JP2000516228A - 3―ヘテロ原子置換シクロペンタジエニル含有金属錯体及びオレフィン重合方法 - Google Patents
3―ヘテロ原子置換シクロペンタジエニル含有金属錯体及びオレフィン重合方法Info
- Publication number
- JP2000516228A JP2000516228A JP10509759A JP50975998A JP2000516228A JP 2000516228 A JP2000516228 A JP 2000516228A JP 10509759 A JP10509759 A JP 10509759A JP 50975998 A JP50975998 A JP 50975998A JP 2000516228 A JP2000516228 A JP 2000516228A
- Authority
- JP
- Japan
- Prior art keywords
- dimethyl
- metal complex
- hydrocarbyl
- dimethylethyl
- titanium
- 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
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 94
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 65
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 31
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 125000000058 cyclopentadienyl group Chemical class C1(=CC=CC1)* 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 108
- 239000003054 catalyst Substances 0.000 claims abstract description 101
- 229910052751 metal Inorganic materials 0.000 claims abstract description 71
- 239000002184 metal Substances 0.000 claims abstract description 71
- 239000003446 ligand Substances 0.000 claims abstract description 52
- -1 hydrocarbyl sulfide Chemical compound 0.000 claims description 301
- 239000000243 solution Substances 0.000 claims description 167
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 138
- 239000000203 mixture Substances 0.000 claims description 87
- 229920000642 polymer Polymers 0.000 claims description 52
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 48
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 37
- 239000005977 Ethylene Substances 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 32
- 150000001993 dienes Chemical class 0.000 claims description 32
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 32
- 230000003647 oxidation Effects 0.000 claims description 31
- 238000007254 oxidation reaction Methods 0.000 claims description 31
- 239000004711 α-olefin Substances 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 230000015572 biosynthetic process Effects 0.000 claims description 25
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 24
- 125000005842 heteroatom Chemical group 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 23
- 230000003213 activating effect Effects 0.000 claims description 22
- 125000004122 cyclic group Chemical group 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 17
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 16
- 229920000098 polyolefin Polymers 0.000 claims description 15
- 125000000129 anionic group Chemical group 0.000 claims description 14
- 230000002452 interceptive effect Effects 0.000 claims description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 12
- 239000002685 polymerization catalyst Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 230000000737 periodic effect Effects 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 10
