最好为1到4个碳原子。最优选的卤代取代基为氯代,碘代和溴代。芳基取代基的例子包括有6到20个碳原子,更好为6到10个碳原子的芳基。同样芳烷基取代含7到20个碳原子,更好为7到10个碳原子。应该意识到在某此情况下,如果桥基和芴基上的取代基特别大,很难制配位体,二烷基盐或金属茂。
本发明的金属茂及有关的金属茂可在适宜的溶剂中在适宜的条件下将桥联芴基化合物的碱金属盐与适宜的过渡金属化合物反应来制备。
制备桥联配位体的技术公开在美国专利5,191,132和上述美国专利申请序列号08/064,630和07/984,054中。亚甲基桥联配位体能用6或6,6-取代的富烯制备。富烯反应的例子公开在美国专利4,892,851和J.organomet.Chem.435,299-310(1992)中。通常该技术包括2,7-二取代芴的碱金属盐与选择的富烯型化合物反应。6,6-二苯基富烯能通过适宜的芳基溴如苯基溴,对甲苯基溴,对-氟苯基溴来对叔丁基苯基溴反应形成格利雅试剂,随后水解制得。然后滴加甲酸甲酯生成二芳基醇。然后将该二芳基甲基醇优选使用硫酸或铬酸缓缓氧化得相应的取代的苯酮。然后将所得的取代的苯酮与环戊二烯在含钠的乙醇中反应得6,6-二取代富烯。
该技术也涉及通过1-茚酮与环戊二烯在乙醇和乙醇钠存在下反应制备2,3-二氢化茚基富烯(它也被称为2,3-二氢化亚茚基富烯)。2,3-二氢化茚基富烯特别有用,在于它能与芴化合物碱金属盐反应得2,3-二氢化茚基桥联的芴基环戊二烯基化合物。例子是1-(2,7-二苯基芴基)-1-(环戊二烯基)-2,3-二氢化茚。
用来制备桥联配位体的对称取代的芴基化合物能用先有技术公知的方法来制备。下面进一步详细描述生成一些取代的芴基化合物的一些具体的方法。
用于本文的术语过渡金属化合物包括式MeQk化合物其中Me,Q和K定义同上。一些非限定例子包括四氯化锆;四氯化铪,四氧化钛,三氯化环戊二烯基锆,二氯化芴基环戊二烯基锆。三氯化3-甲基环戊二烯基锆,二氯化-2,3-二氢化茚基环戊二烯基锆,三氯化4-甲基芴基锆等。
金属茂(其中Q不是卤素)能很容易地在先有技术金属茂中用来形成这类配位体的条件下将卤化物与烃基或烃基氧基碱金属盐反应来制备。参见例如上述的J.org.chem.113,331-339(1976)。另一种方法涉及式MeQk所示化合物(其中至少一个Q是烃基或烃基氧基)与桥联或未桥联芴基化合物反应。
本发明的一个实施方案包括在非卤化且对过渡金属化合物不配位的液体稀释剂存在下进行含芴基的盐和过渡金属化合物的反应。这类适宜的液体的例子包括烃如甲苯,戊烷,或己烷及非环醚化合物如乙醚。人们发现使用这类非卤化不配位的溶剂较使用THF作稀释剂通常能获得的更多的基本纯的更稳定的金属茂且能使反应在更高温度条件下反应。在一特别优选的实施方案中,用作配位体的含芴基盐也是在非卤化和对过渡金属不配位的液体稀释中制备的。
桥联或未桥联的芴基化合物通常能使用本领域已知的任何技术来制备,例如它们能通过烷基碱金属与环戊二烯基化合物或每分子有两个环戊二烯基基团的桥联化合物反应来制备。烷基碱金属与环戊二烯基的摩尔比可以变化,然而通常该摩尔比为约0.5/1到约1.5/1的范围之内,优选约1/1。通常烷基碱金属的碱金属选自钠,钾和锂,和烷基有1到8个碳原子,更优选有1到4个碳原子。优选如果芴基盐使用四氢呋喃(THF)作为液体溶剂来制备,则在该盐与过渡金属卤化物接触之前分离该盐并除去基本上所有的THF。根据最终结果,桥联或未桥联芴基化合物与过渡金属化合物的摩尔比能在相当宽的范围内变化。然而通常当使用未桥联的芴基化合物时,未桥联芴基化合物与过渡金属化合物的摩尔比在约1∶1到约2∶1的范围内;当使用桥联化合物时,桥联化合物与过渡金属化合物的摩尔比约为1∶1。
所得金属茂能用本领域已知的常规方法如过滤,萃取,结晶和重结晶来回收和纯化。通常希望回收的金属茂无明显的付产品杂质。因此为获得比较纯的金属茂重结晶和部分结晶是需要的。二氯甲烷对这类重结晶特别有用。通常由未桥联芴基化合物形成的金属茂不如由桥联化合物形成的金属茂稳定。因为各种金属茂的稳定性不同,通常希望在金属茂制成后就使用或至少将金属茂储存在有利于其稳定的条件。例如金属茂通常可储存在低温如低于0℃和无氧或水的条件下。
所得的含芴基金属茂能与用于聚合烯烃单体的适宜助催化剂组合。在这类方法中,金属茂或助催化剂能用在不溶性固体颗粒载体上。
适且的助催化剂的例子通常包括任何过去一直与含过渡金属烯烃聚合催化剂共用的有机金属助催化剂。一些典型的例子包括周期表ⅠA,ⅡA和ⅢB族金属的有机化合物。这类化合物的例子包括有机金属卤化物,有机金属氢化物甚至金属氢化物。一些具体的例子包括三乙基铝,三异丁基铝,氯化二乙基铝,氢化二乙基铝等等。已知的助催化剂的其它例子包括使用诺如公开在美国专利5,155,080中的稳定的不配位的反阴离子技术例如使用三苯基碳翁四(五氟苯基)硼酸盐。另一个例子是使用诸如由Zambelli等人在Maro-molecules,22,2186(1989)中公开的三甲基铝和二甲基氟铝的混合物。在这类方法中,金属茂或助催化剂能用在不溶性固体载体上。
最优选的助催化剂是铝噁烷。这类化合物包括有下式所示重复单元的化合物:其中R是烷基,通常有1到5个碳原子。铝噁烷(有时也称聚(氧化烃基铝))在本领域是公知的且通常通过有机烃基铝化合物与水反应来制备。这类制技术公开在U.S.3242,099和4,808,5614,其公开的内容作为文献并入本文。最优选的助催化剂由三甲基铝或三乙基铝(有时也分别称为聚(氧化甲基铝)和聚(氧化乙基铝))来制备。将铝噁烷与三烷基铝(如公开在美国专利4,794,096中,其内容作为文献并入本文)混合使用也在本发明范围之内。
