CN1247873A - A dinuclear cyclopentadiene metal complex catalyst for the preparation of high molecular weight olefin polymers - Google Patents
A dinuclear cyclopentadiene metal complex catalyst for the preparation of high molecular weight olefin polymers Download PDFInfo
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- CN1247873A CN1247873A CN 98119815 CN98119815A CN1247873A CN 1247873 A CN1247873 A CN 1247873A CN 98119815 CN98119815 CN 98119815 CN 98119815 A CN98119815 A CN 98119815A CN 1247873 A CN1247873 A CN 1247873A
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- CN
- China
- Prior art keywords
- metal complex
- group
- cyclopentadiene
- complex according
- cyclopentadiene metal
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 77
- -1 cyclopentadiene metal complex Chemical class 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 4
- 239000000203 mixture Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- 125000004122 cyclic group Chemical group 0.000 claims description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000004711 α-olefin Substances 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 7
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 6
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 claims description 2
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical group C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 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 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 3
- 150000002430 hydrocarbons Chemical group 0.000 claims 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims 2
- 125000003545 alkoxy group Chemical group 0.000 claims 2
- 239000003426 co-catalyst Substances 0.000 claims 2
- 230000003647 oxidation Effects 0.000 claims 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- NWNPESVXYXCGLH-UHFFFAOYSA-N 4-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C=C)C2 NWNPESVXYXCGLH-UHFFFAOYSA-N 0.000 claims 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- 125000002877 alkyl aryl group Chemical group 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 229910052798 chalcogen Inorganic materials 0.000 claims 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical group C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims 1
- 229910052696 pnictogen Inorganic materials 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 238000003756 stirring Methods 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 16
- 229920002943 EPDM rubber Polymers 0.000 description 14
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 13
- 230000002902 bimodal effect Effects 0.000 description 13
- HPYIUKIBUJFXII-UHFFFAOYSA-N Cyclopentadienyl radical Chemical class [CH]1C=CC=C1 HPYIUKIBUJFXII-UHFFFAOYSA-N 0.000 description 12
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 125000002837 carbocyclic group Chemical group 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 125000001118 alkylidene group Chemical group 0.000 description 4
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 241001441571 Hiodontidae Species 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000004956 cyclohexylene group Chemical group 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 2
- 238000001640 fractional crystallisation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 125000000743 hydrocarbylene group Chemical group 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 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
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-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
- KOGSPLLRMRSADR-UHFFFAOYSA-N 4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine Chemical compound CC(C)(N)C1CCC(C)(N)CC1 KOGSPLLRMRSADR-UHFFFAOYSA-N 0.000 description 1
- GOASFHFFYPRKJU-UHFFFAOYSA-N C(=C)=C1C2C=CC(C1)C2.C(=C)=C2C1C=CC(C2)C1 Chemical compound C(=C)=C1C2C=CC(C1)C2.C(=C)=C2C1C=CC(C2)C1 GOASFHFFYPRKJU-UHFFFAOYSA-N 0.000 description 1
- MPBGGBCUUFZSLQ-UHFFFAOYSA-N C=C1C2C=CC(C1)C2.C=C2C1C=CC(C2)C1 Chemical compound C=C1C2C=CC(C1)C2.C=C2C1C=CC(C2)C1 MPBGGBCUUFZSLQ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- QTMBNCMQGRJAAA-UHFFFAOYSA-N chloro-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane Chemical compound CC1=C(C)C(C)=C(C)C1[Si](C)(C)Cl QTMBNCMQGRJAAA-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical compound [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 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
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 238000012856 packing Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000013638 trimer Substances 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
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a novel dinuclear cyclopentadiene metal complex shown in the formula , wherein M is1、M2、X、Y1、Y2、R1－R10、R16、R17And i and j are as defined in the specification. Using the dinuclear cyclopentadiene metal complex as a catalyst, an olefin polymer having a high molecular weight can be obtained.
Description
The present invention relates to a kind of double-core cyclopentadiene metal (metallocene) title complex of novelty, particularly be suitable for preparing a kind of novel double-core CYCLOPENTADIENYL ORGANOMETALLIC COMPLEES of high molecular weight olefin polymkeric substance.
Olefin polymer is widely used for a long time.Wherein modal a kind of olefin polymer promptly is polyolefine (polyolefins), that is, the homopolymer of alkene or multipolymer.These polyolefin plasticss generally are to be used for blow-molded, ejection formation, extrusion coated, film, binder, pipe fitting, electric wire and cable.
Polyolefinic most of physical properties and mechanical properties, as high strength, high impact resistance, stress, anti-penetration power and high-tenacity are considered at least a portion and are controlled by quite high molecular weight.