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 7
- 150000004678 hydrides Chemical class 0.000 claims description 7
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 7
- 150000002602 lanthanoids Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001350 alkyl halides Chemical class 0.000 claims description 6
- 150000001502 aryl halides Chemical class 0.000 claims description 6
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Chemical group CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 5
- 239000002879 Lewis base Substances 0.000 claims description 5
- 229910052768 actinide Inorganic materials 0.000 claims description 5
- 150000001255 actinides Chemical class 0.000 claims description 5
- 239000012458 free base Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000007527 lewis bases Chemical class 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 125000000719 pyrrolidinyl group Chemical group 0.000 claims description 4
- 150000005839 radical cations Chemical class 0.000 claims description 4
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- OMIVCRYZSXDGAB-UHFFFAOYSA-N 1,4-butanediyl Chemical group [CH2]CC[CH2] OMIVCRYZSXDGAB-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 125000002757 morpholinyl group Chemical group 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical group C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 claims description 2
- 241001024304 Mino Species 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 238000005192 partition Methods 0.000 claims 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 125000005641 methacryl group Chemical group 0.000 claims 1
- 125000000168 pyrrolyl group Chemical group 0.000 claims 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 abstract description 11
- 229920006158 high molecular weight polymer Polymers 0.000 abstract description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 481
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 415
- 229910000077 silane Inorganic materials 0.000 description 337
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 329
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 300
- 239000010936 titanium Substances 0.000 description 300
- 229910052719 titanium Inorganic materials 0.000 description 292
- COOXAWDWHWRVRD-UHFFFAOYSA-N C[Ti]C Chemical compound C[Ti]C COOXAWDWHWRVRD-UHFFFAOYSA-N 0.000 description 247
- UHOVQNZJYSORNB-MZWXYZOWSA-N deuterated benzene Substances [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 195
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 157
- 230000002829 reductive effect Effects 0.000 description 130
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 127
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 108
- 239000000047 product Substances 0.000 description 94
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 78
- 239000002904 solvent Substances 0.000 description 77
- 239000007787 solid Substances 0.000 description 72
