CN1032008C - 加聚催化剂的制备方法 - Google Patents
加聚催化剂的制备方法 Download PDFInfo
- Publication number
- CN1032008C CN1032008C CN91104485A CN91104485A CN1032008C CN 1032008 C CN1032008 C CN 1032008C CN 91104485 A CN91104485 A CN 91104485A CN 91104485 A CN91104485 A CN 91104485A CN 1032008 C CN1032008 C CN 1032008C
- Authority
- CN
- China
- Prior art keywords
- cyclopentadienyl
- alkyl
- zirconium
- metal
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000012644 addition polymerization Methods 0.000 title claims abstract description 12
- 239000002685 polymerization catalyst Substances 0.000 title claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 title description 11
- 230000004913 activation Effects 0.000 title description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 53
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000004678 hydrides Chemical group 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 claims abstract description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 56
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 230000000737 periodic effect Effects 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- FWUHUNUOUDQTFG-UHFFFAOYSA-N (3,4,5-trifluorophenoxy)boronic acid Chemical class OB(O)OC1=CC(F)=C(F)C(F)=C1 FWUHUNUOUDQTFG-UHFFFAOYSA-N 0.000 claims 1
- HFKJQIJFRMRSKM-UHFFFAOYSA-N [3,5-bis(trifluoromethyl)phenoxy]boronic acid Chemical class OB(O)OC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 HFKJQIJFRMRSKM-UHFFFAOYSA-N 0.000 claims 1
- 150000001450 anions Chemical class 0.000 abstract description 9
- 239000007800 oxidant agent Substances 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 6
- 150000001412 amines Chemical class 0.000 abstract description 5
- 125000002091 cationic group Chemical group 0.000 abstract description 3
- 230000002452 interceptive effect Effects 0.000 abstract description 3
- 125000001424 substituent group Chemical group 0.000 abstract description 3
- 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 abstract 1
- -1 lanthanide metal compound Chemical class 0.000 description 49
- 150000001875 compounds Chemical class 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 15
- 239000000178 monomer Substances 0.000 description 15
- 230000001976 improved effect Effects 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 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 10
- 150000002738 metalloids Chemical class 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052752 metalloid Inorganic materials 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- XIPFMBOWZXULIA-UHFFFAOYSA-N pivalamide Chemical compound CC(C)(C)C(N)=O XIPFMBOWZXULIA-UHFFFAOYSA-N 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- RQDMEYLMEMRZME-UHFFFAOYSA-N C=1C=CC=CC=1C[Zr]CC1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C[Zr]CC1=CC=CC=C1 RQDMEYLMEMRZME-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- ZRDHAWVFZDSFOW-UHFFFAOYSA-N methanidylbenzene;titanium(2+) Chemical compound [Ti+2].[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1 ZRDHAWVFZDSFOW-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000006884 silylation reaction Methods 0.000 description 3
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 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 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000001457 metallic cations Chemical class 0.000 description 2
- SIADVQHXJYEEAB-UHFFFAOYSA-N methanidylbenzene;titanium(3+) Chemical compound [Ti+3].[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1 SIADVQHXJYEEAB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 241000894007 species Species 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- VJTFBKZTQWRDKE-UHFFFAOYSA-N 2-methanidyl-2-methylpropane;titanium(4+) Chemical compound [Ti+4].CC(C)(C)[CH2-].CC(C)(C)[CH2-].CC(C)(C)[CH2-].CC(C)(C)[CH2-] VJTFBKZTQWRDKE-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N Acetylene Chemical group C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- GABVPFWMOLKWPV-UHFFFAOYSA-N C(=CC=CC)[Hf](C)C Chemical compound C(=CC=CC)[Hf](C)C GABVPFWMOLKWPV-UHFFFAOYSA-N 0.000 description 1
- CADYJHFTXAUABE-UHFFFAOYSA-N C(C)(C)O[Zr].C1(C=CC=C1)C1=C(C=CC=C1)C1=CC=CC=C1 Chemical compound C(C)(C)O[Zr].C1(C=CC=C1)C1=C(C=CC=C1)C1=CC=CC=C1 CADYJHFTXAUABE-UHFFFAOYSA-N 0.000 description 1
- HBOUWMKLSJVLEI-UHFFFAOYSA-N C(C)C=1C(=C(C(C=1)(CC)[Zr](CC1=CC=CC=C1)(CC1=CC=CC=C1)CC1=CC=CC=C1)CC)CC Chemical compound C(C)C=1C(=C(C(C=1)(CC)[Zr](CC1=CC=CC=C1)(CC1=CC=CC=C1)CC1=CC=CC=C1)CC)CC HBOUWMKLSJVLEI-UHFFFAOYSA-N 0.000 description 1