A polyolefinic example be ethylene-propylene elastomeric (ethylene-propylene rubber, EPM).Because its weathering resistance is good, thermal ageing property is good, and can mix with a large amount of filler and softening agent, therefore generally is employed industrial.Typical purposes on automotive industry, for example scatterer, heating tube, valve tube, weather proof patch (weather stripping), sponge door envelope (spongedoorseals) or the like.
Another kind of common olefin polymer is the trimer (terpolymer of ethylene, propylene, and a non-conjugateddiene) of ethene, propylene and a non-conjugated diene, so-called EPDM elastomerics or EPDM.The EPDM elastomerics has excellent weathering resistance, acid resistance and high temperature and low temperature usefulness.Such character makes EPDM be especially suitable for use as flexible pipe, packing ring, belt, safety lever, can be used as the fusion composition of plastics and the sidewall of vehicle.In addition, owing to be isolator, EPDM is particularly suitable for the insulation as electric wire and cable.
In order to make EPMs and EPDMs have commercial acceptable character, in general, must meet following condition: the Mooney under 127 ℃ (Mooney) viscosity is greater than 10, weight-average molecular weight is greater than 110,000, the glass tansition temperature is less than-40 ℃, and degree of crystallinity is not more than 25%.
Yet, until today, be 100,000 or littler by resulting EPMs of cyclopentadiene metal catalytic and the common weight-average molecular weight of EPDMs, this does not meet commercial for elastomeric requirement.
Found to have multimodal line (multimodal) in recent years (as bimodal line; Bimodal) molecular weight distribution (molecular weight distribution; MWD) polyolefine has not only kept the high-molecular weight advantage, also can promote its processibility.
Bimodal line MWD polymkeric substance (also can be described as bimodal line polymkeric substance simply) is to be defined as at gel permeation chromatography (gel permeation chromatography; GPC) polymkeric substance that has two molecular weight distribution curves on.That is bimodal line MWD polymkeric substance is the mixture that high-molecular weight polymer and low-molecular weight polymer mix.
Many different researchs provide the polyolefinic method of bimodal line of making.The simplest method for the polymer physics of two different molecular weights mix.But only under the complete fused situation of polymkeric substance, can mix equably.
U.S. Patent number 5,284,613 and 5,338,589 reports prepare bimodal line polyolefine with two stage polymerization process.In the fs, olefin monomer contacts with catalyzer under the polymerization situation, produces high molecular (high molecular weight; HMW) polymkeric substance, wherein this polymer deposition is on granules of catalyst.Second stage, the HMW polymkeric substance that contains catalyzer further with other olefinic monomer polymerization, produce lower (LMW) polymkeric substance of molecular weight, this polymer deposition on by HMW polymkeric substance/granules of catalyst that the fs obtained or within.The shortcoming of this dual stage process is to need two reactors in the reaction process, so Financial cost can be very high.
U.S. Patent number 5,369, a kind of polyolefinic method of bimodal line that in single reaction vessel, prepares of 194 reports.Employed catalyst system capable comprises that two different transition metal catalyst are stated from the same solid carrier substance.Thereby high-molecular weight polymer all can form on identical catalyst grains with low-molecular weight polymer.The shortcoming of this method is that preparation is stated from the suitable complexity of process and the difficulty height of the solid carrier material of two different catalyst.Moreover, two kinds of catalyst have active condition may and different, therefore, when a catalyst was activated, another catalyst may not had an activity.
The present invention's purpose is to solve the above problems, and a kind of double-core CYCLOPENTADIENYL ORGANOMETALLIC COMPLEES of novelty is provided, and it can be used for preparing the high-molecular weight olefin polymer.In addition, because two different catalytic sites are arranged on independent CYCLOPENTADIENYL ORGANOMETALLIC COMPLEES catalyst, therefore, can use independent a kind of catalyst, in single reactor, and olefinic monomer is aggregated into bimodal line olefin polymer, and the catalytic activity of this catalyst is suitable with commercial catalyst.