- 238000004519 manufacturing process Methods 0.000 description 71
- 125000003963 dichloro group Chemical group Cl* 0.000 description 61
- 125000004214 1-pyrrolidinyl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 58
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 46
- 239000013078 crystal Substances 0.000 description 44
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 38
- 239000000178 monomer Substances 0.000 description 38
- 229910052744 lithium Inorganic materials 0.000 description 37
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 37
- 238000002360 preparation method Methods 0.000 description 37
- 238000007792 addition Methods 0.000 description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 33
- 159000000002 lithium salts Chemical class 0.000 description 32
- 239000007788 liquid Substances 0.000 description 31
- 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 30
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 29
- 239000011541 reaction mixture Substances 0.000 description 29
- 238000003756 stirring Methods 0.000 description 29
- 239000002244 precipitate Substances 0.000 description 28
- 150000003839 salts Chemical class 0.000 description 26
- 238000001914 filtration Methods 0.000 description 25
- 150000001450 anions Chemical class 0.000 description 24
- 229910003002 lithium salt Inorganic materials 0.000 description 22
- 239000003921 oil Substances 0.000 description 22
- 235000019198 oils Nutrition 0.000 description 22
- 239000000126 substance Substances 0.000 description 22
- 150000001412 amines Chemical class 0.000 description 20
- 238000012937 correction Methods 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 18
- 229920002943 EPDM rubber Polymers 0.000 description 17
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 17
- 239000012071 phase Substances 0.000 description 17
- 238000013480 data collection Methods 0.000 description 16
- 150000002081 enamines Chemical class 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 16
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 16
- KEDCKEFNGOUWPJ-UHFFFAOYSA-N C=1C=CC=CC=1C[Ti]CC1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C[Ti]CC1=CC=CC=C1 KEDCKEFNGOUWPJ-UHFFFAOYSA-N 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 238000004364 calculation method Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000003085 diluting agent Substances 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 12
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 12
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 12
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 12
- 150000004820 halides Chemical class 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 11
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 11
- 238000005868 electrolysis reaction Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 230000006870 function Effects 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 10