含芴基的金属茂与铝噁烷组合使用能用来聚合烯烃。通常这类聚合在均相系统中进行,其中催化剂和助催化剂是可溶的,然而在带载体形式的催化剂和助催化剂存在下以浆液或气相聚合的方式进行聚合也在本发明范围内。使用两个或多个含芴基金属茂的混合物或本发明的含芴基的金属茂与一个或多个其它环戊二烯型金属茂的混合物也在本发明的范围之内。
含芴基的金属茂与铝噁烷组合使用能用来聚合烯烃。通常这类聚合在均相系统中进行,其中催化剂和助催化剂是可溶的,然而在带载体形式的催化剂和助催化剂存在下以浆液或气相聚合的方式进行聚合也在本发明范围内。使用两个或多个含芴基金属茂的混合物或本发明的含芴基的金属茂一个或多个其它环戊二烯型金属茂的混合物也在本发明的范围之内。
含芴基的金属茂当与铝恶烷一起使用时对聚合单取代的有2到10个碳原子的脂肪α-烯烃特别有用。这类烯烃的例子包括乙烯,丙烯,丁烯-1,戊烯-1,3-甲基丁烯-1,己烯-1,4-甲基戊烯-1,3-乙基丁烯-1.庚烯-1,辛烯-1,癸烯-1,4,4-二甲基-1-戊烯,4,4-二乙基-1-己烯,3,4-二甲基-1-己烯等及其混合物。该催化剂对制备乙烯或丙烯共聚物特别有用,且通常较高分子量的烯烃占少量即约20%到10%(摩尔),更通常为约12%(摩尔),优选小于约10%(摩尔)。
根据所用具体金属茂和所需最终产品,聚合可在相当宽的条件下进行。金属茂在聚合烯烃中应用的通常条件包括诸如公开在美国专利3,242,099;4,892,851和4,530,914中的条件,这些专利公开的内容作为文献并入本文。通常认为用于先有技术中的任何聚合方法及任何过渡金属基催化剂体系都能与本发明的含芴基金属茂一起使用。
通常铝噁烷中的铝与金属茂中的过渡金属摩尔尔约为0.1∶1到约105∶1范围之内,更优选约5∶1到约104∶1。通常聚合将在对催化剂体系没有不利影响的液体稀释剂存在下进行的。这类液体稀释剂的例子包括丙烷,丁烷,异丁烷,戊烷,己烷,庚烷,辛烷,环己烷,甲基环己烷,甲苯,二甲苯等。聚合温度可在相当宽的范围内变化,通常在约-60℃到约280℃,更优选为约20℃到约160℃。通常压力为从约1到约500大气或更高。
用本发明制得的聚合物可有相当宽的应用范围,这对本领域技术人员由各个聚合物的物理性质是很容易明白的。一些催化剂对制备间规聚合物是有用的。用于本文中的术语间规聚合物意指取些有多于10个单体重复单元的嵌段的聚合物其中在重复单元中每个连续的单体单元的烷基在聚合物平面相对排列。对称二取代芴基化合物的制备
如上所述,本领域已知的各种方法都用来制备许多对称二取代芴基化合物。2,7-二氯芴的制备可由A.Roedig,Houben/Weyl 5/4330-41所公开的方式进行,即由芴与氯在N-氯化琥珀酰亚胺存在下接触。化合物2,7-二溴芴能通过芴在CHCl3或CH2Cl2中在0℃通常使用如在J.Am.chem.Soc,84,1238~41(1962);Bull.Chem.Soc.JP.,44,1614-19(1971);或J.chem.soc.,43,164-5(1883)中所述的方法进行溴化来制备。化合物2,7-二碘芴能使用在Helv.chem.Acta,53,1311-23(1970)中描述的方法获得。二碘芴能与一碘芴通过用热THF或甲苯重结晶来分离。化合物2,7-二叔丁基芴能使用在Synthesis,335-7(1984)和Bull.Chem.Soc.JP.,59,97-103(1986)中所述的方法来获得。
用于制备2,7-二甲氧基芴的多步法在本领域是已知的。惊奇地发现该化合物能用一步法制得,即在类似于在Tetrahedron letters,34,1007-1010(1993)中公开的条件(包括使用乙酸乙酯和浓甲醇钠溶液)下使用铜催化甲醇分解2,7-二溴芴。
化合物2,7-二(二甲基苯基二价碳基)芴(据信是一个新化合物)通过苯甲酸与芴于热多磷酸中于约100℃下反应得2,7-二苯甲酰芴,随后将其与三甲基铝在沸腾的甲苯中反应来制备。
化合物2,7-二(1-环己-1-烯基)芴能首先2,7-二碘芴和镁及在FHF中的溴乙烷加热几天形成成格利雅试剂,然后加入环己酮,在热甲苯中酸处理后得2,7-二环己烯基芴来制备。
新的更简化的制备制2,7)-二取代烷基和芳基的芴是本发明的另一个方面。取代基的例子包括甲基到环己基甚至有空间应力的
基或萘基。该方法包括在乙醚中将2,7-二碘芴与适当的格利雅试剂反应。通常需要使用瞵镍即Ni(dPPP)Cl2作为用于交联偶合反应的催化剂。公开了类似使用瞵镍的文献见Pure.Appl.Chem.52;669-79(1980);J.Chem.Soc.1490~4(1962);和Inorg.Chem.,5,1968~74(1966)。根据所需结果,用于反应的液体稀释剂可在相当宽的范围内变化。通常液体稀释剂包括四氢呋喃,二乙醚,甲苯等。分离通常通过酸水解和用沸腾的甲苯革取来完成。
能制备的2,7-二取代芴的例子包括2,7-二环己基芴;2,7-二甲基芴;2,7-二异丙基芴;2,7-二苯基芴;2,7-二(1-萘基)芴;2,7-二(4-甲基苯基)芴;2,7-二(2,4-二甲基苯基)芴;2,7-二
芴;2,7-二(4-氟苯基)芴;等。
对于制备2,7-二取代芴化合物也可有其它方法。化合物2,7-二乙酰基芴能通过用乙酸酐和三氯化铝对芴乙酰化作用来获得。在先有技术中,这类反应是在1,2-二氯乙烷中进行的。现在发现使用更安全的溶剂二氯甲烷甚至可获得更高的产率。用在碳上的Pd加氢还原二乙酰基芴得2,7-二乙基芴。另一方面,用三甲基铝还原二乙酰基得2,7-二叔丁基芴。这种新方法较先有技术(包括用丁基甲酚对芴叔丁基化)先进在于它对2,7-异构体有更高的选择性。
类似地,2,7-二(二甲基苯基二价碳基)芴能通过在约100℃下于多磷酸中搅拌芴和苯甲酸来获得2,7-二苯甲酰芴,随后将其与三甲基铝反应得2,7-二(二甲基苯基二价碳基)芴。