In order to reach above-mentioned purpose, the invention provides double-core cyclopentadiene metal (metallocene) title complex of a kind of following formula (I):
In the formula
M
1And M
2Can be identical or different, and be independently selected from IIIB family, the transitional metal of IVB family and VB family,
Each X can be identical or different, and the anion ligand of-1 valency for to have independently, and it is selected from H, C
1-20Alkyl, halogen, C
1-20Alkoxyl group, C
1-20Aryloxy (aryloxy), NH
2, NHR
11, NR
11R
12The NH of ,-(C=O)
2The NHR of ,-(C=O)
13And-(C=O) NR
13R
14, R wherein
11, R
12, R
13And R
14Be C
1-20Alkyl,
I is 1 to 3 integer,
J is 1 to 3 integer,
R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Can be identical or different, and be H independently, C
1-20Straight chain, side chain or cyclic hydrocarbon group, or C
2-4Ring-type alkylene (hydrocarbylene), and form C
4-6The condensed ring system,
Y
1And Y
2Can be identical or different, and be the electron-donating group of the 15th family or the 16th family's element independently,
R
9And R
10Can be identical or different, and be (C (R
15)
2-)
P, (Z (R
15)
2-)
POr (Z (R
15)
2-C (R
15)
2-)
PDivalent group, Z is silicon, germanium or tin, wherein R
15Be C
1-6Alkyl, p are 1 to 4 integer,
R
16Be not replacing or cyclic alkylidene (alkylene) that alkyl replaces of divalence, and
Each R
17Be C independently
1-20Straight chain, side chain or cyclic alkyl.
Fig. 1 shows the GPC figure of embodiment 9 products therefroms, and the expression resulting polymers is the ethylene/propylene polymers of bimodal line.
The present invention relates to a kind of double-core CYCLOPENTADIENYL ORGANOMETALLIC COMPLEES of novelty, and a kind of catalyst composition that comprises this novel double-core CYCLOPENTADIENYL ORGANOMETALLIC COMPLEES and activation accelerator. Particularly, the present invention relates in the presence of the novel double-core CYCLOPENTADIENYL ORGANOMETALLIC COMPLEES of catalytic amount, prepare the method for high molecular weight olefin polymer.
M
1And M2Can be identical or different, and M1And M2Be independently selected from scandium, yttrium, lanthanide series, and titanium, zirconium, hafnium, vanadium, niobium and tantalum. Best, M1And M2Be independently selected from titanium, zirconium and hafnium. Work as M1And M2Can be titanium when identical.
X can be identical or different, and the anion ligand of-1 valency for to have independently. X is preferably and is selected from H, C1-20Alkyl, halogen, C1-20Alkoxyl, C1-20Aryloxy group (aryloxy) ,-(C=O) NH2、-(C＝O)NHR
13And-(C=O) NR13R
14, R wherein13And R14C1-20Alkyl, preferred X is halogen.
About i and j, preferably i+2 equals M1Oxidation number, preferred i is 2, M1Be titanium, and j+2 equals M2Oxidation number, preferred j is 2, M2Be titanium.
About the substituting group of cyclopentadiene, R1、R
2、R
3、R
4、R
5、R
6、R
7And R8Can be identical or different, and be H or C independently1-20Straight chain, side chain or cyclic hydrocarbon group perhaps are C2-4Ring-type alkylene (hydrocarbylene group), and form C4-6Carbocyclic fused ring system.
In details of the words, C1-20Straight chain, side chain or cyclic hydrocarbon group can be C1-20Alkyl, C1-20Thiazolinyl, C6-20Aryl, C7-20Alkaryl or C7-20Aralkyl. Concrete example comprises H, methyl, ethyl, propyl group, butyl, isobutyl group, amyl group, isopentyl, hexyl, 2-ethylhexyl, heptyl, octyl group, vinyl, pi-allyl, isopropenyl, phenyl and tolyl.
In details of the words, can form C4-6The C of carbocyclic fused ring system2-4The ring-type alkylene can be C2-4Cyclic alkylidene (alkylene group). In some cases, R1、R
2、R
3And R4In at least one is C2-4Cyclic alkylidene and form C4-6Carbocyclic fused ring system. For example, work as R1、R
2、R
3And R4In one of be butylidene when to form a carbon number be six carbocyclic fused ring system, so can form indenyl (indenyl) with cyclopentadiene. Work as R1、R
2、R
3And R4In two be butylidene when to form two carbon numbers be six carbocyclic fused ring system, so can form fluorenyl (fluorenyl) with cyclopentadiene.
Similarly, in some cases, R5、R
6、R
7And R8In at least one is C2-4Cyclic alkylidene and form C4-6Carbocyclic fused ring system. For example, work as R5、R
6、R
7And R8In one of be butylidene when to form a carbon number be six carbocyclic fused ring system, so form indenyl with cyclopentadiene, work as R5、R
6、R
7And R8In two be butylidene when to form two carbon numbers be six carbocyclic fused ring system, so form fluorenyl with cyclopentadiene.
C
5R
1R
2R
3R
4And C5R
5R
6R
7R
8Object lesson comprise η5-cyclopentadienyl group, η5-methyl cyclopentadienyl, η5The tetramethyl-ring pentadienyl, η5-n-butyl cyclopentadienyl, indenyl, tetrahydro indenyl, fluorenyl and octahydrofluorenyl etc.