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 10
- 239000003115 supporting electrolyte Substances 0.000 description 10
- 239000003039 volatile agent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 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 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- 150000004703 alkoxides Chemical class 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 8
- 239000002841 Lewis acid Substances 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 8
- 150000002576 ketones Chemical class 0.000 description 8
- 150000007517 lewis acids Chemical class 0.000 description 8
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 8
- 239000007983 Tris buffer Substances 0.000 description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- 239000000284 extract Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 125000002524 organometallic group Chemical group 0.000 description 7
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 6
- INGMFAOZILACFX-UHFFFAOYSA-N C1(=CC=CC=C1)C[Ti](CC(C)(C)C)(CC(C)(C)C)CC1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C[Ti](CC(C)(C)C)(CC(C)(C)C)CC1=CC=CC=C1 INGMFAOZILACFX-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- JGALSKCCWGCHHM-UHFFFAOYSA-N [Ti]C Chemical compound [Ti]C JGALSKCCWGCHHM-UHFFFAOYSA-N 0.000 description 6
- 229910000085 borane Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 6
- 150000002170 ethers Chemical class 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
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- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- VOYMPSZBODLRKS-UHFFFAOYSA-N trimethylsilanylium Chemical group 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
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
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- 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+
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- 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
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
Claims (1)
- 【特許請求の範囲】 1. 式: (式中、Mは、元素の周期律表の3−13族の1、ランタニド又はアクチニドか らの金属であり、それは+2、+3又は+4形式酸化状態にあり、そして5個の 置換基、即ちRA、(RB)j−T(但し、jは0、1又は2である)、RC、RD 及びZ(但し、RA、RB、RC及びRDはR基である)を有する環状の非局在化π −結合リガンド基である1個のシクロペンタジエニル(Cp)基にπ結合してお り、さらに Tは、jが1又は2であるとき、Cp環そしてRBに共有結合しているヘテロ原 子であり、さらにjが0のとき、TはF、Cl、Br又はIであり;jが1のと き、TはO又はS、又はN又はPであり、そしてRBはTへの二重結合を有し; jが2のとき、TはN又はPであり、さらに RBは、それぞれの場合独立して、水素であるか、又はヒドロカルビル、ヒドロ カルビルシリル、ハロゲン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、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル ヒドロカルビル、ヒドロカルビルアミノ、ジ(ヒドロカルビル)アミノ、ヒドロ カルビルオキシである1−80個の非水素原子を有する基であり、各RBは任意 にそれぞれの場合独立して1−20個の非水素原子を有するヒドロカルビルオキ シ、ヒドロカルビルシロキシ、ヒドロカルビルシリルアミノ、ジ(ヒドロカルビ ルシリル)アミノ、ヒドロカルビルアミノ、ジ(ヒドロカルビル)アミノ、ジ( ヒドロカルビル)ホスフィノ、ヒドロカルビルスルフィド、ヒドロカルビル、ハ ロゲン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、ヒドロ カルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル又はヒドロカルビ ルシリルヒドロカルビル又は1−20個の非水素原子を有する非干渉基である1 