JPH11514376A - 置換インデニル含有金属錯体およびオレフィン重合法 - Google Patents
置換インデニル含有金属錯体およびオレフィン重合法Info
- Publication number
- JPH11514376A JPH11514376A JP9516620A JP51662097A JPH11514376A JP H11514376 A JPH11514376 A JP H11514376A JP 9516620 A JP9516620 A JP 9516620A JP 51662097 A JP51662097 A JP 51662097A JP H11514376 A JPH11514376 A JP H11514376A
- Authority
- JP
- Japan
- Prior art keywords
- dimethyl
- methylindenyl
- silanetitanium
- silane titanium
- silane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 title claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 33
- 229910052751 metal Inorganic materials 0.000 title abstract description 24
- 239000002184 metal Substances 0.000 title abstract description 24
- 150000001336 alkenes Chemical class 0.000 title abstract description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 9
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 title description 37
- 239000000203 mixture Substances 0.000 claims abstract description 121
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 50
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 claims abstract description 8
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 7
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims abstract 5
- -1 atoms Compound Chemical class 0.000 claims description 228
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 96
- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical compound C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 claims description 56
- 239000003054 catalyst Substances 0.000 claims description 49
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 44
- 150000001993 dienes Chemical class 0.000 claims description 42
- 230000003647 oxidation Effects 0.000 claims description 28
- 238000007254 oxidation reaction Methods 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 23
- 239000004711 α-olefin Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 230000003213 activating effect Effects 0.000 claims description 16
- 150000004696 coordination complex Chemical class 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000002879 Lewis base Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 229910000085 borane Inorganic materials 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 150000007527 lewis bases Chemical class 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052735 hafnium Chemical group 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000012718 coordination polymerization Methods 0.000 claims 5
- 150000001408 amides Chemical class 0.000 claims 1
- 125000004663 dialkyl amino group Chemical class 0.000 claims 1
- BUEBLNVFMGQFGA-UHFFFAOYSA-N fluoro(phenyl)boron Chemical compound F[B]C1=CC=CC=C1 BUEBLNVFMGQFGA-UHFFFAOYSA-N 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 150000002739 metals Chemical group 0.000 abstract description 4
- ZCBSOTLLNBJIEK-UHFFFAOYSA-N silane titanium Chemical compound [SiH4].[Ti] ZCBSOTLLNBJIEK-UHFFFAOYSA-N 0.000 description 641
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 334
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 317
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 126
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 122
- HBGGBCVEFUPUNY-UHFFFAOYSA-N cyclododecanamine Chemical compound NC1CCCCCCCCCCC1 HBGGBCVEFUPUNY-UHFFFAOYSA-N 0.000 description 119