In formula (I), Y1And Y2Can be identical or different, be an electron-donating group, it is the 15th family or the 16th family's element independently. Concrete example comprises nitrogen, phosphorus, arsenic, antimony, oxygen, sulphur and selenium, is preferably nitrogen or phosphorus.
R
9And R10Can be identical or different, be divalent group, it is selected from (C (R15)
2-)
P、(-Z(R
15)
2-)
POr (Z (R15)
2-C(R
15)
2-)
P Z is silicon, germanium or tin, preferably silicon. R15C1-6Alkyl. P is 1 to 4 integer.
R
9And R10Object lesson comprise dimethylated methylene base (dimethylmethylene) and dimethyl silicylene (dimethylsilanylene).
R
16Be not replacing or cyclic alkylidene that alkyl replaces of divalence, the preferably is the not replacement or the C of divalence
1-10The C that alkyl replaces
5-12Cyclic alkylidene, better person is the not replacement or the C of divalence
1-10The cyclohexylene (cyclohexylene group) that alkyl replaces.R
16An object lesson be
The invention still further relates to a kind of catalyst composition that is used to prepare the double-core CYCLOPENTADIENYL ORGANOMETALLIC COMPLEES of olefin polymer, it comprises:
(a) the CYCLOPENTADIENYL ORGANOMETALLIC COMPLEES catalyst of formula (I), and
(b) activation accelerator, this activation accelerator can be aikyiaiurnirsoxan beta (methyl aluminoxane; MAO), trialkylaluminium, aluminum dialkyl monohalide (a dialkyl aluminum halide), inertia and non-coordination anion salt, or its mixture.
Trialkylaluminium is selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisopropylaluminiuand, tri-butyl aluminum and triisobutyl aluminium (TIBA).
The non-coordination anion of this inertia can be borate.Be suitable for borate of the present invention and comprise N, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (N, N-dimethyl anilinium tetrakis (pentafluorophenyl) borate), triphen carbene four (pentafluorophenyl group) borate (triphenyl carbenium tetrakis (pentafluorophenyl) borate), trimethyl ammonium four (pentafluorophenyl group) borate (trimethyl ammonium tetrakis (pentafluorophenyl) borate), ferrocene four (pentafluorophenyl group) borate (ferrocenium tetrakis (pentafluorophenyl) borate), dimethyl four (pentafluorophenyl group) borate (dimethyl tetrakis (pentafluorophenyl) borate).
The activatory accelerator is preferably the mixture of aikyiaiurnirsoxan beta or trialkylaluminium and borate.
Use catalyst composition of the present invention (comprising novel double-core CYCLOPENTADIENYL ORGANOMETALLIC COMPLEES and activation accelerator), can synthesize olefin polymer.In the presence of the CYCLOPENTADIENYL ORGANOMETALLIC COMPLEES of the present invention of catalytically effective amount, and under the polymeric condition, can make at least one olefinic monomer carry out polymerization, maybe can make at least one olefinic monomer and other monomer carry out polymerization.
Suitable olefinic monomer can be ethene, or alpha-olefin.Can be Alathon by the polymkeric substance that method for making of the present invention obtained, alpha-olefin homo, alpha-olefin copolymer, and ethene and alpha-olefin copolymer.Alpha-olefin comprises the alkene of 3 to 12 carbon atoms, as 1-propylene, 1-butylene, 1-amylene, 1-hexene and 1-octene.The alpha-olefin that wherein can be ethene and 3 to 12 carbon atoms of at least one tool carries out copolymerization, also can two or the alpha-olefin of 3 to 12 carbon atoms of a plurality of tool carry out equal polymerization or copolymerization.
More particularly, catalyst system capable of the present invention is particularly useful for making Alathon, comprises the high density polyethylene(HDPE) (HDPE) of tool wide molecular weight distribution, multimodal line or bimodal line molecular weight distribution, and it can be applicable to high molecular weight film and blow molding.
In addition, specifically, catalyst system capable of the present invention is particularly useful for making multipolymer (a copolymer of ethylene and propylene of ethene and propylene; EPM), and, also be suitable for preparing ethene, C
3-12The multipolymer of alpha-olefin and non-conjugated diene.Particularly, work as C
3-12When alpha-olefin is propylene, can obtain the multipolymer of ethene, propylene and non-conjugated diene, be called EPDM.Suitable non-conjugated diene can be 5-ethylidene-2-norbornene (5-ethylidene-2-norbornene; ENB), 5-methylene-2-norbornene (5-methylene-2-norbornene), 5-vinylidene-2-norbornylene (5-vinylidene-2-norbornene), 1, the 4-hexadiene (1,4-hexadiene; Or Dicyclopentadiene (DCPD) (dicyclopentadiene HD); DCPD).