- ZRJVZVUQYMJULO-UHFFFAOYSA-N C(C1=CC=CC=C1)[Zr]CC1=CC=CC=C1.CCC Chemical compound C(C1=CC=CC=C1)[Zr]CC1=CC=CC=C1.CCC ZRJVZVUQYMJULO-UHFFFAOYSA-N 0.000 description 1
- JXWFFNQVHWCXFI-UHFFFAOYSA-N C(CCC)C1(C=CC=C1)[Ti](OCCCC)(C)C Chemical compound C(CCC)C1(C=CC=C1)[Ti](OCCCC)(C)C JXWFFNQVHWCXFI-UHFFFAOYSA-N 0.000 description 1
- QSMJPWFVPDYNCV-UHFFFAOYSA-N C([Zr](CC1=CC=CC=C1)C1C=CC2=CC=CC=C12)C1=CC=CC=C1 Chemical compound C([Zr](CC1=CC=CC=C1)C1C=CC2=CC=CC=C12)C1=CC=CC=C1 QSMJPWFVPDYNCV-UHFFFAOYSA-N 0.000 description 1
- QZRMMDZNYKGEFD-UHFFFAOYSA-N C1(=C(C=CC=C1)[Zr])C Chemical compound C1(=C(C=CC=C1)[Zr])C QZRMMDZNYKGEFD-UHFFFAOYSA-N 0.000 description 1
- ZDDDOQAFTDLCBT-UHFFFAOYSA-N C1(=CC=C(C=C1)C)[Zr] Chemical compound C1(=CC=C(C=C1)C)[Zr] ZDDDOQAFTDLCBT-UHFFFAOYSA-N 0.000 description 1
- YTZNVGDDHSTYSD-UHFFFAOYSA-N C1(=CC=CC=C1)C(C1=CC=CC=C1)[Zr] Chemical compound C1(=CC=CC=C1)C(C1=CC=CC=C1)[Zr] YTZNVGDDHSTYSD-UHFFFAOYSA-N 0.000 description 1
- HCUIAGUHWDFYHZ-UHFFFAOYSA-N C1(=CC=CC=C1)[Si](C)(C)[Zr] Chemical compound C1(=CC=CC=C1)[Si](C)(C)[Zr] HCUIAGUHWDFYHZ-UHFFFAOYSA-N 0.000 description 1
- TUJZUXQQNBRSRT-UHFFFAOYSA-N C1(C=CC=C1)[Ti](CC(C)(C)C)CC(C)(C)C Chemical compound C1(C=CC=C1)[Ti](CC(C)(C)C)CC(C)(C)C TUJZUXQQNBRSRT-UHFFFAOYSA-N 0.000 description 1
- RYPLBAFKYUPVNL-UHFFFAOYSA-N C1(CCCCC1)CC1(C=CC=C1)[Zr](CC1=CC=CC=C1)(CC1=CC=CC=C1)C1C=CC=C1 Chemical compound C1(CCCCC1)CC1(C=CC=C1)[Zr](CC1=CC=CC=C1)(CC1=CC=CC=C1)C1C=CC=C1 RYPLBAFKYUPVNL-UHFFFAOYSA-N 0.000 description 1
- ZMIATORLXUVUJO-UHFFFAOYSA-N C=1C=CC=CC=1C[Hf]CC1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C[Hf]CC1=CC=CC=C1 ZMIATORLXUVUJO-UHFFFAOYSA-N 0.000 description 1
- BOPSDEKAKVOVBM-UHFFFAOYSA-N C=1C=CC=CC=1C[Zr](C1C=CC=C1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C[Zr](C1C=CC=C1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 BOPSDEKAKVOVBM-UHFFFAOYSA-N 0.000 description 1
- IBVSPCYHSJJRBP-UHFFFAOYSA-N CC1=C(C)C(C)=C(C)C1(C)[Zr](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 Chemical compound CC1=C(C)C(C)=C(C)C1(C)[Zr](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 IBVSPCYHSJJRBP-UHFFFAOYSA-N 0.000 description 1
- AXQPJFRGCOYWIB-UHFFFAOYSA-N CCCC[Ti]CCCC Chemical compound CCCC[Ti]CCCC AXQPJFRGCOYWIB-UHFFFAOYSA-N 0.000 description 1
- UIDLAUCBDVKQJT-UHFFFAOYSA-N CN(C)C.[Zr+4] Chemical compound CN(C)C.[Zr+4] UIDLAUCBDVKQJT-UHFFFAOYSA-N 0.000 description 1
- AWRSKMDJAJASLT-UHFFFAOYSA-N C[Si](C)(C)C[Zr] Chemical compound C[Si](C)(C)C[Zr] AWRSKMDJAJASLT-UHFFFAOYSA-N 0.000 description 1
- AJYKXADOGHNGGB-UHFFFAOYSA-N C[Ti](C)(C1C=CC=C1)C1=CC=CC2=C1CC1=CC=CC=C21 Chemical compound C[Ti](C)(C1C=CC=C1)C1=CC=CC2=C1CC1=CC=CC=C21 AJYKXADOGHNGGB-UHFFFAOYSA-N 0.000 description 1
- COOXAWDWHWRVRD-UHFFFAOYSA-N C[Ti]C Chemical compound C[Ti]C COOXAWDWHWRVRD-UHFFFAOYSA-N 0.000 description 1
- HRCNWDPGYQRDAF-UHFFFAOYSA-N C[Zr]C1C=CC=C1 Chemical compound C[Zr]C1C=CC=C1 HRCNWDPGYQRDAF-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DBONNYQBNVXXTE-UHFFFAOYSA-N FC(F)(F)C1(C=CC=C1)[Zr](CC1=CC=CC=C1)(CC1=CC=CC=C1)CC1=CC=CC=C1 Chemical compound FC(F)(F)C1(C=CC=C1)[Zr](CC1=CC=CC=C1)(CC1=CC=CC=C1)CC1=CC=CC=C1 DBONNYQBNVXXTE-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BMGJLKOCMSRCEN-UHFFFAOYSA-N [Ti+4].C1(C=CC=C1)[N+](C)(C)C Chemical compound [Ti+4].C1(C=CC=C1)[N+](C)(C)C BMGJLKOCMSRCEN-UHFFFAOYSA-N 0.000 description 1
- FNNJDVNOXAXSDH-UHFFFAOYSA-N [Zr+4].C1(C=CC=C1)[N+](C)(C)C Chemical compound [Zr+4].C1(C=CC=C1)[N+](C)(C)C FNNJDVNOXAXSDH-UHFFFAOYSA-N 0.000 description 1
- RUMPJKFMCQWQCW-UHFFFAOYSA-N [Zr].C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Zr].C1(=CC=CC=C1)C1=CC=CC=C1 RUMPJKFMCQWQCW-UHFFFAOYSA-N 0.000 description 1
- LREUFPOQFXNWRE-UHFFFAOYSA-N [Zr].C1(C=CC=C1)C1=C(C=CC=C1)C1=CC=CC=C1 Chemical compound [Zr].C1(C=CC=C1)C1=C(C=CC=C1)C1=CC=CC=C1 LREUFPOQFXNWRE-UHFFFAOYSA-N 0.000 description 1
- ODFJOVXVLFUVNQ-UHFFFAOYSA-N acetarsol Chemical compound CC(=O)NC1=CC([As](O)(O)=O)=CC=C1O ODFJOVXVLFUVNQ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- DBDNZCBRIPTLJF-UHFFFAOYSA-N boron(1-) monohydride Chemical compound [BH-] DBDNZCBRIPTLJF-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- JQZUMFHYRULBEN-UHFFFAOYSA-N diethyl(methyl)silicon Chemical compound CC[Si](C)CC JQZUMFHYRULBEN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- QSLMQGXOMLSFAW-UHFFFAOYSA-N methanidylbenzene;zirconium(4+) Chemical compound [Zr+4].[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1 QSLMQGXOMLSFAW-UHFFFAOYSA-N 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- NOUWNNABOUGTDQ-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2+] NOUWNNABOUGTDQ-UHFFFAOYSA-N 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
-