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 117
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 97
- 239000000243 solution Substances 0.000 description 95
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 94
- 238000004519 manufacturing process Methods 0.000 description 92
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 81
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 80
- 229910000077 silane Inorganic materials 0.000 description 79
- 239000000047 product Substances 0.000 description 71
- 239000007787 solid Substances 0.000 description 52
- 230000035484 reaction time Effects 0.000 description 50
- 239000003039 volatile agent Substances 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 46
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 40
- 229920000642 polymer Polymers 0.000 description 37
- 239000002904 solvent Substances 0.000 description 34
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 30
- 239000005977 Ethylene Substances 0.000 description 30
- 238000001914 filtration Methods 0.000 description 28
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 27
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 25
- 239000003921 oil Substances 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 21
- 239000000178 monomer Substances 0.000 description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- 150000001450 anions Chemical class 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- 229920002943 EPDM rubber Polymers 0.000 description 17
- 238000005481 NMR spectroscopy Methods 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 17
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000002002 slurry Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 14
- 238000000746 purification Methods 0.000 description 14
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 230000004913 activation Effects 0.000 description 11
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000005868 electrolysis reaction Methods 0.000 description 10
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 10
- 229940060942 methylin Drugs 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 10
- 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 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- BNCWJGVCZSBZRK-UHFFFAOYSA-N C=CC=CC.[La+2] Chemical compound C=CC=CC.[La+2] BNCWJGVCZSBZRK-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 8
- 239000003115 supporting electrolyte Substances 0.000 description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 7
- WVLVQQZPXUGTTK-UHFFFAOYSA-N C1(=CC=CC=C1)C=CC=CC1=CC=CC=C1.[La+2] Chemical compound C1(=CC=CC=C1)C=CC=CC1=CC=CC=C1.[La+2] WVLVQQZPXUGTTK-UHFFFAOYSA-N 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 7
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 7
- 239000000284 extract Substances 0.000 description 7
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000001273 butane Substances 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 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 description 5
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 150000001639 boron compounds Chemical class 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- NGFQXYLWQODUIL-UHFFFAOYSA-N cyclohexylazanide Chemical compound [NH-]C1CCCCC1 NGFQXYLWQODUIL-UHFFFAOYSA-N 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 5