制备4,5-二甲基芴的改进的缩短的方法包括将发烟硝酸与间-甲苯甲酸反应形成3-甲基-2-硝基苯甲酸,然后它被还原成2-氨基-3-甲基苯甲酸。优选使用氢和在碳上的Pd催化剂进行还原反应。将该产品重氮化和偶合得6,6’-二甲基联苯甲酸,然后用多磷酸环化得4,5-二甲基芴酮,最后将其用在碳上的钯加氢得4,5-二甲基芴。
化合物3,6-二叔丁基芴能用较先有技术有更高选择性的方法通过将4-叔丁基甲苯溴化和使用Ni(tpp)2Cl2催化剂在THF中用镁与该产品反应来制备。进行溴化作用的优选的方法包括使用过量的在CCl4中的N-溴琥珀酰亚胺随后在水/二噁烷中用CaCaO3水解粗产品。将偶合后的取代二苯基产品在含水丙酮中用KMnO4氧化。然后用热多磷酸进行闭环。不需要的付产品通过使用乙醚/碳酸盐水溶液萃取来分离。回收的3,6-二叔丁基芴酮然后使用在碳上的钯催化剂加氢。
下面的实施例可提供对本发明,它的各个方面,目的和优点的进一步理解。
在下列实施例中给出有关用13CNMR测定的聚合物微观结构,该谱使用标准可接受的分光镜技术来测定。将聚合物溶在三氯苯中,该谱参照相对于六甲基硅氧烷(它是已知的相对于四甲基硅烷的参考点)内标来测定。从观察的有关峰的积分值计算有关微观结构的细节:
对于测定这些值的细节,可参考Frand A.Bovey所著书的第3章。
实施例Ⅰ
1-溴-2-(芴基)乙烷的制备
在该反应中,将8.3g(0.05摩尔)芴溶在150ml四氢呋喃中。然后将31.8ml(0.05摩尔)丁基锂(在1.6摩尔己烷中)滴加到该溶液中。1小时后,该溶液在2小时内被逐渐滴加到搅拌的由9ml(0.1摩尔)二溴乙烷和300ml戊烷组成的溶液中。然后将反应混合物用50ml NH4Cl水溶液处理,用50ml水洗涤。有机相用Na2SO4干燥。在真空中除去溶剂。将黄色残留物溶在戊烷中。用硅石过滤戊烷溶液。将该溶浓缩到约为原体积的20%并在-30℃下结晶。得10.88g1-溴-2-(芴基)乙烷。产品用1H NMR,13CNMR和质谱表征。
实施例Ⅱ
反应类似于实施例1进行用其它二卤烷代替1,2-二溴乙烷。例子包括1,3-二溴丙烷,1,2-二溴甲烷,1,2-二溴-2-甲基乙烷,和二氯甲烷,得相应的卤代芴基烷。
实施例Ⅲ
将环戊二烯与丁基锂在四氢呋喃中反应得环戊二烯基锂。将-40℃的环戊二烯基锂(0.002摩尔)的四氢呋喃(150ml)溶液和1-溴-2-(芴基)乙烷的THF(50ml)溶液在室温下混合。然后加入六甲基膦三酰胺(HMPT)。在室温下搅拌3小时后,用50ml NH4Cl水溶液洗涤该溶液,然后用50ml水洗涤,用Na2SO4洗涤有机相。真空中除去溶剂。得到的1-(芴基)-2-环戊二烯基乙烷通过溶在戊烷中然后结晶来纯化。产品用质谱和气相色谱来表征。
实施例Ⅳ
进行类似于实施例Ⅲ所述的反应,用其它芴基溴烷代替芴基溴乙烷。其它溴烷的例子包括1-芴基-3-溴丙烷,1-(2,7-二叔丁基芴基)-1-溴甲烷和1-甲基-2-芴基-1-溴乙烷。得相应的烷基桥联的芴基-环戊二烯基化合物。使用类似于实施例Ⅲ的反应但没用HMPT,2,7-二叔丁基芴代替环戊二烯得1-(2,7-二叔丁基芴基)-2-芴基乙烷。
实施例Ⅴ
使用乙醚或甲苯作溶剂制备大量的含芴基金属茂
当使用乙醚作溶剂时,将约1毫摩尔桥联或未桥联芴基化合物溶在200ml乙醚中。然后将在乙醚中的1.6摩尔甲基锂加到该溶液中以使每毫摩尔环戊二烯基基团有1毫摩尔甲基锂。(对需要制备桥联芴基化合物单价盐的情况是一个例外,在这种情况下,对于每毫摩尔环戊二烯基基团使用约0.5毫摩尔甲基锂)。将反应混合物搅拌直至没有甲烷气放出。这是在室温下进行的。然后将过渡金属卤化物缓缓加到芴基盐溶液中。当芴基化合物是单价盐时过渡金属量约为0.5毫摩尔;当芴基化合物是二价盐时,该量为约1毫摩尔。所得溶液通常再搅拌30分钟然后浓缩到50毫升并过滤。将过滤板上的桔红色固体溶在二氯甲烷中,将所得溶液浓缩并通常在约-78℃下结晶。
在使用甲苯作溶剂的制备试验中,将约1毫摩尔的桥联或未桥联芴基化合物在250ml甲苯中混合。该溶液与其量足以使未桥联化合物有1毫摩尔甲基锂和使桥联芴基化合物有2毫摩尔甲基锂的甲基锂(在1.6摩尔乙醚中)混合。(上段所述的例外情况也适用)。然后将反应混合物在回流下加热直到不再有甲烷气放出。然后将该溶液冷到室温。将过渡金属卤化物缓缓加到该溶液中。对于二价芴基盐使用约0.5毫摩尔过渡金属化合物;对单价芴基盐使用约1毫摩尔。将该悬浮液搅拌约30分钟。浓缩溶液到约50到75毫升并过滤。将滤板上的桔红色固体溶在二氯甲烷中,将所得溶液浓缩并冷却到-78℃得作为固体沉淀物的金属茂。
使用这类方法制备下列金属茂:二氯化(1,2-二芴基乙烷)合锆;二氯化(1-芴基-2-茚基乙烷)合锆和合铪;二氧化(1-芴基-1-环戊二烯基甲烷)合锆;三氧化(1-芴基-1-环戊二烯基甲烷)合锆;二氯化(1,2-二(2-叔丁基芴基)乙烷)合锆和合铪;二氯化(1,2-二(2-甲基芴基)乙烷)合锆;二氯化(1,2-二芴基乙烷)合铪;二氯化二(2,7-二叔丁基-4-甲基芴基)合锆;二氯化(1,3-二芴基丙烷)合锆和合铬;二氯化(1-芴基-2-甲基-2-芴基乙烷)合锆;二氯化二甲基甲硅烷基二芴基合锆;二氯化(1,2-二(1-甲基芴基)乙烷)合锆;二氯化(1,2-二(1-叔丁基芴基)乙烷)合锆和合铪;二氯化(1,2-二(2-乙基芴基)乙烷)合锆和合铪;二氯化(1,2-二(4-叔丁基芴基)乙烷)合锆;二氯化(1-芴基-2-环戊二烯基乙烷)合锆;二氯化((1-芴基-2-(3-甲基环戊二烯基)乙烷)合锆;二氯化(1-芴基-3-茚基丙烷)合锆;二氯化(1-芴基-2-甲基-2-环戊二烯基乙烷)合锆;二氯化(1-芴基-2-甲基-2-茚基乙烷)合锆,二氯化(1-芴基-2-甲基-2-(3-甲基环戊二烯基)乙烷)合锆;二氯化(1-(1-甲基芴基)-2-(4-甲基芴基)乙烷)合锆;二氯化(1-(1-叔丁基芴基)-2-(4-叔丁基芴基)乙烷)合锆;二氯化二(2,7-二叔丁基-4-甲基芴基)合锆;二氯化(1,2-二芴基乙烷)合钒;二氯化(1,1-二芴基甲烷)合钒,二氧化二(1-甲基芴基)合锆;二氯化二(1-甲基芴基)合铪;二氯化二(2-乙基芴基)合锆;二氯化二(4-甲基芴基)合锆;和二氯化二(4-甲基芴基)合铪。