個以上の基により置換されていてもよく;そしてRA、RC及びRDのそれぞれは 、水素であるか、又はヒドロカルビル、ハロゲン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、ヒドロカルビルアミノ置換ヒドロカルビル、 ヒドロカルビルシリル、ヒドロカルビルシリルヒドロカルビルである1−80個 の非水素原子を有する基であり、RA、RC及びRDのそれぞれは、任意にそれぞ れの場合独立して1−20個の非水素原子を有するヒドロカルビルオキシ、ヒド ロカルビルシロキシ、ヒドロカルビルシリルアミノ、ジ(ヒドロカルビルシリル )アミノ、ヒドロカルビルアミノ、ジ(ヒドロカルビル)アミノ、ジ(ヒドロカ ルビル)ホスフィノ、ヒドロカルビルスルフィド、ヒドロカルビル、ハロゲン置 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、ヒドロカルビル アミノ置換ヒドロカルビル、ヒドロカルビルシリル又はヒドロカルビルシリルヒ ドロカルビルであるか、又は1−20個の非水素原子を有する非干渉基である1 個以上の基により置換されていてもよく;又は任意に、RA、RB、RC及びRDの 2個以上は、互いに共有結合してそれぞれのR基について1−80個の非水素原 子を有する1個以上の縮合環又は環系を形成し、1個以上の縮合環又は環系は、 置換されていないか、又はそれぞれの場合独立して1−20個の非水素原子を有 するヒドロカルビルオキシ、ヒドロカルビルシロキシ、ヒドロカルビルシリルア ミノ、ジ(ヒドロカルビルシリル)アミノ、ヒドロカルビルアミノ、ジ(ヒドロ カルビル)アミノ、ジ(ヒドロカルビル)ホスフィノ、ヒドロカルビルスルフィ ド、ヒドロカルビル、ハロゲン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、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシ リル又はヒドロカルビルシリルヒドロカルビル、又は1−20個の非水素原子を 有する非干渉基である1個以上の基により置換されており; Zはσ結合を介してCp及びMの両者に結合している2価の基であり、Zは硼素 であるか又は元素の周期律表の14族の一員であり、さらに窒素、燐、硫黄又は 酸素からなり; Xは、環状の非局在化π結合リガンド基であるリガンドの群を除く、60個以内 の原子を有するアニオン性又はジアニオン性リガンド基であり; X’は、それぞれの場合独立して20個以内の原子を有する中性のルイス塩基配 位結合性化合物であり; pは0、1又は2であり、そしてXがアニオン性リガンドであるときMの形式酸 化状態より2少なく;Xがジアニオン性リガンドであるとき、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: (式中、RW、RX、RY及びRZはR基であり、それらのそれぞれは独立して水素 であるか、又はヒドロカルビル、ハロゲン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、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロ カルビルシリル、ヒドロカルビルシリルヒドロカルビルである1−80個の非水 素原子を有する基であり、RW、RX、RY及びRZのそれぞれは、任意にそれぞれ の場合独立して1−20個の非水素原子を有するヒドロカルビルオキシ、ヒドロ カルビルシロキシ、ヒドロカルビルシリルアミノ、ジ(ヒドロカルビルシリル) アミノ、ヒドロカルビルアミノ、ジ(ヒドロカルビル)アミノ、ジ(ヒドロカル ビル)ホスフィノ、ヒドロカルビルスルフィド、ヒドロカルビル、ハロゲン置換 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、ヒドロカルビルア ミノ置換ヒドロカルビル、ヒドロカルビルシリル又はヒドロカルビルシリルヒド ロカルビルであるか、又は1−20個の非水素原子を有する非干渉基である1個 以上の基により置換されていてもよく;又は任意に、RW、RX、RY、RZ、RA 及びRBの2個以上は、互いに共有結合してそれぞれのR基について 1−80個の非水素原子を有する1個以上の縮合環又は環系を形成し、1個以上 の縮合環又は環系は、置換されていないか、又はそれぞれの場合独立して1−2 0個の非水素原子を有するヒドロカルビルオキシ、ヒドロカルビルシロキシ、ヒ ドロカルビルシリルアミノ、ジ(ヒドロカルビルシリル)アミノ、ヒドロカルビ ルアミノ、ジ(ヒドロカルビル)アミノ、ジ(ヒドロカルビル)ホスフィノ、ヒ ドロカルビルスルフィド、ヒドロカルビル、ハロゲン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、ヒドロカルビルアミノ置換ヒドロカルビ ル、ヒドロカルビルシリル又はヒドロカルビルシリルヒドロカルビル、又は1− 20個の非水素原子を有する非干渉基である1個以上の基により置換されている )に相当する請求項1の金属錯体。 3. RBがヒドロカルビル、ヒドロカルビルシリル、ヒドロカルビルオキシ−置 換ヒドロカルビル、ヒドロカルビルアミノ−置換ヒドロカルビルであり、そして TがO又はNである請求項1又は2の金属錯体。 4. RBがヒドロカルビル又はヒドロカルビルシリルであり、そしてTがO又は Nである請求項3の金属錯体。 5. RBがヒドロカルビル又はヒドロカルビルシリルでありそしてTがNである 請求項4の金属錯体。 6. (RB)j−T基がメトキシ、エトキシ、プロポキシ、メチルエチルオキシ、 1,1−ジメチルエチルオキシ、トリメチルシロキシ、1,1−ジメチルエチル (ジメチルシリル)オキシ、ジメチルアミノ、ジエチルアミノ、メチルエチルア ミノ、メチルフェニルアミノ、ジプロピルアミノ、ジブチルアミノ、ピペリジニ ル、モルホリニル、ピロリジニル、ヘキサヒドロ−1H−アゼピン−1−イル、 ヘキサヒドロ−1(2H)−アゾシニル、オクタヒドロ−1H−アゾニン−1− イル又はオクタヒドロ−1(2H)−アゼシニルである請求項3の金属錯体。 7. (RB)j−T基がジメチルアミノ、メチルフェニルアミノ、ピペリジニル又 はピロリジニルである請求項4の金属錯体。 8. 1以上の縮合環又は環系がN、O、S又はPである1以上の環ヘテロ原子を 含有する請求項1又は2の金属錯体。 9. 環ヘテロ原子がN又はOである請求項8の金属錯体。 10.それぞれの環ヘテロ原子がNである請求項9の金属錯体。 11.式: (式中、符号は前記定義のとおりである)に相当する請求項2の金属錯体。 12.式: (式中、符号は前記定義のとおりである)に相当する請求項11の金属錯体。 