- 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
- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61908—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
公开了一类无干扰性胺或膦副产物的式L1MX+A的加聚催化剂,其制备方法是用式(Ox+a)b(A-)d的氧化剂氧化式L1MX2的4族或镧系金属衍生物,其中各符号如说明书所定义。
Description
本发明涉及可用作催化剂物质的组合物,这些催化剂组合物的制备方法,和用这类组合物作为加聚催化剂的方法。更具体地说,本发明涉及催化剂组合物及其制备方法和用这些催化剂聚合烯烃、二烯烃和/或炔属不饱和单体的方法。
当然,用齐格勒-纳塔型催化剂聚合可加聚单体是本技术领域中公知的。一般来说,这些可溶性系统含4族或镧系金属化合物和金属烷基化物助催化剂,特别是烷基铝助催化剂。
EP-A-0277,004公开了某类二(环戊二烯基)金属化合物,它是通过二(环戊二烯基)金属配合物与含非配位相容阴离子的质子酸(Bronsted acid)盐反应形成的。该文献公开了这样的配合物可用作聚合烯烃的催化剂。上述EP-A-0277,004所述内容在此援引以供参考。
遗憾的是,现已发现按上述技术制得的催化剂受所含的副产物胺或由形成催化剂产生的膦化合物的不利影响。也就是说,EP-A-0277,004方法涉及金属化合物的配位体和质子酸盐的阳离子之间的不可逆反应。实际上,这种阳离子一般是在催化剂形成过程上由质子专移到配位体上形成叔胺或膦的三烷基铵或膦离子。这种胺或膦化合物因对加聚反应有抑制作用,所以是所得催化剂的不需要的组分。
如果提供一种能以只形成非干扰性和惰性副产物的方式而活化的加聚催化剂,则是很理想的。
美国化学学会杂志109,4111—413(1987)公开了一种通过d°有机金属化合物的一个电子氧化制备阳离子锆(IV)苄基配合物的方法。用于制备茂锆的溶剂是四氢呋喃或二氯甲烷,这两种物质均干扰所需催化剂的形成和(或)对后序烯烃聚合选成不利影响。另外,该文献使用了一种含四苯基硼酸根的氧化剂。现已发现,这种阴离子用于制备加聚催化剂的氧化活化法时是不能接受的。
现已发现,采用本发明的方法可以避免或至少可以降低现有技术的烯烃离子聚合催化剂的前述和其它缺点。另外,本发明提供了一种改进的催化剂活化工序和改进的加聚方法。所以,本发明一个目的是提供可用于聚合包括烯烃、二烯烃和/或炔属不饱和单体在内的可加聚单体的改进的离子催化剂系统。本发明的另一目的是提供这种改进的催化剂的制备方法。本发明的又一个目的是提供一种用这种改进的催化剂的改进的聚合方法。本发明的又一个目的是提供一种不形成干扰化合物的改进的催化剂。本发明最后一个目的是提供一种可更好地控制聚合产物分子量和分子量分布的改进的催化剂。
本发明提供一种可用于加聚反应的催化剂,这种催化剂基本上无胺付产物,其结构式如下:
LlMX+A-
其中:L各次出现相互无关地是一配位体或配位系,M是元素周期表4族金属或镧系金属;X是氢化物或具有20个以下的碳、硅或锗原子的烃基、甲硅烷基或甲锗烷基;l是大于或等于
优选M是元素周期表的4族金属,最优选是钛或锆。而且,优选X是氢化物或C1—C10烃基。
此外,本发明提供了一种制备上述加聚催化剂的方法,该方法包括使一种符合下式的4族金属或镧系金属的衍生物
LlMX2(式中L,l,M和X定义如上)与一种在还原态不干扰所得催化剂的氧化剂接触,所述氧化剂含有一种阳离子氧化剂和相容的非配位阴离子。
该氯化剂具有以下结构式:
(Ox+a)b(A-)d (I)其中:Ox +a是一种非质子酸、具有能氧化4族或镧系金属的衍生物的(+a)电荷的阳离子氧化剂,A-定义如前;以及b和d选自能提供电荷平衡的整数。
根据情况可在一种惰性稀释剂(如有机液)中使4族或镧系金属的衍生物与上述氧化剂接触而制取催化剂。
这里所用的元素周期表均指由CRC新闻有限公司1989年出版和具有版权的元素周期表。还有,所述族指的是采用IUPAC命名系统在元素周期表中反映的族。
术语“配位体或配位系”指的是辅助供电子或共享电子部分。这样的配位体包括阴离子配位体和中性供体配位体。
合适的阴离子的配位体的典型但非限制例有:R,-R′(OR′)mOR,(OR′)mOR,-PR2,-SR,-OR,-NR2氢化物和含14族元素的有机准金属基,其中在所述有机准金属的有机部分中所含的各烃基相互无关地含有1—20个碳原子。在这些配位体中:
R是烃基,甲硅烷基,甲锗烷基,或具有1—24个碳、硅或锗原子的取代的烃基、甲硅烷基或甲锗烷基;R′是C2-10亚烷基,以及m是整数0—10。
合适的中性供体配位体(L′)的典型但非限制例有:ROR,NR3,PR3和SR2,其中R定义如上。
这里所用的术语“阳离子氧化剂”指的是具有足以使4族金属或镧系金属衍生物分子氧化成催化物质的氧化电位的有机或无机离子。一般且优选衍生物的4族或镧系金属已是最高原子氧化态。本发明的方法包括分子氧化。大多数优选的阳离子氧化剂具有至少+0.20V,最好至少+0.25V的氧化电位。阳离子氧化剂不是质子酸。
这里所用的术语“相容的非配位阴离子”意指这样的阴离子,当它在本发明催化剂系统中起着电荷平衡阴离子的作用时不将其阴离子取代基或链段转移给任何阳离子物形成中性的4族或镧系金属的产物。“相容阴离子”是在催化剂的制备或使用过程中不降鲜成中性的阴离子。
这里所用的术语“准金属”包括那些显示出半金属特性的非金属,如硼、磷等等。
进一步优选的衍生物以式L″MX2表示,其中L″是将受限几何形状给与金属活性部位并含有20个以下的非氢原子的取代的环戊二烯基或类似的非定域П键基的衍生物,以及M和X定义如上。
这里所用的术语“受限几何形状”意指因环戊二烯基或取代的环戊二烯基上的一个或多个取代基形成了部分环状结构,金属原子被迫很大程度上露出活性金属,环状结构金属连到相邻的共价部分上并通过η5其它П键相互作用保持与环戊二烯基或取代二环戊二烯基缔合。可以理解,金属原子和环戊二烯基或取代的环戊二烯基的构原子之间的各个键不必是相同的。也就是说,金属可对称或不对称地П键合到环戊二烯或取代的环戊二烯基上。
以下进一步定义活性金属部位的几何形状。环戊二烯基或取代的环戊二烯基的重心可定义为构成环戊二烯基或取代的环戊二烯基原子中心的各X、Y和Z坐标的平均值。在环戊二烯基或取代的环戊二烯基的重心与金属配合物的相互配位体之间的金属中心处形成的角Q通过单一晶体X-射线衍射的标准技术容易地计算出。每个这样的角可依受限金属配合物的分子结构的不同而提高或降低。这样的配合物,即其中一个或多个角Q比类似相当的配合物(不同的只是氢取代了受限诱导取代基)中的小,具有本发明所要求的受限几何形状。与相当的配合物相比,优选一个或多个上述角Q降低至少5%,更优选降低7.5%。特别优选的是,所有键角的平均值也比相当的配合物中低。
本发明的4族金属或镧系金属的单环戊二烯基金属配位配合物最好具有受限几何结构,以便最小的角Q低于115℃,更好低于110℃,最佳低于105℃。
特别优选的衍生物化合物是下式I表示的单环戊二烯基化合物:其中:M是钛或锆;Cp *是以η5合方式键合到M上的环戊二烯基或取代的环戊二烯基;Z是含氧、硼或元素周期14族元素的二价部分;Y的含氮、磷、氧或硫的连接基,或Z和Y一起构成一稠合环系;以及X定义如前。
在分子氧化之后,本发明特别优选的催化剂由下式II表示:其中:Cp *,Z,M,X和A-定义如前。
环戊二烯基中的各碳原子可以被选自烃基、取代的烃基(其中一个或多个氢原子被卤素原子所取代)、烃取代的准金属基(其中准金属选自元素周期表14族元素)和卤素基团的相同或不同的基团取代或未取代。另外,两个或多个这样的取代基可一起构成稠合环系。可用于取代环戊二烯基中至少一个氢原子的合适的烃基和烃取代基含有1—20个碳原子,包括直链或支化烷基、环烃基、烷基取代的环烃基、芳基和烷基取代的芳基。合适的有机准金属基包括14族元素的一-,二-和三-取代的有机准金属基,其中各烃基含有1—20个碳原子。更具体地说,合适的有机准金属基包括三甲基甲硅烷基,三乙基甲硅烷基,乙基二甲基甲硅烷基,甲基二乙基甲硅烷基,三苯基甲锗烷基,三甲基甲锗烷基等等。
最优选的衍生物化合物是下式表示的酰氨基硅烷或酰氨基联二亚烷基(alkanediyl)化合物:其中;M是键合到η5-环戊二烯基上的钛或锆;R′每次出现相互无关地选自氢、具有10个以下碳或硅原子的甲硅烷基、烷基、芳基和它们的混合物;E是硅或碳;X每次出现相互无关地是氢化物、C10以下的烷基或芳基;和m是1或2。
上述最优选的金属的配位化合物的例子包括这样的化合物,其中酰氨基上的R′是甲基、乙基、丙基、戊基、己基(包括其异构体在内)、降冰片基、苄基、苯基等等;该环戊二烯基是环戊二烯基、茚基、四氢茚基、芴基、八氢芴基、等等;上述环戊二烯基上的R′每次出现分别是氢、甲基、乙基、丙基、丁基、戊基、己基(包括异构体在内)、降冰片基、苄基、等等;且X是甲基、新戊基、三甲基甲硅烷基、降冰片基、苄基、甲基苄基、苯基等等。具体化合物有(叔丁酰氨基)(四甲基η5-环戊二烯基)-1,2-联二亚乙基二甲基锆,(叔丁酰氨基)甲基-η5-环戊二烯基)-1,2-联二亚乙基二甲基苄基钛,(甲酰氨基)(四甲基-η5-环戊二烯基)-1,2-联二亚乙基二苯甲基锆,(甲酰氨基)(四甲基-η5-环戊二烯基)-1,2-联二亚乙基三辛基钛,(乙酰氨基)(四甲基-η5-环戊二烯基-亚甲基二苯基钛,(叔丁酰氨基)二苄基(四甲基-η5-环戊二烯基)硅烷二苄基锆,(苄酰氨基二甲基)(四甲基-η5-环戊二烯基)硅烷二(三甲基甲硅烷基)钛,以及(苯基磷酰基)二甲基(四甲基-η5-环戊二烯基)硅烷二苄基锆。
在最优选的方案中,-Z-Y-是具有10个以下非氢原子的酰氨基硅烷或酰氨基烷基,即:(叔丁酰氨基)(二甲基甲硅烷基),(叔丁酰氨基)-1-乙烷-2-基,等等。