芴基金属茂的应用
对按本发明制备的大量的含芴基金属茂进行了它们用作烯径聚合催化剂的效果的评价。
用于评价的具体的金属茂:
催化剂
A二氯化(1,2-二芴基乙烷)合锆
B二氯化(1-芴基-2-茚基乙烷)合锆
C二氯化(1-芴基-1-环戊二烯基甲烷)合锆
D二氯化(1,2-二(2-叔丁基芴基)乙烷)合锆
E二氯化二(2,7-二叔丁基-4-甲基芴基)合锆
F三氯化(1-芴基-1-环戊二烯基甲烷)合锆
H二氯化(1-芴基-2-甲基-2-茚基乙烷)合锆
I二氯化(1,2-二芴基乙烷)合铪。
聚合是在高压釜反应器中使用甲基铝恶烷作为助催化剂来进行的。甲基铝噁烷的来源不同。在一些试验中使用由SChering AG获得的30%(重量)的甲基铝噁烷的甲苯溶液。在其它试验中使用由EthylCorp获得的10%(重量)的甲基铝噁烷的甲苯溶液。在干燥箱中在基本惰性条件下将固体金属茂加到乳胶管形瓶中,然后将已知量的金属茂溶液加到该管形瓶中。铝噁烷中的铝与金属茂中的金属的克原子比为约200∶1。一些制成的催化剂体系溶液被用于多于一次聚合中。因此不是所有的催化剂体系溶液在制备后立即使用。为获得最佳结果,认为催化剂体系最好在制备后很快就使用。
将催化剂体系加到为进行特定聚合反应而制得的反应器中。通常为聚合丙烯,反应器含有液体丙烯作为反应稀释剂。为聚合乙烯或4-甲基-1-戊烯,使用液体异丁烷稀释剂。在加入催化剂后,在室温下将单体和氢气(如果使用)加入。将反应进行一段时间同时冷却反应器以维持选的反应温度。在大多数情况下,完成聚合后将稀释剂闪蒸出去,回收聚合物固体并表征。在一些情况下聚合物是低分子量或基本上所有都在溶液中,排出液体通过蒸发回收未反应单体,共聚用单体和/或稀释剂。
表征聚合物和聚合反应的各种特性。在各种情况下测定的特性例子包括密度(以g/毫升(ASTM D1505-68)表示),熔融流动指数(以克聚合物/10分钟(ASTM D1238-65T,Condition L)表示);高载荷熔融流动指数(HIMI)(以克聚合物/10分钟190℃(ASTMD1238,Condition E)表示);熔融指数(MI)(克聚合物/10分钟190℃(ASTM D 1238,Condition E)表示),庚烷不溶物(通过用沸腾的庚烷萃取后残留的不溶性聚合物百分数来表示);熔点(0℃,用差示扫描量热法测量);分子量(用空间排阻色谱法测量)即重均分子量用Mw除以Mn表示)。空间排阻色谱法(SEC)使用能分辩通常在聚烯烃如聚乙烯观察列的相当宽的分子量范围围的线性柱来进行。SEC使用140℃的聚合物的1,2,4-三氯苯溶液。特性粘度度使用Mark-Houwink-Sakrada常数即K·MWa由SEC来计算,用分升/克表示,在下表中表示为Ⅳ。除非另有说明用来表征各种性质的条件对每一个被评价的聚合物是相同的。在一些情况下,测定聚合物的红外谱和13CNMR。NMR谱是对聚合物的1,2,4-三氯苯溶液进行测定的。在NMR谱中的基标是0ppm(基于四甲基硅烷)。
实施例Ⅵ
使用二氯化(1,2-二芴基乙烷)合锆聚合乙烯
进行大量的聚合试验以评价二氧化(1,2-二芴基乙烷)合锆作为用于单独聚合乙烯和聚合乙烯与共聚用单体中的催化剂的效果。各种聚合作用的变量和结果综述在下表中。在所有下表中的单体都以克表示。产量也用克表示。
表1
表中数据表明的含芴基金属茂能制备有相当宽范围性能的乙烯聚合物。在无氢气下聚合物是很高分子量材料,这可由低HLMI(高载荷熔融表数)证实。数据进一步表明乙烯和己烯共聚能获得低密度聚合物。
试验 | 温度℃ | 催化剂mg· | △PC2 | △PH2 | 己烯 | 时间 | 产量 | HLMI/MI | 密度 | Mw×103 | HI | IV |
12345678910 | 90707070907070707070 | 0.660.66110.661.653111 | 7070705070501357070150 | NA2525252.7NA10252525 | NANANANA909050502550 | 20606060607045606060 | 29.725.831.9818.1516113072.562.179 | HLMI=0448/2.43668/1.42363.2/7.195.1/.0042HLMI=0.13288.5/0.5900/7.97蜡状79.8 M3 | 0.93840.97320.97590.96960.89810.88810.91540.92970.94780.9307 | 63311411671.917033216515924.153.5 | 3.921.819.410.646.616.823.227.17.18.9 | 5.751.321.347.12.033.511.881.80.410.79 |
实施例Ⅶ
用各种桥联芴基金属茂聚合乙烯
使用其它金属茂也进行了大量乙烯的聚合。各种聚合变量和结果综述在下表中。试验4和5来自表Ⅰ供比较。
表Ⅱ
试验 | 催化剂 | 温度 | 催化剂,mg· | 己烯 | 时间 | 产量 | 密度 | ||||||
4111213145 | ABCCCA | 707070707070 | 11.41220.66 | 5050702507070 | 2525252532.7 | NANANANA9090 | 606060606060 | 8110021371378.15 | 363.2/7.19811.8/19.60.06 HLMI0.07 HLMI18.3/0.155.1/0.042 | 0.96980.97270.95170.95680.88170.8981 | 7.94.7--1.71 | 10.66.6--4.456.6 | 7.10.78--1.62.03 |