- XUWVIABDWDTJRZ-UHFFFAOYSA-N propan-2-ylazanide Chemical compound CC(C)[NH-] XUWVIABDWDTJRZ-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000001976 improved effect Effects 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- RURFJXKOXIWFJX-UHFFFAOYSA-N (2,3,4,6-tetrafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C=C(F)C(F)=C1F RURFJXKOXIWFJX-UHFFFAOYSA-N 0.000 description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 3
- CCUYEVNCRQDQRF-UHFFFAOYSA-N 2-bromo-1h-indene Chemical compound C1=CC=C2CC(Br)=CC2=C1 CCUYEVNCRQDQRF-UHFFFAOYSA-N 0.000 description 3
- YSAXEHWHSLANOM-UHFFFAOYSA-N 2-methyl-1h-indene Chemical compound C1=CC=C2CC(C)=CC2=C1 YSAXEHWHSLANOM-UHFFFAOYSA-N 0.000 description 3
- FDTQPWCIJGYMNG-UHFFFAOYSA-N 4-phenylbuta-1,3-dienylbenzene;titanium(2+) Chemical compound [Ti+2].C=1C=CC=CC=1C=CC=CC1=CC=CC=C1 FDTQPWCIJGYMNG-UHFFFAOYSA-N 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 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 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
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- CXKQHHJKHZXXPZ-UHFFFAOYSA-N triethylsilanylium Chemical compound CC[Si+](CC)CC CXKQHHJKHZXXPZ-UHFFFAOYSA-N 0.000 description 1
- VOYMPSZBODLRKS-UHFFFAOYSA-N trimethylsilanylium Chemical compound C[Si+](C)C VOYMPSZBODLRKS-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- RERMPCBBVZEPBS-UHFFFAOYSA-N tris(2,6-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(C)=C1P(C=1C(=CC=CC=1C)C)C1=C(C)C=CC=C1C RERMPCBBVZEPBS-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-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
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims (1)
- 【特許請求の範囲】 1.式 ただし、 Mは+2,+3又は+4の形式酸化状態のチタン、ジルコニウム又はハフニウ ムであり; A’は少なくとも2位または3位において、ヒドロカルビル、フルオロ置換ヒ ドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ジアルキルアミノ− 置換ヒドロカルビル、シリル、ゲルミル、及びそれらの混合物からえらばれた基 で置換された置換インデニル基であり、該基は40以下の非水素原子を含み、そ して該A’は更に2価Z基によってMに共有結合している; ZはA’とMの両方にσ−結合を介して結合している2価の基であり、該Zは ホウ素又は元素の周期律表の14族の一員を含み、そして窒素、リン、イオウ又 は酸素をも含み; Xは、環式の非局在化したπ結合配位子基である種類の配位子を除いて、60 以下の原子をもつアニオン性またはジアニオン性の配位子基であり; X’はそれぞれの場合独立に、20以下の原子をもつ中性ルイス塩基配位性化 合物であり; pは0,1,又は2であり、Mの形式酸化状態より2だけ小さい、ただしXが ジアニオン性配位子基であるとき、pは1であり;そして qは0,1又は2である、 に相当する金属錯体。 2.式 ただし、 R1とR2は独立に、水素、ヒドロカルビル、パーフルオロ置換ヒドロカルビル 、シリル、ゲルミル及びそれらの混合物からえらばれた基であり、該基は20以 下の非水素原子を含む、ただしR1又はR2の少なくとも1は水素ではない; R3,R4,R5及びR6は独立に水素、ヒドロカルビル、パーフルオロ置換ヒド ロカルビル、シリル、ゲルミル、およびそれらの混合物からえらばれる基であり 、該基は20以下の非水素原子を含み; Mはチタン、ジルコニウム、またはハフニウムであり; Zはホウ素又は元素の周期律表の14族の一員を含む2価の基であって、また 窒素、リン、イオウ又は酸素をも含み、そして該基は60以下の非水素原子を含 む; pは0,1または2であり qはゼロまたは1である; ただし、 pが2であり、qがゼロであるとき、Mは+4形式酸化状態にあり、そしてX はハライド、ヒドロカルビル、ヒドロカルビルオキシ、ジ(ヒドロカルビル)ア ミド、ジ(ヒドロカルビル)ホスフィド、ヒドロカルビルスルフィド、およびシ リル基、ならびにそれらのハロ−、ジ(ヒドロカルビル)アミノ−、ヒドロカル ビルオキシ−、およびジ(ヒドロカルビル)ホスフィノ−置換誘導体からなる群 からえらばれたアニオン性配位子であり、そして該X基は20以下の非水素原子 をもち、 pが1であり、qがゼロであるとき、Mは+3形式酸化状態にあり、Xはアリ ル、2−(N,N−ジメチルアミノメチル)フェニル、および2−(N,N−ジ メチル)−アミノベンジルからなる群からえらばれた安定化用アニオン性配位子 基であるか、又はMは+4形式酸化状態にあり、Xは共役ジエンの2価誘導体で あり、そしてMとXは一緒になってメタロシクロペンテン基を形成し、そして pが0であり、qが1であるとき、Mは+2形式酸化状態にあり、X’は中性 の共役または非共役ジエンであって、任意に1以上のヒドロカルビル基で置換し ていてもよく、該X’は40以下の原子をもちそしてMとπ結合を形成している 、に相当する請求項1の金属錯体。 3.