可用于制备本发明改进的催化剂的衍生物化合物是无活性氢(除氢化物离去基X之外)或其中可能的活性氢被大的保护基保护住的共价键合的金属化合物。在这类金属衍生物化合物上合适的有机取代基有降冰片基,新戊基,三甲基甲硅烷基和二苯基甲基。合适的衍生物化合物的典型但非限制例有:四降冰片基钛,四苄基锆,四新戊基钛,二苯氧基二(三甲基甲硅烷基)锆,二(2,6-二异丙基-4-甲基)苯氧基二苄基钛,三(叔丁基硅氧基)三甲基锆,二甲氧基二苯甲基钛,二(2,4,6-三甲基苯氧基)二苄基钛,丁氧基三[(三甲基甲硅烷基)甲基]锆,二降冰片基二甲基钛,三苄基氢化钛等等;环戊二烯基和二(环戊二烯基)金属化合物,例如二(环戊二烯基)二甲基锆,环戊二烯基三苄基锆,环戊二烯基三甲基钛,环戊二烯基三甲基锆,二(环戊二烯基)二新戊基钛,环戊二烯基三(二苯基甲基)锆,二(环戊二烯基)二苯基锆,环戊二烯基三新戊基钛,二(环戊二烯基)二(间甲苯基)锆,二环戊二烯基二(对甲苯基)锆;烃基取代的环戊二烯基或二(环戊二烯基)化合物,例如五甲基环戊二烯基)-(环戊二烯基)二甲基锆,二(乙基环戊二烯基)二甲基锆,(五甲基环戊二烯基)三苄基锆,(正丁基环戊二烯基)三新戊基钛,环戊二烯基二甲基氢化钛,二(环戊二烯基)二(二苯基甲基)锆,二(叔丁基环戊二烯基)二(三甲基甲硅烷基甲基)锆,二(环已基环戊二烯基)二甲基锆,(苄基环戊二烯基)二(间甲苯基)甲基钛,(二苯基环戊二烯基)二降冰片基甲基锆,二甲基环戊二烯基)二苯基锆,(四乙基环戊二烯基)三苄基锆,(丙基环戊二烯基)(环戊二烯基)二甲基锆,二(丙基环戊二烯基)二甲基锆,(正丁基环戊二烯基)二甲基(正丁氧基)钛,环戊二烯基二苯基异丙氧基锆,(环已基甲基环戊二烯基)环戊二烯基二苄基锆,二[(环已基)甲基环戊二烯基]二苄基锆,二(环戊二烯基)二氢化锆,苄基环戊二烯基二甲基铪,二(茚基)二苄基锆,(叔丁酰氨基)二甲基(四甲基-η5-环戊二烯基硅烷二苄基锆,(苄酰氨基)二甲基(四乙基-η5-环戊二烯基)硅烷二丁基钛等等;金属烃基取代的环戊二烯基金属化合物,如[(三甲基甲硅烷基)环戊二烯基]三甲基锆,二[(三甲基甲锗烷基)环戊二烯基]二甲基钛,[(三甲基甲锡烷基)环戊二烯基]三苄基锆,[(五-三甲基甲硅烷基)环戊二烯基](环戊二烯基)二甲基锆,二[(三甲基甲硅烷基)环戊二烯基]二甲基锆,五[(三甲基甲硅烷基)环戊二烯基]三苄基钛,二[三甲基甲锗烷基)环戊二烯基]二苄基铪,卤代环戊二烯基化合物,如[三氟甲基)环戊二烯基](环戊二烯基)二甲基锆,二[(三氟甲基)环戊二烯基]二降冰片基锆,[(三氟甲基)环戊二烯基]三苄基锆;甲硅烷基取代的(环戊二烯基)金属化合物,如二(环戊二烯基)二(三甲基甲硅烷基)锆,环戊二烯基三(苯基二甲基甲硅烷基)锆;桥基环戊二烯基金属化合物,如亚甲基二[(环戊二烯基)二甲基锆],亚乙基-二[(环戊二烯基)二苄基锆],(二甲基亚甲硅烷基)-二-[(环戊二烯基)二甲基钛],亚甲基-二-(环戊二烯基)二(三甲基甲硅烷基)锆,(二甲基亚甲硅烷基)-二-(环戊二烯基二辛戊二烯基铪),亚乙基-二-(四氢茚基)二苄基锆和二甲基亚甲硅烷基(芴基)(环戊二烯基)二甲基钛。
当然,可应用于本发明催化剂组合物的其它化合物、特别是含有其它4族或镧系金属的化合物对于本技术领域专业人员来说是很明显的。在制备本发明化合物中可用作氧化剂的化合物包含一种阳离子氧化剂和前述一种或多种相容的非配位阴离子。
在优选方案中,前式(I)的A-c包括一种含多个亲油基的单一配位配合物,所述亲油基共价键合到并屏蔽住带有中心形成电荷的金属或准金属原子,其阴离子很大,在氧化条件和随后聚合条件下是稳定的,并与所得的含4族金属或镧系金属的催化剂相容且不与其发生配合。所用的阴离子只提供电荷平衡而不干扰O的氧化能力或所得催化剂的催化性质。能形成在本发明反应条件下稳定的配位配合物的任何金属或准金属均可包含在阴离子中。合适的金属包括但不局限层于铝、金和铂。合适的准金属包括但不限于硼、磷和硅。最优选含阴离子的氧化剂,包括含单一硼原子的配位配合物。
特别适用于制备本发明催化剂的含硼阴离子由以下通式表示:
[BX1X2X3X4]-其中:B是3价态硼;X1-X4是含6—20个碳或硅原子的相同或不同的非反应性有机或甲硅烷基。另外,两个或多个X1-X4可通过一稳定的桥基相互连接。优选X1-X4无活性氢部分。也就是说,这些基团无氢、只在非活性部位中含氢或含有足够的位阻来保护潜在的活性氢部位。X1-X4合适的基团的例子是含6-20个碳原子的全氟烃基,3,4,5-三氟苯基等等。
最优选的相容的非配位阴离子是四(五氟苯基)硼根(borate)。
本发明所用的合适的有机阳离子氯化剂包括二茂铁鎓离子,二茚基Fe(III)离子和取代的二茂铁的阳离子衍生物,以及类似的分子物。合适的金属阳离子氧化剂包括Ag+1,Pd+2,Pt+2,Hg+2,Hg2 +2,Ag+和Cu+。最优选的阳离子氧化剂是二茂铁鎓和Ag+1阳离子。
在制备本发明改进的催化剂中用的氧化剂的典型但非限制例是四(五氟苯基)硼化二茂铁,四-3,4,5-三氟苯基硼化金(I),四(五氟苯基)硼化银和四-3,5-双三氟甲基苯基硼化1,1-二甲基二茂铁。
可以列出类似的含有其它金属和准金属用作氯化剂的合适的化合物,但为了公开而列出这样的化合物是没有必要的。在这方面应指出,列出所有化合物不仅不能完全,而且从前面通式本领域专业人员很容易发现适用的其它硼化合物以及含有其它金属如准金属的有用的化合物。
不希望受任何具体操作理论的束缚,据信阳离子氧化剂使4族或镧系金属衍生物的分子氧化,在本方法中成为中性物。氧化的金属衍生物通过单分子脱除反应丢掉氢或烃基(·R)。两个或多个这样的烃基形成氢分子或式Rx的中性有机物(其中x是大于或等于2的整数)。这些付产物当然是中性的,不会干扰后面的聚合反应,而且还可从反应混合物中除掉。这种结果远比会形成胺或类似反应付产物的前面公知的催化剂活化法要好。
应指出,必须选择这两种用于制备活性催化剂的结合的化合物,以避免阴离子链段、特别是芳基转移到金属阳离子上形成催化惰性物。这可通过位阻,即在连接4族或镧系金属的基因上进行取代或在阴离子的芳碳原子上进行取代而实现。然后,含有例如全烃取代的环戊二烯基的4族金属和镧系金属化合物(第一种组分)可有效地与比第一种组分范围更宽的第二种化合物一起使用。但是,由于金属取代基的含量和尺寸下降,用含有更耐降解的阴离子的第二种化合物(例如在苯环的间位和/或对位上有取代基的化合物,得到了更有效的催化剂。使阴离子更耐降解的另一种方法是在阴离子中进行氟取代,特别是全氟取代。这样,含氟取代的稳定阴离子的第二种组分可与范围更宽的第一种组分一起便用。
一般来说,在-100℃-300℃的某一温度及在一种合适的溶剂中合并这两种组分可制取催化剂。
可使用这种催化剂聚合单独的或混合物形式的α-烯烃和/或C2-C18炔属不饱和单体和/或C4-C18二烯烃。催化剂也可用于聚合α-烯烃、二烯烃和/或炔属不饱单体与其它不饱和单体。一般来说,聚合可在本领域公知的齐格勒一纳塔型或Kaminsky—Sinn型聚合反应条件下进行,也就是说,温度为0—250℃,压力为大气压-1000大气压(100MPa)。需要的活,可采用悬浮液溶液、淤浆或其它工艺条件。可使用载体,但最好以均相方式使用催化剂。当然,如果直接将组分加到聚合工艺中而且在所述聚合工艺中使用合适的溶剂或稀释剂(包括浓缩单体在内),不用说催化剂系统将就地形成。但是,优先选择在加到聚合混合物之前,在合适的溶剂及单独步骤中形成催化剂。
如上所述,本发明改进的催化剂最好在一合适的溶剂如稀释剂中制备。合适的溶剂如稀释剂包括现有技术中公知的、能用作聚合烯烃、二烯烃和炔属不饱和单体的溶剂的任何溶剂。合适的溶剂包括直链和支链的烃,如异丁烷,丁烷、戊烷、己烷、庚烷、辛烷、以及它们的混合物,环烃或脂环烃,如环已烷、环庚烷、甲基环已烷、甲基环庚烷;全氟烃,如全氟C4-10烷和芳基和烷基取代的芳基化合物,如苯,甲苯和二甲苯。合适的溶剂还包括液体烯烃,它们可起着单体或共聚用单体的作用,其例子有乙烯、丙烯、丁二烯、环戊烯、1-己烯、3-甲基-1-戊烯、4-甲基-1-戊烯、1,4-已二烯、1-辛烯、1-癸烯、苯乙烯、二乙烯、二乙基苯、烯丙基苯和乙烯基甲苯(包括全部单独或混合物形式的异构体在内)。
据信,本发明活性催化剂物质含有一个金属中心,它仍保持阳离子性、不饱和性和具有与烯烃、二烯烃和炔属不饱和化合物反应的全属碳键。式A-的电荷平衡的阴离子残余也与该金属中心缔合。
按本发明方法形成的催化剂可保持在溶液中,或从溶剂中分出、隔离和贮藏,便于以后使用。如前指出,催化剂也可在聚合反应中就地加以制备,即将各组分加入到聚合反应器中,在此各组分接触和反应,得到本发明改进的催化剂。
4族金属或镧系金属化合物衍生物与所用的氧化剂的当量比优选为0.1∶1—10∶1,更优选为0.75∶1—2∶1,最佳1.0∶1.0。在大多数聚合反应中,催化剂与所用的可聚合化合物的当量比为10-12∶1—10-1∶1,更优选10∶1—10-3∶1。
某些本发明催化剂(特别是那些以单环戊二烯基取代的钛化合物为基础并结合含硼氧化剂的催化剂)的有利特点是,当本发明的催化剂用于单独共聚合α-烯烃类、或共聚合α-烯烯与二烯烃的混合物时,与用比较普通的齐格勒-纳塔型催化剂制得的共聚物相比,结合到共聚物中的较高分子量的烯烃或二烯烃的量显著提高。乙烯和较高级α-烯烃与前述本发明钛基催化剂反应的相对速率如此相似,以至在用本发明催化剂制得的共聚均中的单体分布可通过单体反应物之比得以控制。
按照本发明通常可聚合的“可加聚单体”的例子有烯属不饱和单体,炔属化合物,共轭或非共轭二烯烃,多烯,一氧化碳,等等。优选单体包括C2-10α-烯烃,特别是乙烯、丙烯、异丁烯、1-丁烯、1-己烯、4-甲基-1-戊烯和1-辛烯。其它优选单体包括苯乙烯、卤代-或烷基取代的苯乙烯,四氟乙烯,乙烯基苯并环丁烷和1,4-已二烯。
一般来说,可以选择催化剂,以便得到的聚合物产物中无某些微量的杂质,例如在用齐格勒纳塔型催化剂制得的聚合物中常见的铝、镁和氯化物。因此,用来发明催化剂制得的聚合物产物应具有比比较常用的、含金属烷基化物(如烷基铝)的齐格勒-纳塔型催化剂制得的聚合物更宽的应用范围。
在对本发明进行了介绍之后,以下用实施例进一步说明本发明,但这些实施例并不意味着限制本发明。所有份数和百分数均以重量计,除非另外注明。
实施例1
通过在50ml纯化脱气的甲苯中合并50毫摩尔二(环戊二烯基)二苄基锆和50毫摩尔全氟四苯基硼化二茂铁,制备催化剂混合物。搅拌混合物约30秒,直至放出蓝色二茂铁鎓。聚合反应
在4升反应器中,将催化剂与含有2升混合的烷烃溶剂(Isopar ETM,Exxon化学有限公司产)、75ml氢(于50psi,350kPa)和乙烯(31大气压,3.1MPa)的混合物合并。反应物预先脱气和纯化,并将反应器中的物料加热到170℃。加入10ml实施例1的催化剂。乙烯立即迅速地被摄取且反应器内的温度显著上升(乙烯摄取率高于每分钟100克,温度升高大于17℃)。反应10分钟后,将反应器中的物料取出并脱挥发份,得到46克高密度聚乙烯。
实施例2
往25ml脱气纯化的甲苯中加入25毫摩尔(叔丁酰氨基)二甲基(四甲基-η5-环戊二烯基)硅烷二苄基锆和25毫摩尔全氟四苯基硼化二茂铁。搅拌混合物约1分钟,直至排出蓝色固体二茂铁鎓。聚合反应
往4反应器中加入2升混合烷烃溶剂(IsoparETM)和300ml 1-辛烯,加热到150℃并用乙烯加压到31大气压(3.1MPa)。所有组分预先脱气和纯化。加入2ml上述催化剂溶液后乙烯立即迅速地被摄取,且反应器温度大幅度上升(乙烯摄取率为每分钟50克,温升26℃)。10分钟后,将反应器中的物料取出并脱挥发份,剩下78克乙烯/1-辛烯共聚物。根据物料衡算测定,聚合物的1-辛烯含量为7.5摩尔%。
实施例3
在5毫升甲苯中混合各为10毫摩尔的(叔丁酰氨基)二甲基(η5-2,3,4,5-四甲基环戊二烯基)硅烷二苄基钛和全氟四苯基硼化二茂铁,以制备催化剂溶液,搅拌30秒后,消耗了蓝色二茂铁并形成了褐绿色溶液。聚合反应