Polyreaction of the present invention also can be carried out in the presence of hydrogen and catalyst composition common.So the molecular weight of polymkeric substance can control to required scope on demand and in addition.
Catalyst system capable of the present invention is applicable to the paste-like reaction conditions, gas phase and solution polymerization condition.Polyreaction and is pressed onto 3 in an atmosphere usually under 0 ℃ to 250 ℃ temperature, carries out between the 000psi.
The most important advantage of the present invention is use novel double-core CYCLOPENTADIENYL ORGANOMETALLIC COMPLEES as catalyst, but synthetic molecular weight to be higher than 200,000 olefin polymer.And when using traditional cyclopentadiene metal, the molecular weight of resulting olefin polymer can only reach about 100,000.
In addition, because cyclopentadiene metal of the present invention is a double-core, that is, two metal centers are arranged, near the chemical environment these two metal centers is also inequality, so, in independent cyclopentadiene metal, two different catalytic sites are arranged.Therefore, by using such double-core cyclopentadiene metal, can obtain the olefin polymer of bimodal line as catalyst.
Illustrate further method of the present invention, feature and advantage by following examples.
The synthetic embodiment 1 of cyclopentadiene metal
1, (1,8-diamino-p-menthane) (7.37g, 30.3mmole, purity 70-75%) places the 300mL round-bottomed bottle to 8-diamino-p- alkane, with the 150mL ether dissolution.This yellow solution is cooled to-78 ℃, injects 2 equivalent 1.6M n-Butyl Lithiums (n-BuLi) with syringe then.This mixture is risen again to room temperature and stirring overnight.Obtain 6.8 gram dilithium salts (dilithiumsalt) after the filtration, it is a white solid.
Embodiment 2
With embodiment 1 resulting dilithium salt (1.97g, 10.8mmole) (4.65g 21.67mmole) is dissolved in respectively among the THF of 50mL and 20mL with the silica-based chlorine of tetramethyl-ring pentadienyl dimethyl (tetramethylcyclopentadienyl-dimethylsilylchloride).This two solution is merged under room temperature.Mixture stirring overnight.This yellow mixture drained be heavy-gravity oily matter to extract again with 40mL toluene.Remove by filter the LiCl solid, filtrate drained once more, obtain xanchromatic oily matter (5.6g, 10.63mmole).
Embodiment 3
(5.6g 10.63mole) is dissolved among the 100mL THF, to obtain yellow solution with the ligand of embodiment 2 gained.This solution is cooled to-78 ℃, adds 4 equivalent 1.6Mn-BuLi (42.5mmole) with syringe again.This light brown solution mixture is slowly risen again to room temperature, to color transition be the tangerine look.After the stirring overnight, mixture is drained to about 10mL, added the toluene of 20mL and the pentane of 20mL then.Filter this mixture, collect 5.1 grams, four lithium salts, it is a white solid.
Embodiment 4
(3.0g, 5.45mmole) THF with 30mL dissolves fully with four lithium salts of embodiment 3 gained.With two equivalent TiCl
3(thf)
3(4.03g 10.9mmole) is suspended among the THF.This two solution is cooled to-30 ℃, combines then.This mixture was stirred 3 hours, add 2.5 gram AgCl (excessive) again.Reaction mixture becomes black soon, and becomes when stirring overnight slightly redly.This mixture is drained, extracted with 35mL toluene again.Remove by filter any insolubles, reddish-brown filtrate is concentrated into small volume.This concentrated filtrate through fractional crystallization (fractionalcrystallization), is restrained final product and obtain 0.5, and it is the light brown solid.
Synthesizing of polymkeric substance
Synthetic EPM (ethylene propylene rubber)
Embodiment 5
The reactive tank temperature is risen to 105 ℃, and, vacuumized about 2 hours, all valve closess by after the nitrogen purging 5 minutes.500mL toluene is pressed in the reactive tank with nitrogen, and temperature of reactor is kept 80 ℃ of desired reaction temperatures.After treating temperature-stable, with 8mL (1.2 * 10
-2Mole) MAO (being dissolved in toluene) adds in the reactive tank, and stirs.After treating 5 minutes, add 2mL (4 * 16
-6Mole) 4 winner's catalyst of embodiment, and stir.After stirring 1 minute under 80 ℃, with volume ratio 40/50 blended ethene and propylene monomer, add in the reactive tank in level pressure (100psi) mode, with this moment the time opening.