13.−Z−が−Z*−Y−であり、ここでZ*はCpにそしてYはMに結合してお り、そして Yは−O−、−S−、−NR*−、−PR*−であり; ZはSiR* 2、CR* 2、SiR* 2SiR* 2、CR* 2CR* 2、CR*=CR*、CR* 2 SiR* 2、CR* 2SiR* 2CR* 2、SiR* 2CR* 2SiR* 2、CR* 2CR* 2S iR* 2、CR* 2CR* 2CR* 2又はGeR* 2であり;そして R*はそれぞれの場合独立して水素であるか、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、ハロゲン化アリール及びそれらの組 合せから選ばれる1員であり、そして該R*は20個以下の非水素原子をもち、 そして任意に、Zからの2個のR*基(R*が水素でないとき)、又はZからの1 個のR*基及びYからの1個のR*基が環系を形成しており; ここでpは2であり、qは0であり、Mは+4形式酸化状態にあり、そしてXは それぞれの場合独立してメチル、ベンジル、トリメチルシリルメチル、アリル、 ピロリルであるか又は2個のX基がいっしょになって1,4−ブタン−ジイル、 2−ブテン−1,4−ジイル、2,3−ジメチル−2−ブテン−1,4−ジイル 、2−メチル−2−ブテン−1,4−ジイル又はキシリルジイルである、請求項 1〜12のいずれか1項の金属錯体。 14.Zが−Z*−Y−であり、Z*がCpにそしてYがMに結合しており、そして Yが−O−、−S−、−NR*−、−PR*−であり; Z*がSiR* 2、CR* 2、SiR* 2SiR* 2、CR* 2CR* 2、CR*=CR*、C R* 2SiR* 2、CR* 2SiR* 2CR* 2、SiR* 2CR* 2SiR* 2、CR* 2CR* 2 SiR* 2、CR* 2CR* 2CR* 2、又はGeR* 2であり;そして R*がそれぞれの場合独立して水素であるか、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、ハロゲン化アリール及びそれらの組 合せから選ばれる1員であり、該R*が20個以下の非水素原子をもち、そして 任意に、Zからの2個のR*基(R*が水素でないとき)、又はZからの1個のR* 基とYからの1個のR*基が環系を形成しており; ここでpは1であり、qは0であり、Mは+3形式酸化状態にあり、そしてXは 2−(N,N−ジメチル)アミノベンジル、2−(N,N−ジメチルアミノメチ ル)フェニル、アリル、メタクリル又はトリメチルシリルアリルである請求項1 〜12のいずれか1項の金属錯体。 15.−Z−が−Z*−Y−であり、Z*がCpに結合しそしてYがMに結合してお り、そして Yが−O−、−S−、−NR*−、−PR*−であり; Z*がSiR* 2、CR* 2、SiR* 2SiR* 2、CR* 2CR* 2、CR*=CR*、C R* 2SiR* 2。、CR* 2SiR* 2CR* 2、SiR* 2CR* 2SiR* 2、CR* 2CR* 2 SiR* 2、CR* 2CR* 2CR* 2又はGeR* 2であり;そして R*がそれぞれの場合独立して水素であるか、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、ハロゲン化アリール及びそれらの組 含せから選ばれる1員であり、該R*が20個以下の非水素原子をもち、そして 任意に、Zからの2個のR*基(R*が水素でないとき)、又はZからの1個のR* 基とYからの1個のR*基が環系を形成しており; pは1であるとき、qは1であり、Mは+2形式酸化状態にあり、そしてXは1 ,4−ジフェニル−1,3−ブタジエン、1,3−ペンタジエン又は2,4−ヘ キサジエンである請求項1〜12のいずれか1項の金属錯体。 16.Mが3〜6族の1、7〜9族の1又は10〜12族の1からの金属である請 求項1〜15のいずれか1項の金属錯体。 17.Mが3〜6族の1からの金属である請求項16の金属錯体。 18.Mが7〜9族の1からの金属である請求項16の金属錯体。 19.Mが10〜12族の1からの金属である請求項16の金属錯体。 20.Mが4族の金属である請求項17の金属錯体。 21.MがTiである請求項20の金属錯体。 22.MがZrである請求項20の金属錯体。 23.Mが+4形式酸化状態のTiである請求項21の金属錯体。 24.Mが+3形式酸化状態のTiである請求項21の金属錯体。 25.Mが+2形式酸化状態のTiである請求項21の金属錯体。 26.Mが+4形式酸化状態のZrである請求項22の金属錯体。 27.Mが+2形式酸化状態のZrである請求項22の金属錯体。 28.Yが−NR*である請求項13〜27のいずれか1項の金属錯体。 29.R*がNに結合した1級又は2級炭素をもつ基である請求項28の金属錯体 。 30.R*がシクロヘキシル又はイソプロピルである請求項29の金属錯体。 31.式:に相当する請求項23の金属錯体。 32.式: に相当する請求項23の金属錯体。 33.式: に相当する請求項23の金属錯体。 34.式: に相当する請求項23の金属錯体。 35.式: に相当する請求項23の金属錯体。 36.式: に相当する請求項23の金属錯体。 37.式:に相当する請求項25の金属錯体。 38.式: に相当する請求項23の金属錯体。 39.式: に相当する請求項23の金属錯体。 40.式:に相当する請求項23の金属錯体。 41.式: に相当する請求項23の金属錯体。 42.式: に相当する請求項23の金属錯体。 43.式:に相当する請求項23の金属錯体。 44.式: に相当する請求項23の金属錯体。 45.式: に相当する請求項23の金属錯体。 46.式:に相当する請求項23の金属錯体。 47.式: に相当する請求項23の金属錯体。 48.式: に相当する請求項23の金属錯体。 49.式:に相当する請求項23の金属錯体。 50.式: に相当する請求項25の金属錯体。 51.式: に相当する請求項25の金属錯体。 52.式:に相当する請求項26の金属錯体。 53.式: に相当する請求項26の金属錯体。 54.式: に相当する請求項23の金属錯体。 55.式:に相当する請求項23の金属錯体。 56.式: に相当する請求項25の金属錯体。 57.式: に相当する請求項25の金属錯体。 58.式:に相当する請求項23の金属錯体。 59.式: に相当する請求項24の金属錯体。 60.式: に相当する請求項23の金属錯体。 61.式:に相当する請求項24の金属錯体。 62.式: に相当する請求項23の金属錯体。 63.式: に相当する請求項23の金属錯体。 64.式:に相当する請求項23の金属錯体。 65.式: に相当する請求項23の金属錯体。 66.式: に相当する請求項23の金属錯体。 