表Ⅱ表明二氯化(1-芴基-2-茚基乙烷)合锆即催化剂B和催化剂C即二氯化(1-芴基-1-环戊烯基)乙烷)合锆适合用于乙烯的聚合。HLMI的值表明催化剂C给出更高分子量的材料。试验14表明催化剂C也能制备乙烯和己烯的共聚物。在该试验中制备的特定共聚物的不寻常之处在于它含12.4%(摩尔)的共聚用单体和共聚用单体相对分散度为105.9。共聚用单体摩尔百分数和共聚用单体相对分散度使用公开在U.S.4,522,987(其公开的内容以文献并入本文)中的技术由NMR谱来确定。这类聚合物也称为低密度超级无规共聚物即有共聚用单体超级无规分布的聚合物。
实施例Ⅷ
用各种芴基金属茂聚合丙烯
用各种含芴基金属茂进行一系列丙烯聚合。反应变量和结果综述在下表中。
表Ⅲ
试验 | 催化剂类型 | 温度℃ | 催化剂mg | 时间 | 产量 | 密度 | 不溶物 | 熔点℃ | |||||
1516171819202122232426272829 | CCCCCDEEFFBHAI | 6060607070606023.4707070707070 | 311112.31.61.62.52.55235.2 | NANA3.5105NA100252510101010 | 306060606050606060606060560 | 360230431400162709.50354608230182 | 19.614.615.627蜡状 | 0.88430.88120.88290.8797 | 83.39489.374.6-51.6------- | 3.64.32.32.1-2.3------- | 0.780.860.830.72-0.55------- | 96.692.498.178.394.793.4-------- | 132.6133.6134.6134.8133 |
表Ⅲ表明催化剂C即二氯化(1-芴基-1-环戊二烯基甲烷)合锆能用来制备聚丙烯。试验15-17中的数据表明聚丙烯是高度结晶物(由庚烷不溶物值证实)。据信该聚合物含大量间规分子结构。
试验20表明催化剂D即二氯化(1,2-二(2-叔丁基芴基)乙烷)合锆能用来制备晶体聚丙烯。
试验21表明催化剂E即未桥联金属茂二氯化二(2,7-二叔丁基-4-甲基芴基)合锆在60℃仅能制得少量固体聚丙烯。试验22表明催化剂在23.4℃下不是特别有效。
试验23和24使用非夹心键联的金属茂即其中只有一个环戊二烯基型基团键联到过渡金属上的金属茂。该催化剂仅制得3到5克固体聚合物及约45到55克低分子量丙烯可溶的聚合物。除非用分子式或其它方式另有表示,用于本文的所有桥联金属茂都是夹心键联的。
试验26使用桥联金属茂二氯化(1-芴基-2-茚基乙烷)合锆。虽然该催化剂制得460g固体聚合物,但94.4%(重量)的聚合物是低分子量二甲苯可溶的聚合物。类似地,试验27中的桥联金属茂二氯化(1-芴基-2-甲基-2-芴基乙烷)合锆得82克固体物料,但其中88%(重量)是低分子量二甲苯可溶的物料。
试验28和29使用基于1,2-二芴基乙烷的桥联金属茂。锆和铪金属茂都能制得固体聚丙烯。
实施例Ⅸ
对作为4-甲基-1-戊烯的聚合催化剂的催化剂C即二氯化(1-芴基-1-环戊二烯基甲烷)合锆进行了评价。所用金属茂的量是5mg。聚合是在氢(其差压为25)存在下进行的。聚合温度是120℃,聚合时间是2小时。聚合得96.7mg固体,其重均分子量为33330;不均匀指数为1.8和计算的特性粘度为0.12。约92%(重量)的固体在沸腾的甲苯中是不可溶的。该聚合物熔点为197.9℃。测定了回收的聚合物(即没有除去庚烷不溶物)的13CNMR谱图,它表聚合物含大量的间规官能度13CNMR谱图的有效峰出现在约22.8,24.8,26,31.8,42.8,43.1,46.1和46.2ppm处。在43.1ppm处的峰的强度比在42.0到43.5ppm处出现的所有峰的强度大0.5。在约46.2ppm处的峰的强度比在46.1和43.1ppm间的主峰的强度都大。此外,在约42.8ppm处的峰强度比在46.1和43.1ppm处间任何主峰的强度都大。这些峰的位置是相对于0ppm的峰(使用四甲基硅烷)。
实施例Ⅹ
在与实施例Ⅷ中所用的基本相同的条件下,用催化剂A即桥联催化剂二氯(1,2-二芴基乙烷)合锆进行4-甲基-1-戊烯的聚合。在这种情况下使用7mg催化剂并获得180克固体无规蜡状聚合物。
用未桥联的金属茂二氯化二(2-甲基)芴基)合锆代替用于聚合4-甲基-1-戊烯中催化剂A进行类似的实验。
在该试验中使用5mg金属茂,回收得9.7克固体聚合物。将两个试样进行庚烷萃取。萃取得庚烷不溶物值为54.8和68.8。该催化剂既不始上述的桥联催化剂活泼也不如桥联催化剂A活泼。
实施例Ⅺ
进行聚合以比较不同金属茂对丙烯聚合的效果。聚合是在颗粒形条件下使用丙烯作稀释剂进行的。金属茂与甲基铝恶烷助催化剂一起使用。聚合是在有和无氢气下进行的。每个聚合包括在干燥箱中称重金属茂并将其溶在从Schering AG获得的10%甲基铝恶烷和甲苯的溶液中。铝与锆的摩尔比为1000/1。加料顺序是金属茂/MAO,150 PSi氢(通过测量300CC气缸(当使用时)的压降来控制),和
加仑的液体丙烯。将这些物料加热到70℃后,将反应器中物料在该温度下搅拌1小时。然后通过加入剩余的丙烯来终止聚合反应。回收聚合物、干燥并称重以确定产量。结果综述在表Ⅳ中。
表Ⅳ
试验30-33是使用含未取代芴基金属茂的对比试验。
试验序号 | 金属茂 | 活性g PP/mol Zr | Mw | Mw/Mn | [r]% | [m]% | [rr]% | [m]% | [mr]% | MF |