Reaction times to be reached, solution is poured out, after the cooling, add methyl alcohol product is precipitated out.The product oven dry is handled, for physical property measurement, and weighing, calculated activity.The result is as shown in table 1.
Embodiment 6-11
Step is with embodiment 5, but change temperature of reaction, reactant ratio (ethylene/propene, E/P) or reaction pressure.The result is as shown in table 1.
Fig. 1 shows the GPC figure of embodiment 9 products therefroms, and the expression resulting polymers is the ethylene/propylene polymers of bimodal line.
Table 1
| Embodiment | Reaction conditions | Active (* 10 4g/g -metal-hr) | Product characteristics | |||||
| Temperature (℃) | The E/P volume ratio | Pressure (psi) | ??Tm ?(℃) | The E/P mol ratio | ??Mw | ??MWD | ||
| ????5 | ??80 | 40/50 | ??100 | ????4.22 | -47.8 | ?68/32 | 394,468 | ??4.6 |
| ????6 | ??100 | 40/50 | ??100 | ????4.07 | -48.2 | ?68/32 | 292,923 | ??2.7 |
| ????7 | ??120 | 40/50 | ??100 | ????3.64 | -47.5 | ?70/30 | 249,935 | ??5.9 |
| ????8 | ??80 | 50/50 | ??100 | ????3.12 | -47.3 | ?68/32 | 519,131 | ??3.7 |
| ????9 | ??80 | 40/60 | ??100 | ????2.37 | -48.3 | ?68/32 | 190,826 | ??6.00 |
| ????10 | ??100 | 40/50 | ??80 | ????3.62 | -45 | ?70/30 | 539,527 | ??3.3 |
| ????11 | ??100 | 40/50 | ??120 | ????4.12 | -45.1 | ?75/25 | 387,194 | ??3.3 |
Synthetic EPDM (propylene diene rubber)
Embodiment 12
The reactive tank temperature is risen to 105 ℃, and, vacuumized about 2 hours, all valve closess by after the nitrogen purging 5 minutes.500mL toluene is pressed in the reactive tank with nitrogen, and temperature of reactor is kept 80 ℃ of desired reaction temperatures.After treating temperature-stable, with 8mL (1.2 * 10
-2Mole) MAO (being dissolved in toluene) adds in the reactive tank, and stirs.After treating 5 minutes, add 2mL (4 * 10
-6Mole) 4 winner's catalyst of embodiment, and stir.After stirring 5 minutes under 80 ℃, add 10mL 5-ethylidene-2-norbornene (5-ethylidene-2-norbornene; And stir ENB).After 1 minute, will add in the reactive tank in level pressure (100psi) mode with volume ratio 40/50 blended ethene and propylene monomer, be the time opening with this moment.
Reaction times to be reached, solution is poured out, after the cooling, add methyl alcohol generation is precipitated out.The product oven dry is handled, for physical property measurement, and weighing, calculated activity.The result is as shown in table 2.
Embodiment 13
Step is with embodiment 12, but the charge ratio of change ethylene/propene (E/P).The result is as shown in table 2.
Table 2
| Embodiment | Reaction conditions | Active (* 10 4g/g -metal-hr) | Product characteristics | |||||||
| Temperature (℃) | The E/P volume ratio | ENB (mL) | Pressure (psi) | ??Tm ?(℃) | The E/P mol ratio | ENB (mole %) | ??Mw | ??MWD | ||
| ??5 | ??80 | ?40/50 | ??0 | ??100 | ????4.22 | -47.8 | ?68/32 | ????0 | ?394,468 | ??4.6 |
| ??12 | ??80 | ?40/50 | ??10 | ??100 | ????3.06 | -31.4 | ?79/21 | ????1 | ?325,050 | ??4.32 |
| ??13 | ??80 | ?50/50 | ??10 | ??100 | ????2.4 | -49.1 | ?79/21 | ????1.7 | ?499,008 | ??2.71 |
| ??14 | ??80 | ?40/50 | ??0 | ??100 | ????3.9 | -46.8 | ?60/40 | ????0 | ?339,038 | ??4.2 |
With hydrogen control Mw
Embodiment 14
The reactive tank temperature is risen to 105 ℃, and, vacuumized about 2 hours, all valve closess by after the nitrogen purging 5 minutes.500mL toluene is pressed in the reactive tank with nitrogen, and temperature of reactor is kept 80 ℃ of desired reaction temperatures.After treating temperature-stable, with 8mL (1.2 * 10
-2Mole) MAO (being dissolved in toluene) adds in the reactive tank, and stirs.After treating 5 minutes, add 2mL (4 * 10
-6Mole) 4 winner's catalyst of embodiment, and stir.After stirring 1 minute under 80 ℃, with the 7%H of 7psi
2/ N
2Gas mixture adds reactive tank, and stirs.After treating 1 minute, with volume ratio 40/50 blended ethene and propylene monomer, adding in the reactive tank in level pressure (100psi) mode, is the time opening with this moment.