67.(A)請求項1〜66のいずれか1項の金属錯体からなる触媒成分;及び( B)活性化用共触媒からなる共触媒成分を(A):(B)のモル比1:10,0 00〜100:1で有するか;又は活性化技術によって(A)を活性化させてな る触媒系成分からつくられたオレフィン重合用触媒系。 68.さらに(C)アルミニウム有機金属成分をもつ請求項67の触媒系。 69.アルミニウム有機金属触媒系がアルモキサン、アルミニウムアルキル又はそ れらの組合せからなる請求項68の触媒系。 70.共触媒成分が非イオン性又はイオン性の有機ホウ素化合物からなる請求項6 7〜69のいずれか1項の触媒系。 71.共触媒成分がトリス(ペンタフルオロフェニル)ボランからなる請求項70 の触媒系。 72.共触媒は成分がアルモキサン及びトリス(ペンタフルオロフェニル)ボラン をモル比1:1〜5:1でもつ請求項71の触媒系。 73.さらに(D)ポリマー、無機酸化物、ハロゲン化金属又はそれらの混合物で ある支持物質からなる支持成分をもつ請求項67〜72のいずれか1項の触媒系 。 74.(A)請求項1〜66のいずれか1項の金属錯体からなる触媒成分;及び( B)活性化用共触媒からなる共触媒成分を(A):(B)のモル比1:10,0 00〜100:1で有し、且つ金属錯体がラジカルカチオンの形態にある触媒系 からつくられたオレフィン重合用触媒系。 75.請求項67〜74のいずれか1項の触媒系に1以上のC2-20α−オレフィン を重合条件下に接触させることを特徴とするオレフィンの重合方法。 76.エチレン、プロピレン、及び所望により非共役ジエンを共重合させる請求項 75の方法。 77.エチレン、プロピレン、又はエチレン及びプロピレン、及び1以上のC4-20 α−オレフィンを共重合させる請求項75の方法。 78.溶液中で行う請求項75〜77のいずれか1項の方法。 79.気相で行う請求項75〜77のいずれか1項の方法。 80.スラリー中で行う請求項75〜77のいずれか1項の方法。 81.1以上のC2-20α−オレフィンを重合条件下に請求項67〜74のいずれか 1項の触媒系と約100℃〜約50℃の温度で接触させるオレフィン重合用高温 溶液重合方法。 82.温度が約120℃〜約200℃である請求項81の方法。 83.温度が約150℃〜約200℃である請求項82の方法。 84.請求項75〜83のいずれか1項の方法でつくられたポリオレフィン生成物 。 85.生成物が炭素原子1000当り0.01〜3の長鎖分枝をもつ請求項84の ポリオレフィン生成物。 86.生成物が1.10以上のコモノマー分配係数Cpfをもつか又は1.15以上 の分子量分配係数Mpfをもつか、又は1.10以上のコモノマー分配係数と1. 15以上の分子量分配係数Mpfとをもつコポリマー組成物である請求項84のポ リオレフィン生成物。 87.コポリマー組成物が1.20以上のコモノマー分配係数Cpfをもつか又は1 .30以上の分子量分配係数Mpfをもつか、又は1.20以上のコモノマー分配 係数と1.30以上の分子量分配係数Mpfとをもつコポリマー組成物である請求 項86のポリオレフィン生成物。 88.配位子が (A)脱プロトン化されうる2プロトンをもつ遊離塩基; (B)ジリチウム塩; (C)マグネシウム塩;又は (D)モノ又はジシリル化ジアニオンの形態にある請求項1〜66のいずれか1 項のシクロペンタジエニル−含有配位子。 89.請求項1〜66のいずれか1項の金属錯体を生成させる合成に請求項88の 配位子を使用する方法。 90.元素の周期律表の3〜13族の1、ランタニド又はアクチニドからの金属、 及び1〜4個の該配位子からなる金属錯体を生成させる合成に請求項88の配位 子を使用する方法。
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| US60/034,819 | 1996-12-19 | ||
| PCT/US1997/013170 WO1998006727A1 (en) | 1996-08-08 | 1997-07-28 | 3-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process |
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| ATE198207T1 (de) * | 1992-08-03 | 2001-01-15 | Targor Gmbh | Verfahren zur herstellung eines olefinpolymers unter verwendung spezieller metallocene |
| BR9407034A (pt) | 1993-06-24 | 1996-03-19 | Dow Chemical Co | Complexos de titânio ( I) ou zircônio (II) e catalisadores de polimerização por adição dos mesmos |
| KR100350544B1 (ko) | 1993-09-17 | 2003-01-24 | 비피 케미칼즈 리미티드 | 올레핀의기상중합 |
| 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 |
| DE4406963A1 (de) * | 1994-03-03 | 1995-09-07 | Basf Ag | Metallocenkomplexe mit heterofunktionellen Gruppen am Cyclopentadienylsystem |
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| DE19517851A1 (de) * | 1995-05-16 | 1996-11-21 | Hoechst Ag | Organometallverbindung |
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1997
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- 1997-07-28 JP JP50975998A patent/JP3407074B2/ja not_active Expired - Lifetime
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- 1997-07-28 CN CN97197837A patent/CN1114609C/zh not_active Expired - Lifetime