在130℃下将该催化剂溶液加到搅拌着的(500rpm)含Isopar-E(1000ml)、1-辛烯(200ml)、氢(于50psi下50ml,350kPa)和乙烯(于450psi下饱和,3MPa)的2升反应器中,从而温升了45℃。催化剂溶液加到反应器中10分钟后,从反应器中取出反应器内的物料,汽提挥发物,得到104克线型低密度聚乙烯。
实施例4
在5ml甲苯中,用各为10毫摩尔的全氟四苯基硼化二茂铁和2-(η5-环戊二烯基)-2-(η5-芴基)丙烷二苄基锆制备催化剂混合物。搅拌1分钟后,得到浅绿色溶液。聚合反应
在50℃下,将该催化剂溶液加到搅拌着的(500rpm)内含丙烯(200克)、Isopar-E(600ml)和1-苯烯(200ml)的反应器中。加入催化剂后温升了10℃,尽管-10℃的乙二醇/水混合物通过反应器内冷却盘管循环,仍维持了3分钟。30分钟后,取出反应器内的物料,脱挥发份,得到167克透明的橡胶状间规丙烯/1-辛烯共聚物。
Claims (7)
1.一种制备下式加聚催化剂的方法:
LlMX+A-其中:
L每次出现相互无关地是一配位体或配位体系;
M是元素周期表4族金属或镧系元素;
X是氢化物,至多20个碳、硅或锗原子的烃基、甲硅烷基或甲锗烷基,
l是大于或等于1的整数;以及
A-是四(五氟苯基)硼酸根、四(3,4,5—三氟苯基)硼酸根或四(3,5—双三氟甲基苯基)硼酸根,该方法包括使式LlMX2表示的4族或镧系金属衍生物(其中L,l,M和各X分别定义如上)与一种满足下式的氧化剂接触,
(Ox +a)b(A-)d其中:Ox +a是二茂铁鎓基或Ag+;A-定义如上;以及b和d选自能提供电荷平衡的整数。
2.根据权利要求1所述的方法,其中M是钛或锆。
3.根据权利要求1所述的方法,其中L是
a)一种选自R、-R′(OR′)mOR、(OR′)mOR、-PR2、-SR、-OR、-NR2、氢化物和含有一个14族元素的有机准金属基,其中有机准金属的有机部分中所含的各烃取代基相互无关地含有1—20个碳原子,其中
R是烃基,甲硅烷基,甲锗烷基或含1—24个碳、硅或锗原子的取代的烃基、甲硅烷基或甲锗烷基;
R′是C2-20亚烷基,以及
m是0—10的整数;或
b)一种选自ROR、NR3、PR3、和SR2的中性供体配位体,其中R定义如上。
5.根据权利要求4所述的方法,其中各X相互无关地为氢化物,至多C10的烷基或芳基;Y是NR′,且Z是(ER2′)m,其中E是硅或碳,各R′相互无关地是氢,含至多10个碳或硅原子的甲硅烷基、烷基、芳基或其组合。
6.根据权利要求4所述的方法,其中X是氢化物或C1—C10烃基。
7.根据权利要求6所述的方法,其中X是苄基。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US54771890A | 1990-07-03 | 1990-07-03 | |
US547,718 | 1990-07-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1057845A CN1057845A (zh) | 1992-01-15 |
CN1032008C true CN1032008C (zh) | 1996-06-12 |
Family
ID=24185852
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN91104485A Expired - Fee Related CN1032008C (zh) | 1990-07-03 | 1991-07-02 | 加聚催化剂的制备方法 |
Country Status (17)
Country | Link |
---|---|
US (1) | US5321106A (zh) |
EP (2) | EP0698618B1 (zh) |
JP (1) | JP2545006B2 (zh) |
KR (1) | KR100203235B1 (zh) |
CN (1) | CN1032008C (zh) |
AU (1) | AU651599B2 (zh) |
BR (1) | BR9102815A (zh) |
CA (1) | CA2046075C (zh) |
DE (2) | DE69133543T2 (zh) |
ES (2) | ES2267097T3 (zh) |
FI (1) | FI105559B (zh) |
MX (1) | MX9100063A (zh) |
MY (1) | MY108636A (zh) |
NO (1) | NO180720C (zh) |
RU (1) | RU2011652C1 (zh) |
SG (1) | SG52523A1 (zh) |
ZA (1) | ZA915114B (zh) |
Families Citing this family (377)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7163907B1 (en) * | 1987-01-30 | 2007-01-16 | Exxonmobil Chemical Patents Inc. | Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization |
US5384299A (en) * | 1987-01-30 | 1995-01-24 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
USRE37788E1 (en) * | 1987-01-30 | 2002-07-09 | Exxon Chemical Patents, Inc. | Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts |
US5198401A (en) * | 1987-01-30 | 1993-03-30 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
US5621126A (en) * | 1987-01-30 | 1997-04-15 | Exxon Chemical Patents Inc. | Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts |
US5264405A (en) | 1989-09-13 | 1993-11-23 | Exxon Chemical Patents Inc. | Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin-copolymer production catalysts |
US5763547A (en) * | 1992-10-02 | 1998-06-09 | The Dow Chemical Company | Supported catalyst complexes for olefin in polymerization |
US6825369B1 (en) * | 1989-09-14 | 2004-11-30 | The Dow Chemical Company | Metal complex compounds |
US5801113A (en) * | 1990-06-22 | 1998-09-01 | Exxon Chemical Patents, Inc. | Polymerization catalyst systems, their production and use |
US5272003A (en) * | 1990-10-26 | 1993-12-21 | Exxon Chemical Patents Inc. | Meso triad syndiotactic polypropylene fibers |
US5189192A (en) * | 1991-01-16 | 1993-02-23 | The Dow Chemical Company | Process for preparing addition polymerization catalysts via metal center oxidation |
GB9107378D0 (en) * | 1991-04-08 | 1991-05-22 | Ici Plc | Olefin polymerisation |
US6545088B1 (en) | 1991-12-30 | 2003-04-08 | Dow Global Technologies Inc. | Metallocene-catalyzed process for the manufacture of EP and EPDM polymers |
FR2688783A1 (fr) * | 1992-03-23 | 1993-09-24 | Rhone Poulenc Chimie | Nouveaux borates d'onium ou de complexe organometallique amorceurs cationiques de polymerisation. |
US6147184A (en) * | 1992-03-23 | 2000-11-14 | Rhone-Poulenc Chimie | Onium borates/borates of organometallic complexes and cationic initiation of polymerization therewith |
US5374696A (en) * | 1992-03-26 | 1994-12-20 | The Dow Chemical Company | Addition polymerization process using stabilized reduced metal catalysts |
US6143854A (en) | 1993-08-06 | 2000-11-07 | Exxon Chemical Patents, Inc. | Polymerization catalysts, their production and use |
JP3332051B2 (ja) * | 1992-12-18 | 2002-10-07 | 出光興産株式会社 | 重合用触媒及び該触媒系を用いる重合体の製造方法 |
GB9226905D0 (en) * | 1992-12-24 | 1993-02-17 | Wellcome Found | Pharmaceutical preparation |