Reaction times to be reached, solution is poured out, after the cooling, add methyl alcohol product is precipitated out.The product oven dry is handled, for physical property measurement, and weighing, calculated activity.The result is as shown in table 3.
Embodiment 15-17
Step is with embodiment 14, but change H
2/ N
2The pressure of gas.The result is as shown in table 3.
Embodiment 18
The reactive tank temperature is risen to 105 ℃, and after the logical nitrogen purging 5 minutes, vacuumized about 2 hours, all valve closess.500mL toluene is pressed in the reactive tank with nitrogen, and temperature of reactor is kept 80 ℃ of desired reaction temperatures.After treating temperature-stable, with 8mL (1.2 * 10
-2Mole) MAO (being dissolved in toluene) adds in the reactive tank, and stirs.After treating 5 minutes, add 2mL (4 * 10
-6Mole) 4 winner's catalyst of embodiment, and stir.After 5 minutes, add the ENB of 10mL again, and stir.After 1 minute, with the 7%H of 7psi
2/ N
2Gas mixture adds reactive tank, and stirs.After treating 1 minute, with volume ratio 40/50 blended ethene and propylene monomer, adding in the reactive tank in level pressure (100psi) mode, is the time opening with this moment.
Reaction times to be reached, solution is poured out, after the cooling, add methyl alcohol product is precipitated out.The product oven dry is handled, for physical property measurement, and weighing, calculated activity.The result is as shown in table 3.
Table 3
| Embodiment | Reaction conditions | Active (* 10 4g/g -metal-hr) | Product characteristics | ||||
| ????ENB ????(mL) | Hydrogen (7%) pressure (psi) | Tm (℃) | The E/P mol ratio | ?Mw | ????MWD | ||
| ????14 | ????0 | ????7 | ????3.9 | -46.8 | ?60/40 | ?339,038 | ????4.2 |
| ????15 | ????0 | ????14 | ????3.8 | -46.5 | ?53/47 | ?237,453 | ????3.1 |
| ????16 | ????0 | ????28 | ????3.5 | -47.2 | ?58/42 | ?261,720 | ????3.6 |
| ????17 | ????0 | ????42 | ????3.2 | ?57/43 | ?155,291 | ????3.2 | |
| ????18 | ????10 | ????14 | ????3.8 | -42.2 | ?56/44 | ?308,596 | ????2.4 |
Temperature of reaction=80 ℃
E/P charge ratio=40/50
Pressure=100psi
The equal polymerization of ethene
Embodiment 19
450mL reactive tank temperature is risen to 105 ℃, and after the logical nitrogen purging 5 minutes, vacuumized about 2 hours, all valve closess.The reactive tank temperature is adjusted to 100 ℃.After treating temperature-stable, add 250mL toluene and 1.49 * 10
-2The 10%MAO solution of mole, and stir.Stir after 5 minutes, add 2 * 10
-6The main catalyst of mole embodiment 4 gained stirred 3 minutes.Ethylene gas is added in the reactive tank in level pressure (150psi) mode, and reaction was carried out 30 minutes.
Reaction times to be reached, solution is poured out, after the cooling, add Virahol so that catalyst and accelerator lose activity.Add methyl alcohol so that product is precipitated out.Filter and in 80 ℃ dry 10 minutes down, to obtain polyethylene product.The result is as shown in table 4.
Embodiment 20-21
Step is with embodiment 19, but the change temperature of reaction.The result is as shown in table 4.
Table 4
| Embodiment | Temperature of reaction (℃) | Active (* 10 4g/g-metal-hr) | Product characteristics | ||
| ??Tm(℃) | ?Mw | ????MWD | |||
| ????19 | ????80 | ????3.6 | ????132 | ?1,340,673 | ????3.1 |
| ????20 | ????100 | ????4.59 | ????131 | ?521,772 | ????5.4 |
| ????21 | ????120 | ????3.83 | ????132 | ?445,464 | ????2.33 |
The copolymerization of ethene
Embodiment 22
The reactive tank temperature is risen to 105 ℃, and after the logical nitrogen purging 5 minutes, vacuumized about 2 hours, all valve closess.The reactive tank temperature is adjusted to 100 ℃.After treating temperature-stable, add 250mL toluene, 5mL octene-1 and 1.49 * 10
-2The 10%MAO solution of mole, and stir.Stir after 5 minutes, add 2 * 10
-6The main catalyst of mole embodiment 4 gained stirred 3 minutes.Ethylene gas is added in the reactive tank in level pressure (150psi) mode, and reaction was carried out 30 minutes.