30313233343536373839404142434445 | (Flu)(Cp)CH2]ZrCl2-A(Flu)(Cp)CH2]ZrCl2-B(Flu)(Cp)Me2C]ZrCl2-A(Flu)(Cp)Me2C]ZrCl2-B(2,7 Me Flu)(Cp)Me2C]ZrCl2-A(2,7 Me Flu)(Cp)Me2C]ZrCl2-B(2,7 t-Bu Flu)(Cp)Me2C]ZrCl2-A(2,7t-Bu Flu)(Cp)Me2C]ZrCl2-B(2,7 Ph Flu)(CP)Me2C]ZrCl2-A(2,7 Ph Flu)(Cp)Me2C]ZrCl2-B(2,7 Ph Flu)(Cp)Ph2C]ZrCl2-A(2,7 Ph Flu)(Cp)Ph2C]ZrCl2-B(2,7 Br Flu)(Cp)Me2C]ZrCl2-A(2,7 Br Flu)(CP)Me2C]ZrCl2-B(2,7 t-Bu Flu)(Cp)Ph2C]ZrCl2-A(2,7 t-Bu Flu)(Cp)Ph2C]ZrCl2-B | 2.75×1080.86×1081.70×1080.64×1081.18×1080.21×1082.12×1081.28×1081.43×1080.12×1081.86×1080.13×1080.44×1090.16×1084.72×1080.12×108 | 713106778083220830009318086700755907185091170815402129802576405642053600103830111490 | 1.831.912.362.142.182.702.152.012.862.295.443.582.722.812.202.20 | 93.4793.4893.0692.4092.6491.0394.7593.4993.4392.7492.7691.6790.6290.4795.2193.67 | 6.536.526.947.607.368.975.256.516.577.267.248.339.389.534.796.29 | 89.6089.4989.0187.8987.7385.3091.4989.5988.9487.6688.1686.2284.7384.4492.0989.41 | 2.672.532.893.092.443.251.992.602.092.182.632.883.493.511.672.06 | 7.737.738.109.029.8411.446.527.808.9710.169.2110.9011.7812.056.248.53 | 70.799.937.941.824.824.072.084.133.496.30.210.69131.0156.70.410.16 |
在该表中金属茂后的字母A是指试验中使用氢气而金属茂后字母B表示试验中不用氢气。除了在试验40和41中使用的金属茂外,所有的金属茂都产生不寻常的效果在于它们不用氢气制得的聚合物比用氢气制得的聚合物有更低的分子量。在试验34和35中用二氯化((2,6-二甲基芴基)(环戊二烯基)二甲基甲烷)合锆聚合丙烯制得的聚合物较在相同条件下用两个对比金属茂制得的聚合物有更高的分子量。
试验36和37的金属茂二氯化((2,7-二叔丁基芴)(环戊二烯基)二甲基甲烷)合锆比试验32和33的在芴基部分没有取代基的对比催化剂有更高的活性。试验36和37的本发明催化剂也产生较试验32和33的对比催化剂更高的间同立规规整度。
虽然试验38和39的金属茂二氯化((2,7-二苯基芴基)(环戊二烯基)二甲基甲烷)合锆不如试验37和38的活性高;但它制得了高分子量聚合物。且[r]%即外消旋物含量稍高于用试验32和30的对比催化剂获得的。
金属茂二氯化((2,7-二苯基芴基)(环戊二烯基)二苯基甲烷)合锆制得的聚合物的分子量远较其它金属茂制得的为高。
试验42和43的金属茂二氯化((2,7-二溴芴基)(环戊二烯基)二甲基甲烷)合锆得最低的间同立规规整度百分数。聚合物也有更高的烷融流动指数和更低的分子量。
试验44和45的金属茂二氯化(2,7-二叔丁基芴基)(环戊二烯基)二苯基甲烷)合锆特别重要在于加入15psi氢气增加催化剂活性约39倍而不含引起聚合物分子量大的变化。该催化剂也特别重要在于所制备的大部分聚合物是球形颗粒这是特别令人惊奇的,因为聚合是用均相即可溶性催化剂体系而没有任何载体进行的。
Claims (47)
1.式R″(F1Rn)(CpRm)MeQk所示的金属茂,其中F1是芴基,Cp是环戊二烯基,茚基,四氢茚基或芴基,每个R是可相或不同为卤素或有1到20个碳原子的烃基基团,R″是连结(F1Rn)和(CpRm)的有1到20个碳原子的烃基结构桥联基,Me是选自钛、锆、铪、铬或钒,每个Q相同或不同选自有1到2个碳原子的烃基或烃基氧基和卤素,K是足以添满Me余下价的数字,n是2到7的整数,m是0到7的整数。
2.根据权利要求1的金属茂,其中(F1Rn)是对称取代的芴基。
3.根据权利要求2的金属茂,其中(CpRm)是未取代的芴基。
4.根据权利要求2的金属茂,其中(CpRm)和(F1Rn)结构上不同。
5.根据权利要求2的金属茂,其中n是2。
6.根据权利要求5的金属茂,其中m是1到4的数。
7.根据权利要求5的金属茂,其中Me选自Ti,Zr和Hf。
8.根据权利要求1的金属茂,其中Me选自Zr和Hf。
9.根据权利要求5的金属茂,其中Cp选自环戊二烯基和茚基。
10.根据权利要求9的金属茂,其中m是0。
11.根据权利要求1的金属茂,其选自:二氯化(1-(2,7-二叔丁基芴基)-1-(环戊二烯基)甲烷)合锆和二氯化(1-(2,7-二叔丁基芴基)-2-(芴基)乙烷)合锆,和二氯化(1,2-二(2,7-二叔丁基-4-甲基芴基)乙烷)合锆。