式 ただし R1とR2は独立に水素又はC1-6アルキルであるが、R1とR2の両方が水素で あることはなく; R3,R4,R5およびR6は独立に水素またはC1-6アルキルであり; Mはチタンであり; Yは−O−、−S−、−NR*−、または−PR*−であり; Z*はSiR* 2、CR* 2、SiR* 2,SiR* 2、CR* 2CR* 2、CR*=CR* 、CR* 2SiR* 2、またはGeR* 2であり; R*はそれぞれの場合独立に水素又はヒドロカルビル、ヒドロカルビルオキシ 、シリル、ハロゲン化アルキル、ハロゲル化アリールおよびそれらの組合せから えらばれた一員であり、該R*は20以下の非水素原子をもち、そして任意に、 Zからの2のR’基(R*が水素でないとき)、またはZからの1のR*基とYか らの1のR*基は環系を形成していてもよく; Pは0,1または2であり; qはゼロまたは1である; ただし、 pが2で、qがゼロであるとき、Mは+4形式酸化状態にあり、Xはそれぞれ の場合に独立にメチルまたはベンジルであり; pが1で、qがゼロであるとき、Mは+3形式酸化状態にあり、Xは2−(N ,N−ジメチル)アミノベンジルであるか、またはMは+4形式酸化状態にあり 、Xは1,4−ブタジエンであり、そして pが0で、qが1であるとき、Mは+2形式酸化状態にあり、X’は1,4− ジフェニル−1,3−ブタジエンまたは1,3−ペンタジエンである、 に相当する請求項1の金属錯体。 4.請求項1、2または3の金属錯体と活性化用共触媒とからなる配位重合触媒 。 5.活性化用共触媒がトリスペンタフルオロフェニル・ボランからなる請求項4 の配位重合触媒。 6.活性化用共触媒が1:1〜5:1のモル比のアルモキサンとトリスペンタフ ルオロフェニルボランとからなる請求項5の配位重合触媒。 7.1以上のC2-20α−オレフィンを重合条件下に、請求項1、2または3の金 属錯体と活性化用共触媒とからなる触媒に接触させることを特徴とする配位重合 法。 8.エチレン、プロピレン、及び任意に非共役ジエンを共重合させる請求項7の 配位重合法。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US591395P | 1995-10-27 | 1995-10-27 | |
| US60/005,913 | 1995-10-27 | ||
| PCT/US1996/016012 WO1997015583A1 (en) | 1995-10-27 | 1996-10-03 | Substituted indenyl containing metal complexes and olefin polymerization process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11514376A true JPH11514376A (ja) | 1999-12-07 |
| JP4454698B2 JP4454698B2 (ja) | 2010-04-21 |
Family
ID=21718328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51662097A Expired - Lifetime JP4454698B2 (ja) | 1995-10-27 | 1996-10-03 | 置換インデニル含有金属錯体およびオレフィン重合法 |
Country Status (22)
| Country | Link |
|---|---|
| EP (1) | EP0874860B1 (ja) |
| JP (1) | JP4454698B2 (ja) |
| KR (1) | KR100419698B1 (ja) |
| CN (1) | CN1098857C (ja) |
| AR (1) | AR006266A1 (ja) |
| AT (1) | ATE227729T1 (ja) |
| AU (1) | AU717869B2 (ja) |
| BR (1) | BR9611128A (ja) |
| CA (1) | CA2229608C (ja) |
| CZ (1) | CZ129998A3 (ja) |
| DE (1) | DE69624839T2 (ja) |
| ES (1) | ES2183978T3 (ja) |
| HU (1) | HUP9802868A3 (ja) |
| MY (1) | MY127666A (ja) |
| NO (1) | NO322510B1 (ja) |
| PL (1) | PL186283B1 (ja) |
| PT (1) | PT874860E (ja) |
| RO (1) | RO118295B1 (ja) |
| RU (1) | RU2175325C2 (ja) |
| TW (1) | TW430674B (ja) |
| WO (1) | WO1997015583A1 (ja) |
| ZA (1) | ZA969000B (ja) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005519969A (ja) * | 2002-03-14 | 2005-07-07 | ダウ・グローバル・テクノロジーズ・インコーポレイテッド | 置換インデニル金属錯体及び重合方法 |
| JP2015510966A (ja) * | 2012-03-19 | 2015-04-13 | エクソンモービル ケミカル パテンツ インコーポレイテッド | ポリα−オレフィンを製造するための新規触媒 |
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| US5965756A (en) * | 1996-12-19 | 1999-10-12 | The Dow Chemical Company | Fused ring substituted indenyl metal complexes and polymerization process |
| ES2168681T3 (es) * | 1996-12-19 | 2002-06-16 | Dow Chemical Co | Indenilo 3-(aril sustituido) que contiene complejos metalicos y procedimiento de polimerizacion. |
| US6420507B1 (en) | 1997-05-01 | 2002-07-16 | The Dow Chemical Company | Olefin polymers prepared with substituted indenyl containing metal complexes |
| AR012645A1 (es) * | 1997-05-01 | 2000-11-08 | Dow Global Technologies Inc | Polimeros de alfa-olefinas preparados por polimerizacion en presencia de complejos de metales que contienen grupos indenilo |
| US6150297A (en) | 1997-09-15 | 2000-11-21 | The Dow Chemical Company | Cyclopentaphenanthrenyl metal complexes and polymerization process |