Reaction times to be reached, solution is poured out, after the cooling, add Virahol so that catalyst and accelerator lose activity.Add methyl alcohol so that product is precipitated out.Filter and in 80 ℃ dry 10 minutes down, to obtain ethylene/octene.The result is as shown in table 5.
Embodiment 23-25
Step only changes the kind or the consumption of comonomer with embodiment 22.The result is as shown in table 5.
Table 5
| Embodiment | Temperature of reaction (℃) | Comonomer | Active (* 10 4g/g-metal-hr) | Product characteristics | ||
| Tm(℃) | ?Mw | ?MWD | ||||
| ????20 | ??100 | ?????- | ????4.59 | ??131 | ?521,772 | ?5.4 |
| ????22 | ??100 | ??1-C 8，20mL | ????11.2 | ??- | ?196,904 | ?2.75 |
| ????23 | ??100 | ??1-C 8，10mL | ????9.44 | ??- | ?212,650 | ?2.6 |
| ????24 | ??100 | ??1-C 8，5mL | ????5.61 | ??102 | ?397,891 | ?2.77 |
| ????25 | ??100 | ??1-C 6，5mL | ????4,85 | ??97 | ?355,795 | ?3.86 |
Embodiment 26
With four kinds of commercial EPDMs, Uniroyal 509, and Exxon 8731, DuPont Dow 4520, and DuPont Dow 5750P, and the embodiment of the invention 8 gained EPM carry out various analyses respectively, to compare its working properties.Uniroyal 509 and Exxon 8731 be to use the vanadium of non-cyclopentadiene metal be catalyst catalysis and EPDMs.DuPont Dow 4520 and DuPont Dow5750P are to use how much catalyst (constrained geometry catalyst of restriction; CGC) catalysis that (belongs to monokaryon) and EPDMs.Under 170 ℃, record TC90 (min) expression and use dicumyl peroxide (dicumyl peroxide; DCP) in 170 ℃ of following catalysis, the time that 90% crosslinked polymer is required.Less TC90 represents to have hardening rate faster.
Analytical results is as shown in table 6.By can finding out in the table, by the catalyst gained EPM of novelty of the present invention with compare by traditional catalyst gained EPDMs, catalyst gained EPM of the present invention has 125 ℃ of higher following Mooney viscosity, this mainly is because due to its high molecular.In fact, the Mw of embodiment 8 gained EPM is 519,131 (seeing Table 1).Moreover, and compare by traditional catalyst gained EPDMs, have cross-linked speed faster by the catalyst gained EPM of novelty of the present invention, represent that it has preferable processibility.
Table 6
| Sample | Ethene amount (%) | ENB measures (%) | Mooney is under 125 ℃ | ??Tm ??(℃) | TC90 (min) DCP is under 170 ℃ |
| Uniroyal?509 | ????70 | ????9 | ????56 | -46.2 | ????7.94 |
| Exxon?8731 | ????75 | ????3 | ????26 | -41.3 | ????8.63 |
| DuPont-Dow?4520 | ????51 | ????5 | ????20 | -53.6 | ????9.52 |
| DuPont-Dow?5750P | ????69 | ????9 | ????50 | -36.6 | ????9.66 |
| EPM by the embodiment of the invention 8 gained | ????68 | ????-- | ????100 | -47.3 | ????5.1 |
Though the present invention with preferred embodiment openly as above; yet it is not in order to restriction the present invention, any person skilled in the art, without departing from the spirit and scope of the present invention; can do some improvement and variation, it all belongs within protection scope of the present invention.
Claims (44)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98119815 CN1247873A (en) | 1998-09-16 | 1998-09-16 | A dinuclear cyclopentadiene metal complex catalyst for the preparation of high molecular weight olefin polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98119815 CN1247873A (en) | 1998-09-16 | 1998-09-16 | A dinuclear cyclopentadiene metal complex catalyst for the preparation of high molecular weight olefin polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1247873A true CN1247873A (en) | 2000-03-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98119815 Pending CN1247873A (en) | 1998-09-16 | 1998-09-16 | A dinuclear cyclopentadiene metal complex catalyst for the preparation of high molecular weight olefin polymers |
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| Country | Link |
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| CN (1) | CN1247873A (en) |
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1998
- 1998-09-16 CN CN 98119815 patent/CN1247873A/en active Pending
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