12.根据权利要求2的金属茂,其选自:二氯化(1-(2,7-二叔丁基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆;二氯化(1-(2,7-二甲基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆;二氯化(1-(2,7-二苯基芴基)-1-环戊二烯-1,1-(二苯基)甲烷)合铬;二氯化(1-(2,7-二苯基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆;二氯化(1-(2,7-二溴芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆;二氯化(1-(2,7-二溴芴基)-1-环戊二烯-1,1-(二苯基)甲烷)合锆;二氯化(1-(2,7-二氯芴基)-1-环戊二烯-1,1-(二苯基)甲烷)合锆;二氯化(1-(2,7-二叔丁基芴基)-1-环戊二烯基-1,1-(二苯基)甲烷)合锆;二氯化(1-(2,7-二氯芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆;二氯化(1-(2,7-二甲基乙烯基芴基)-1-(环戊二烯基)-1,1-二甲基甲烷)合锆;二氯化(1-(2,7-二
基芴基)-1-(环戊二烯基)-1,1-二甲基甲烷)合铬;二氯化(1-(2,7-二甲氧基芴基)-1-(环戊二烯基)-1,1-二苯基甲烷)合铬;二氯化(1-(2,7-二甲氧基芴基)-1-(环戊二烯基)-1,1-二甲基甲烷)合铬;二氯化(1-(2,7-二苯基芴基)-1-(环戊二烯基)-1-苯基甲烷)合锆;二氯化(1-(2,7-二溴芴基)-1-(环戊二烯基)-1-甲基甲烷)合锆和二氯化(1-(2,7-
基芴基)-1-(环戊二烯)环戊烷)合铬。
13.根据权利要求2的金属茂,其中R”是二价亚甲基基团-CR’2-,其中每个R’相同或不同选自甲基,苯基和氢原子,且附加条件为至少一个R’是烃基。
14.根据权利要求13的金属茂,其主要选自,二氯化(1-(2,7-二苯基芴基)-1-环戊二烯基-1,1-(二苯基)甲烷)合锆。
15.根据权利要求13的金属茂,其主要选自二氯(1-(2,7-二苯基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆。
16.根据权利要求13的金属茂,其主要选自:二氯化(1-(2,7-二叔丁基芴基)-1-环戊二烯基)-1,1-(二甲基)甲烷)合锆。
17.根据权利要求13的金属茂,其主要选自,二氯化(1-(2,7-二叔丁基芴基)-1-环戊基-1,1-(二苯基)甲烷)合锆。
18.根据权利要求13的金属茂,其主要选自二氯化(1-(2,7-二甲基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆。
20.根据权利要求19的金属茂,其中R”是甲基取代的亚乙基。
21.根据权利要求20的金属茂,其中(CpRm)是未取代的芴基。
22.根据权利要求20的金属茂,其中(CpRm)选自未取代的环戊二烯,未取代的茚基,和甲基环戊二烯基。
23.根据权利要求2的金属茂,其中R”是带支链的脂肪亚烷基。
24.根据权利要求2的金属茂,其中Me是锆或铪,K是2和Q是卤素。
25.根据权利要求2的金属茂,其中R”含有2到20个碳原子的烃基,(CpRm)是未取代的环戊二烯基,和(F1Rn)选自2,7-和3,6-二烃基取代的芴基其中每个烃基取代基是相同的,每个Q选自卤素原子、(C1-C10)烷基和芳基,和Me选自Ti,Zr和Hf。
26.根据权利要求25的金属茂,其中R”是有4到20个碳原子的烃基。
27.一种制备间规聚α-烯烃的方法,包括在适宜的条件和在金属茂和一种适宜的助催化剂存在下将有至少3个碳原子的α-烯烃聚合,所述的金属茂选自权利要求25的金属茂。
28.按照权利要求27的方法,其中R″是含4到20个碳原子的烃基。
29.根据权利要求27的方法,其中所述的金属茂基本上由二氯化(1-(2,7-二苯基芴基)-1-环戊二烯基-1,1-(二苯基)甲烷)合锆组成。
30.按照权利要求27的方法,其所述的金属茂基本上由二氯化(1-(2,7-二苯基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆组成。
31.根据权利要求27的方法,其中所述的金属戊基本上由二氯化(1-(2,7-二叔丁基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆组成。
32.根据权利要求27的方法,其中所述的金属戊基本上由二氯化(1-(2,7-二叔丁基芴基)-1-环戊二烯基-1,1-(二苯基)甲烷)合锆组成。
33.根据权利要求27的方法,其中所述的金属戊基本上由二氯化(1-(2,7-二甲基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆组成。
34.一种聚合烯烃的方法,包括在适宜聚合条件下将所述烯烃与含权利要求1的含芴基金属茂和适宜助催化剂的催化剂体系接触。
35.按照权利要求34的方法,其中所述助催化剂包括烷基铝恶烷。
36.根据权利要求35的方法,其中乙烯被聚合。