FR2702485B1 (fr) * | 1993-03-10 | 1995-04-14 | Rhone Poulenc Chimie | Compositions à base de polyorganosiloxanes réticulables par voie cationique et leur utilisation dans le domaine de l'antiadhérence papier, de la protection des fibres optiques et des circuits imprimés. |
EP0629632B2 (en) * | 1993-06-07 | 2015-01-21 | Mitsui Chemicals, Inc. | Polypropylene |
CA2125246C (en) * | 1993-06-07 | 2001-07-03 | Junichi Imuta | Transition metal compound and olefin polymerization catalyst using the same |
US5470993A (en) * | 1993-06-24 | 1995-11-28 | The Dow Chemical Company | Titanium(II) or zirconium(II) complexes and addition polymerization catalysts therefrom |
US5514728A (en) * | 1993-07-23 | 1996-05-07 | Minnesota Mining And Manufacturing Company | Catalysts and initiators for polymerization |
US5455333A (en) * | 1993-08-16 | 1995-10-03 | Albemarle Corporation | Preparation of metallocenes |
US5504223A (en) * | 1994-01-25 | 1996-04-02 | The Dow Chemical Company | Synthesis of cyclopentadienyl metal coordination complexes from metal hydrocarbyloxides |
EP0704463B1 (en) * | 1994-04-11 | 1999-07-28 | Mitsui Chemicals, Inc. | Process for producing propylene polymer composition, and propylene polymer composition |
EP0704462B1 (en) * | 1994-04-11 | 1998-12-23 | Mitsui Chemicals, Inc. | Process for producing propylene polymer composition, and propylene polymer composition |
US6160066A (en) * | 1994-06-24 | 2000-12-12 | Exxon Chemical Patents, Inc. | Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts |
US5955625A (en) * | 1995-01-31 | 1999-09-21 | Exxon Chemical Patents Inc | Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts |
US5486632A (en) * | 1994-06-28 | 1996-01-23 | The Dow Chemical Company | Group 4 metal diene complexes and addition polymerization catalysts therefrom |
US5543480A (en) * | 1994-06-28 | 1996-08-06 | The Dow Chemical Company | Polymerization process using diene containing catalysts |
US5972822A (en) * | 1994-08-02 | 1999-10-26 | The Dow Chemical Company | Biscyclopentadienyldiene complex containing addition polymerization catalysts |
US6111020A (en) * | 1994-09-02 | 2000-08-29 | The Dow Chemical Company | Crosslinked foams from blends of ethylene vinyl acetate and ethylene-styrene interpolymers |
US5495036A (en) * | 1994-09-12 | 1996-02-27 | The Dow Chemical Company | Metal (III) complexes containing conjugated, non-aromatic anionic II-bound groups and addition polymerization catalysts therefrom |
US5541349A (en) * | 1994-09-12 | 1996-07-30 | The Dow Chemical Company | Metal complexes containing partially delocalized II-bound groups and addition polymerization catalysts therefrom |
TW369547B (en) | 1994-09-21 | 1999-09-11 | Mitsui Chemicals Inc | Olefin polymerization catalyst and process for olefin polymerization |
US5536797A (en) * | 1994-10-03 | 1996-07-16 | The Dow Chemical Company | Syndiotactic prochiral olefin polymerization process |
US7153909B2 (en) | 1994-11-17 | 2006-12-26 | Dow Global Technologies Inc. | High density ethylene homopolymers and blend compositions |
US5464906A (en) * | 1994-11-21 | 1995-11-07 | The Dow Chemical Company | Ethylene homopolymerization using group 3 metal complexes |
US5625015A (en) | 1994-11-23 | 1997-04-29 | Exxon Chemical Patents Inc. | Method for making supported catalyst systems and catalyst systems therefrom |
AU4198396A (en) * | 1994-11-23 | 1996-06-17 | Dow Chemical Company, The | Preparation of syndiotactic polyolefins from prochiral olefins |
US5512693A (en) * | 1994-12-07 | 1996-04-30 | The Dow Chemical Company | Preparation of titanium (II) or zirconium (II) complexes |
JP3375780B2 (ja) * | 1995-03-29 | 2003-02-10 | 三井化学株式会社 | 重包装袋用ポリエチレン樹脂組成物およびその組成物からなる重包装袋用ポリエチレン樹脂フィルム |
TW401445B (en) * | 1995-07-13 | 2000-08-11 | Mitsui Petrochemical Ind | Polyamide resin composition |
US6329478B1 (en) | 1995-07-14 | 2001-12-11 | Sumitmo Chemical Company, Limited | Transition metal complex, process for producing the same, olefin polymerization catalyst containing the transition metal complex and process for producing olefin polymers |
EP0852230B1 (en) * | 1995-08-31 | 2001-12-05 | Sumitomo Chemical Company Limited | Transition metal complexes, catalyst for olefin polymerization, and process for producing olefin polymers |
IT1276070B1 (it) | 1995-10-31 | 1997-10-24 | Siac It Additivi Carburanti | Processo per la preparazione di polimeri a base di etilene a basso peso molecolare |
AU717137B2 (en) * | 1995-11-24 | 2000-03-16 | Ciba Specialty Chemicals Holding Inc. | Borate coinitiators for photopolymerization |
US5854362A (en) * | 1995-12-11 | 1998-12-29 | The Dow Chemical Company | Supported biscyclopentadienyl metal complexes |