- 1997-07-28 KR KR1019997000985A patent/KR100528754B1/ko not_active Expired - Lifetime
- 1997-07-28 SK SK153-99A patent/SK15399A3/sk unknown
- 1997-07-28 HU HU9902581A patent/HUP9902581A3/hu unknown
- 1997-07-28 BR BR9711124-4A patent/BR9711124A/pt not_active IP Right Cessation
- 1997-07-28 WO PCT/US1997/013170 patent/WO1998006727A1/en not_active Ceased
- 1997-07-28 TR TR1999/00487T patent/TR199900487T2/xx unknown
- 1997-07-28 EP EP97939348A patent/EP0923589B1/en not_active Expired - Lifetime
- 1997-07-28 DE DE69730718T patent/DE69730718T2/de not_active Expired - Lifetime
- 1997-07-28 AT AT97939348T patent/ATE276263T1/de not_active IP Right Cessation
- 1997-07-28 AU AU41456/97A patent/AU719500B2/en not_active Ceased
- 1997-07-28 ES ES97939348T patent/ES2224266T3/es not_active Expired - Lifetime
- 1997-07-28 US US09/230,185 patent/US6268444B1/en not_active Expired - Lifetime
- 1997-07-28 NZ NZ333878A patent/NZ333878A/xx unknown
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- 1997-08-07 TW TW086111317A patent/TW455595B/zh not_active IP Right Cessation
- 1997-08-08 MY MYPI97003634A patent/MY132554A/en unknown
- 1997-08-08 CO CO97045591A patent/CO4870708A1/es unknown
- 1997-08-08 AR ARP970103617A patent/AR009035A1/es not_active Application Discontinuation
- 1997-08-09 EG EG77997A patent/EG21365A/xx active
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020535251A (ja) * | 2017-09-29 | 2020-12-03 | サビック エスケー ネクスレン カンパニー ピーティーイー. エルティーディー.Sabic Sk Nexlene Company Pte. Ltd. | 新規のインデン系遷移金属化合物、これを含む遷移金属触媒組成物、およびこれを用いたエチレン単独重合体またはエチレンとα‐オレフィンとの共重合体の製造方法 |
| JP7177148B2 (ja) | 2017-09-29 | 2022-11-22 | サビック エスケー ネクスレン カンパニー ピーティーイー. エルティーディー. | 新規のインデン系遷移金属化合物、これを含む遷移金属触媒組成物、およびこれを用いたエチレン単独重合体またはエチレンとα‐オレフィンとの共重合体の製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| ID18004A (id) | 1998-02-19 |
| NO326005B1 (no) | 2008-09-01 |
| TR199900487T2 (xx) | 1999-06-21 |
| CN1114609C (zh) | 2003-07-16 |
| DE69730718T2 (de) | 2005-09-22 |
| HUP9902581A2 (hu) | 1999-11-29 |
| WO1998006727A1 (en) | 1998-02-19 |
| CA2262910C (en) | 2006-04-11 |
| CO4870708A1 (es) | 1999-12-27 |
| AR009035A1 (es) | 2000-03-08 |
| BR9711124A (pt) | 1999-09-28 |
| KR100528754B1 (ko) | 2006-01-09 |
| ES2224266T3 (es) | 2005-03-01 |
| EG21365A (en) | 2001-09-30 |
| TW455595B (en) | 2001-09-21 |
| HUP9902581A3 (en) | 2004-03-01 |
| US6268444B1 (en) | 2001-07-31 |
| JP3407074B2 (ja) | 2003-05-19 |
| EP0923589A1 (en) | 1999-06-23 |
| SK15399A3 (en) | 2000-04-10 |
| ATE276263T1 (de) | 2004-10-15 |
| NO990545L (no) | 1999-03-26 |
| CN1230190A (zh) | 1999-09-29 |
| NZ333878A (en) | 2000-08-25 |
| AU719500B2 (en) | 2000-05-11 |
| CZ42399A3 (cs) | 1999-07-14 |
| DE69730718D1 (de) | 2004-10-21 |
| CA2262910A1 (en) | 1998-02-19 |
| KR20000029833A (ko) | 2000-05-25 |
| AU4145697A (en) | 1998-03-06 |
| EP0923589B1 (en) | 2004-09-15 |
| NO990545D0 (no) | 1999-02-05 |
| MY132554A (en) | 2007-10-31 |
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