| US6630545B2 (en) | 1997-09-15 | 2003-10-07 | The Dow Chemical Company | Polymerization process |
| DE69928185T2 (de) * | 1998-01-30 | 2006-07-20 | Boulder Scientific Co., Mead | Synthese von n-silylierten verbindungen |
| AU1241600A (en) | 1998-11-02 | 2000-05-22 | Dupont Dow Elastomers L.L.C. | Shear thinning ethylene/alpha-olefin interpolymers and their preparation |
| US6806327B2 (en) | 2000-06-30 | 2004-10-19 | Dow Global Technologies Inc. | Substituted polycyclic, fused ring compounds, metal complexes and polymerization process |
| KR20030013479A (ko) * | 2000-06-30 | 2003-02-14 | 더 다우 케미칼 캄파니 | 폴리사이클릭 접합 고리 화합물, 금속 착체 및 중합방법 |
| US6946531B2 (en) | 2001-05-14 | 2005-09-20 | Dow Global Technologies Inc. | Low molecular weight ethylene interpolymers and polymerization process |
| EP1389215B1 (en) * | 2001-05-14 | 2005-06-15 | Dow Global Technologies Inc. | 3-aryl-substituted cyclopentadienyl metal complexes and polymerization process |
| US6927264B2 (en) | 2003-05-28 | 2005-08-09 | Dow Global Technologies Inc. | Metal complexes and polymerization process using same |
| RU2373592C1 (ru) * | 2006-09-11 | 2009-11-20 | Асахи Касеи Кабусики Кайся | Полимерный электролит, способ его получения и электрохимический элемент |
| RU2549541C2 (ru) | 2009-07-28 | 2015-04-27 | Юнивейшн Текнолоджиз, Ллк | Способ полимеризации с использованием нанесенного катализатора с затрудненной геометрией |
| CA2724943A1 (en) | 2010-12-10 | 2012-06-10 | Nova Chemicals Corporation | Catalyst activation in a dual reactor process |
| US9708418B2 (en) | 2011-03-08 | 2017-07-18 | Dow Global Technologies Llc | Process for recycling solvent used in an ethylene-based polymerization reaction and system therefor |
| CN107107025A (zh) | 2015-01-06 | 2017-08-29 | Scg化学有限公司 | SiO2层状双氢氧化物微球及它们的制备方法 |
| KR102010630B1 (ko) * | 2016-01-20 | 2019-08-13 | 한화토탈 주식회사 | 올레핀 중합촉매 및 이를 이용한 올레핀 중합방법 |
| GB201608384D0 (en) | 2016-05-12 | 2016-06-29 | Scg Chemicals Co Ltd | Unsymmetrical metallocene catalysts and uses thereof |
| GB201610457D0 (en) * | 2016-06-15 | 2016-07-27 | Scg Chemicals Co Ltd | Catalysts |
| KR101870513B1 (ko) | 2016-06-29 | 2018-06-22 | 강정영 | 소형 탈취장치 |
| CN112939844B (zh) * | 2019-12-10 | 2023-02-03 | 华东师范大学 | 一种多取代四氢咔唑及其衍生物及其合成方法和应用 |
| US20240124618A1 (en) | 2021-01-12 | 2024-04-18 | Exxonmobil Chemical Patents Inc. | Asymmetric Constrained Geometry Catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8600045A (nl) * | 1986-01-11 | 1987-08-03 | Stamicarbon | Katalysatorsysteem voor hoge temperatuur (co)polymerisatie van etheen. |
| US5096867A (en) * | 1990-06-04 | 1992-03-17 | Exxon Chemical Patents Inc. | Monocyclopentadienyl transition metal olefin polymerization catalysts |
| NZ235032A (en) * | 1989-08-31 | 1993-04-28 | Dow Chemical Co | Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component |
| US5026798A (en) * | 1989-09-13 | 1991-06-25 | Exxon Chemical Patents Inc. | Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system |
| HUT74312A (en) * | 1993-06-24 | 1996-12-30 | Dow Chemical Co | Titanium or zirconium complexes, process for producing thereof, polymerization catalysts containing thereof and polymerization process |
| WO1995014024A1 (en) * | 1993-11-18 | 1995-05-26 | Idemitsu Kosan Co., Ltd. | Transition metal compound, olefin polymerization catalyst, and process for producing olefin polymer by using said catalyst |