US6291695B1 (en) | 1996-02-20 | 2001-09-18 | Northwestern University | Organo-Lewis acids of enhanced utility, uses thereof, and products based thereon |
US6274752B1 (en) | 1996-02-20 | 2001-08-14 | Northwestern University | Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations |
US5856256A (en) * | 1996-02-20 | 1999-01-05 | Northwestern University | Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations |
IT1282666B1 (it) | 1996-02-22 | 1998-03-31 | Enichem Spa | Catalizzatore metallocenico sostituito per la (co) polimerizzazione delle olefine |
CA2248365A1 (en) * | 1996-05-07 | 1997-11-13 | The Dow Chemical Company | Improved syndiotactic vinylidene aromatic polymerization process |
JPH10152509A (ja) * | 1996-05-14 | 1998-06-09 | Mitsui Chem Inc | 気相重合方法及びそのための気相重合装置ならびにブロワー |
JPH09309926A (ja) | 1996-05-17 | 1997-12-02 | Dow Chem Co:The | エチレン共重合体の製造方法 |
US5811379A (en) * | 1996-06-17 | 1998-09-22 | Exxon Chemical Patents Inc. | Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof (PT-1267) |
JP2000513399A (ja) | 1996-06-17 | 2000-10-10 | エクソン・ケミカル・パテンツ・インク | オレフィン重合用の混合遷移金属触媒系 |
US6066603A (en) * | 1996-06-17 | 2000-05-23 | Exxon Chemical Patents Inc. | Polar monomer containing copolymers derived from olefins useful as lubricant and useful as lubricant and fuel oil additivies process for preparation of such copolymers and additives and use thereof |
EP0927187B1 (en) * | 1996-07-22 | 2002-12-04 | Dow Global Technologies Inc. | Metal complexes containing bridged, non-aromatic, anionic, dienyl groups and addition polymerization catalysts therefrom |
JP3407074B2 (ja) | 1996-08-08 | 2003-05-19 | ザ ダウ ケミカル カンパニー | 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 |
TW412560B (en) | 1996-09-04 | 2000-11-21 | Dow Chemical Co | Compositions and adhesives comprising a substantially random interpolymer of at least one vinylidene and at least one vinylidene aromatic monomer or hindered aliphatic vinylidene monomer, and coextruded or laminated multilayer film and tape |
WO1998010160A1 (en) | 1996-09-04 | 1998-03-12 | The Dow Chemical Company | Floor, wall or ceiling covering |
US6015868A (en) * | 1996-10-03 | 2000-01-18 | The Dow Chemical Company | Substituted indenyl containing metal complexes and olefin polymerization process |
US6812289B2 (en) | 1996-12-12 | 2004-11-02 | Dow Global Technologies Inc. | Cast stretch film of interpolymer compositions |
DE69733883T2 (de) | 1996-12-20 | 2006-06-01 | Sumitomo Chemical Co., Ltd. | Verfahren zur zugabe von borverbindungen |
WO1998030519A1 (en) | 1997-01-08 | 1998-07-16 | Hercules Incorporated | Solid acids as catalysts for the preparation of hydrocarbon resins |
KR100432537B1 (ko) | 1997-01-31 | 2004-08-16 | 미쓰이 가가쿠 가부시키가이샤 | 윤활유,윤활유조성물,연료유조성물 |
AR012582A1 (es) | 1997-04-14 | 2000-11-08 | Dow Global Technologies Inc | Composiciones polimericas de elongacion mejorada y formulaciones adhesivas de fusion en caliente que incluyen dicha composicion |
JP3817015B2 (ja) * | 1997-04-14 | 2006-08-30 | 三井化学株式会社 | 環状オレフィン系共重合体およびその用途 |
TW420693B (en) * | 1997-04-25 | 2001-02-01 | Mitsui Chemicals Inc | Olefin polymerization catalysts, transition metal compounds, and <alpha>-olefin/conjugated diene copolymers |
US6420507B1 (en) | 1997-05-01 | 2002-07-16 | The Dow Chemical Company | Olefin polymers prepared with substituted indenyl containing metal complexes |
US6319969B1 (en) | 1997-06-26 | 2001-11-20 | The Dow Chemical Company | Interpolymer compositions for use in sound management |
US6262161B1 (en) | 1997-06-26 | 2001-07-17 | The Dow Chemical Company | Compositions having improved ignition resistance |
US6172015B1 (en) | 1997-07-21 | 2001-01-09 | Exxon Chemical Patents, Inc | Polar monomer containing copolymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such copolymers and additives and use thereof |
KR20010022700A (ko) | 1997-08-08 | 2001-03-26 | 그래햄 이. 테일러 | 바닥, 벽 또는 천장 피복재로 사용하기에 적합한 시이트재, 및 그를 제조하기 위한 방법 및 중간체 |
US7232871B2 (en) | 1997-08-12 | 2007-06-19 | Exxonmobil Chemical Patents Inc. | Propylene ethylene polymers and production process |
US6635715B1 (en) | 1997-08-12 | 2003-10-21 | Sudhin Datta | Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers |
US6921794B2 (en) | 1997-08-12 | 2005-07-26 | Exxonmobil Chemical Patents Inc. | Blends made from propylene ethylene polymers |
JP2001515114A (ja) | 1997-08-15 | 2001-09-18 | ザ ダウ ケミカル カンパニー | 実質的に線状の均一なオレフィン重合体組成物から製造されるフィルム |
DE69807708T2 (de) | 1997-08-27 | 2003-01-02 | Dow Chemical Co | Elastomere mit verbesserter verarbeitbarkeit |
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 |