37.根据权利要求35的方法,其中所述金属茂选自二氯化(1-(2,7-二叔丁基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆;二氯化(1-(2,7-二甲基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆;二氯化(1-(2,7-二苯基芴基)-1-环戊二烯基-1,1-(二苯基)甲烷合锆;二氯化(1-(2,7-二溴芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆;二氯化(1-(2,7-二苯基芴基)-1-环戊二烯基-1,1-(二苯基)甲烷)合锆;二氯化(1-(2,7-二溴芴基)-1-环戊二烯基-1,1-(二苯基)甲烷)合锆;二氯化(1-(2,7-二氯芴基)-1-环戊二烯基-1,1-(二苯基)甲烷)合锆;二氯化(1-(2,7-二叔丁基芴基)-1-环戊二烯基-1,1-(二苯基)甲烷)合锆;和二氯化(1-(2,7-二氯芴基)-1-环戊二烯基-1,1-二(甲基)甲烷)合锆。
38.根据权利要求37的方法,其中制备乙烯均聚物。
39.按照权利要求38的方法,其中所述的金属茂基本上由二氯化(1-(2,7-二叔丁基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆组成。
40.根据权利要求37的方法,其中乙烯是在另一种有4到8个碳原子的α-烯烃存在下被聚合的。
41.根据权利要求34的方法,其中丙烯被聚合。
42.根据权利要求41的方法,其中制备丙烯均聚物。
43.根据权利要求42的方法,其中所述金属茂选自二氯化(1-(2,7-二叔丁基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆;二氯化(1-(2,7-二甲基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆;二氯化(1-(2,7-二苯基芴基)-1-环戊二烯基-1,1-(二苯基)甲烷)合锆;二氯化(1-(2,7-二苯基芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆;二氯化(1-(2,7-二溴芴基)-1-环戊二烯基-1,1-(二甲基)甲烷)合锆;二氯化(1-(2,7-二苯基芴基)-1-环戊二烯基-1,1-(二苯基)甲烷)合锆;二氯化(1-(2,7-二溴芴基)-1-环戊二烯基-1,1-(二苯基)甲烷)合锆;二氯化(1-(2,7-二氯芴基)-1-环戊二烯基-1,1-(二苯基)甲烷)合锆;二氯化(1-(2,7-二叔丁基芴基)-1-环戊二烯基)-1,1-(二苯基)甲烷)合锆;和二氯化(1-(2,7-二氯芴基)-1-环戊二烯基-1,1-二(甲基)甲烷)合锆。
44.根据权利要求42的方法,其中在所述金属茂中F1Rn和CpRm是不同的且(F1Rn)选自2,7和3,6-二烃基取代的基团其中每个烃基取代基是相同的。
45.按照权利要求41的方法,该方法在氢气存在下进行。
46.按照权利要求43的方法,其中所述金属茂基本上由二氯化(1-(2,7-二苯基芴基)-1-(环戊二烯基)-1,1-(二苯基)甲烷)合锆组成。
47.按照权利要求43的方法,其中所述金属茂基本上由二氯化(1-(2,7-二叔丁基芴基)-1-(环戊二烯基)-1,1-(二苯基)甲烷)合锆组成。
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- 1994-11-07 CA CA002135225A patent/CA2135225C/en not_active Expired - Lifetime
- 1994-12-14 ES ES94119735T patent/ES2155841T3/es not_active Expired - Lifetime
- 1994-12-14 DE DE69427117T patent/DE69427117T2/de not_active Expired - Lifetime
- 1994-12-14 NO NO944857A patent/NO944857L/no unknown
- 1994-12-14 EP EP94119735A patent/EP0666267B1/en not_active Expired - Lifetime
- 1994-12-14 RU RU94043773/04A patent/RU94043773A/ru unknown
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Also Published As
Publication number | Publication date |
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NO944857D0 (no) | 1994-12-14 |
ES2155841T3 (es) | 2001-06-01 |
JPH07278169A (ja) | 1995-10-24 |
US5571880A (en) | 1996-11-05 |
CA2135225C (en) | 2001-04-10 |
AU1028495A (en) | 1995-08-10 |
EP0666267B1 (en) | 2001-04-18 |
AU667449B2 (en) | 1996-03-21 |
RU94043773A (ru) | 1996-10-27 |
CA2135225A1 (en) | 1995-08-04 |
DE69427117T2 (de) | 2001-12-06 |
DE69427117D1 (de) | 2001-05-23 |
NO944857L (no) | 1995-08-04 |
EP0666267A2 (en) | 1995-08-09 |
EP0666267A3 (en) | 1995-08-30 |
CN1109472A (zh) | 1995-10-04 |
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