| WO1996007681A1 (en) * | 1994-09-02 | 1996-03-14 | The Dow Chemical Company | Thermoset elastomers |
-
1996
- 1996-10-03 CN CN96197902A patent/CN1098857C/zh not_active Expired - Lifetime
- 1996-10-03 AU AU73929/96A patent/AU717869B2/en not_active Ceased
- 1996-10-03 WO PCT/US1996/016012 patent/WO1997015583A1/en not_active Ceased
- 1996-10-03 JP JP51662097A patent/JP4454698B2/ja not_active Expired - Lifetime
- 1996-10-03 PT PT96936227T patent/PT874860E/pt unknown
- 1996-10-03 CA CA002229608A patent/CA2229608C/en not_active Expired - Fee Related
- 1996-10-03 EP EP96936227A patent/EP0874860B1/en not_active Expired - Lifetime
- 1996-10-03 RU RU98109935/04A patent/RU2175325C2/ru not_active IP Right Cessation
- 1996-10-03 RO RO98-00892A patent/RO118295B1/ro unknown
- 1996-10-03 BR BR9611128A patent/BR9611128A/pt not_active IP Right Cessation
- 1996-10-03 CZ CZ981299A patent/CZ129998A3/cs unknown
- 1996-10-03 ES ES96936227T patent/ES2183978T3/es not_active Expired - Lifetime
- 1996-10-03 DE DE69624839T patent/DE69624839T2/de not_active Expired - Lifetime
- 1996-10-03 AT AT96936227T patent/ATE227729T1/de not_active IP Right Cessation
- 1996-10-03 PL PL96326426A patent/PL186283B1/pl not_active IP Right Cessation
- 1996-10-03 KR KR10-1998-0702982A patent/KR100419698B1/ko not_active Expired - Lifetime
- 1996-10-03 HU HU9802868A patent/HUP9802868A3/hu unknown
- 1996-10-24 TW TW085113065A patent/TW430674B/zh not_active IP Right Cessation
- 1996-10-25 MY MYPI96004449A patent/MY127666A/en unknown
- 1996-10-25 ZA ZA9609000A patent/ZA969000B/xx unknown
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1997
- 1997-03-18 AR ARP970101064A patent/AR006266A1/es active IP Right Grant
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- 1998-04-24 NO NO19981854A patent/NO322510B1/no not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005519969A (ja) * | 2002-03-14 | 2005-07-07 | ダウ・グローバル・テクノロジーズ・インコーポレイテッド | 置換インデニル金属錯体及び重合方法 |
| JP2015510966A (ja) * | 2012-03-19 | 2015-04-13 | エクソンモービル ケミカル パテンツ インコーポレイテッド | ポリα−オレフィンを製造するための新規触媒 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69624839D1 (de) | 2002-12-19 |
| MY127666A (en) | 2006-12-29 |
| KR19990067045A (ko) | 1999-08-16 |
| JP4454698B2 (ja) | 2010-04-21 |
| AU7392996A (en) | 1997-05-15 |
| HUP9802868A3 (en) | 1999-04-28 |
| CZ129998A3 (cs) | 1998-08-12 |
| NO981854D0 (no) | 1998-04-24 |
| DE69624839T2 (de) | 2003-08-28 |
| WO1997015583A1 (en) | 1997-05-01 |
| BR9611128A (pt) | 1999-03-30 |
| HUP9802868A2 (hu) | 1999-03-29 |
| CN1200735A (zh) | 1998-12-02 |
| NO981854L (no) | 1998-06-23 |
| ES2183978T3 (es) | 2003-04-01 |
| CA2229608C (en) | 2005-06-21 |
| RO118295B1 (ro) | 2003-04-30 |
| AR006266A1 (es) | 1999-08-11 |
| TW430674B (en) | 2001-04-21 |
| AU717869B2 (en) | 2000-04-06 |
| ATE227729T1 (de) | 2002-11-15 |
| PT874860E (pt) | 2003-02-28 |
| EP0874860A1 (en) | 1998-11-04 |
| EP0874860B1 (en) | 2002-11-13 |
| PL186283B1 (pl) | 2003-12-31 |
| CN1098857C (zh) | 2003-01-15 |
| RU2175325C2 (ru) | 2001-10-27 |
| ZA969000B (en) | 1998-04-28 |
| KR100419698B1 (ko) | 2004-05-17 |
| CA2229608A1 (en) | 1997-05-01 |
| PL326426A1 (en) | 1998-09-14 |
| NO322510B1 (no) | 2006-10-16 |
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