US6380294B1 (en) | 1997-10-17 | 2002-04-30 | The Dow Chemical Company | COMPOSITIONS OF INTERPOLYMERS OF α-OLEFIN MONOMERS WITH ONE OR MORE VINYL OR VINYLIDENE AROMATIC MONOMERS AND/OR ONE OR MORE HINDERED ALIPHATIC OR CYCLOALIPHATIC VINYL OR VINYLIDENE MONOMERS BLENDED WITH A CONDUCTIVE ADDITIVE |
TR200002404T2 (tr) | 1998-02-20 | 2001-01-22 | The Dow Chemical Company | Genişletilmiş anyonlar ihtiva eden katalizör etkinleştiriciler |
US6716786B1 (en) | 1998-02-20 | 2004-04-06 | The Dow Chemical Company | Supported catalyst comprising expanded anions |
US6699573B1 (en) | 1998-03-16 | 2004-03-02 | Dow Global Technologies Inc. | Liner compositions |
TW568829B (en) | 1998-03-26 | 2004-01-01 | Mitsui Chemicals Inc | Laminated film |
TW562810B (en) | 1998-04-16 | 2003-11-21 | Mitsui Chemicals Inc | Catalyst for olefinic polymerization and method for polymerizing olefine |
WO1999064239A1 (en) | 1998-06-12 | 1999-12-16 | Avery Dennison Corporation | Multilayered thermoplastic film and sign cutting method using the same |
JP2002519497A (ja) | 1998-07-01 | 2002-07-02 | エクソンモービル・ケミカル・パテンツ・インク | 結晶性プロピレンポリマーと結晶化可能プロピレンポリマーとを含んでなる弾性ブレンド |
US6403773B1 (en) | 1998-09-30 | 2002-06-11 | Exxon Mobil Chemical Patents Inc. | Cationic group 3 catalyst system |
AU1241600A (en) | 1998-11-02 | 2000-05-22 | Dupont Dow Elastomers L.L.C. | Shear thinning ethylene/alpha-olefin interpolymers and their preparation |
US6231795B1 (en) | 1998-12-04 | 2001-05-15 | The Dow Chemical Company | Soft and flexible foams made from blends of alkenyl aromatic polymers and alpha-olefin/vinyl or vinylidene aromatic and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymers |
US6048909A (en) * | 1998-12-04 | 2000-04-11 | The Dow Chemical Company | Foams having increased heat distortion temperature made from blends of alkenyl aromatic polymers and alpha-olefin/vinyl or vinylidene aromatic and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymers |
US6187232B1 (en) | 1998-12-04 | 2001-02-13 | The Dow Chemical Company | Acoustical insulation foams |
US5993707A (en) * | 1998-12-04 | 1999-11-30 | The Dow Chemical Company | Enlarged cell size foams made from blends of alkenyl aromatic polymers and alpha-olefin/vinyl or vinylidene aromatic and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymers |
BR9916964A (pt) | 1998-12-08 | 2002-05-28 | Dow Chemical Co | Fibras de polipropileno/etileno ligável por fusão, composição para produzì-la, método para melhorar sua resistência de ligação e processo para produzì-la |
TW576843B (en) | 1998-12-25 | 2004-02-21 | Mitsui Chemicals Inc | Olefin polymerization catalyst and process for olefin polymerization using the olefin polymerization catalyst |
US6632885B2 (en) | 1999-04-13 | 2003-10-14 | Mitsui Chemicals, Inc. | Soft syndiotactic polypropylene composition and molded product |
US6339134B1 (en) | 1999-05-06 | 2002-01-15 | Univation Technologies, Llc | Polymerization process for producing easier processing polymers |
AU3632400A (en) | 1999-05-13 | 2000-12-05 | Dow Chemical Company, The | Metal complexes containing bridging heteroatom for olefin-polymerization-process |
CA2368111A1 (en) | 1999-05-13 | 2000-11-23 | The Dow Chemical Company | Di- and tri-heteroatom substituted indenyl metal complexes |
JP3808243B2 (ja) | 1999-07-27 | 2006-08-09 | 三井化学株式会社 | 軟質樹脂組成物 |
US6331597B1 (en) | 1999-08-09 | 2001-12-18 | The Dow Chemical Company | Azidosilane-modified, moisture-curable polyolefin polymers, process for making, and articles obtained therefrom |
US6362270B1 (en) | 1999-08-12 | 2002-03-26 | The Dow Chemical Company | Thermoplastic compositions for durable goods applications |
US6524702B1 (en) | 1999-08-12 | 2003-02-25 | Dow Global Technologies Inc. | Electrical devices having polymeric members |
WO2001012716A2 (en) | 1999-08-17 | 2001-02-22 | The Dow Chemical Company | Free-flowing polymer composition |
US6559090B1 (en) | 1999-11-01 | 2003-05-06 | W. R. Grace & Co.-Conn. | Metallocene and constrained geometry catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation |
US6399535B1 (en) | 1999-11-01 | 2002-06-04 | W. R. Grace & Co.-Conn. | Coordination catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation |
ES2379243T3 (es) | 1999-12-10 | 2012-04-24 | Dow Global Technologies Llc | Complejos de metal del grupo 4 sustituidos, catalizadores y procedimiento de polimerización de olefinas |
US6281306B1 (en) | 1999-12-16 | 2001-08-28 | Univation Technologies, Llc | Method of polymerization |
WO2001051547A1 (en) | 2000-01-07 | 2001-07-19 | Dow Global Technologies Inc. | Thermoformable ethylene/styrene interpolymer-based polymer blend film for three-dimensional transfer finish foil |
CN1188435C (zh) | 2000-01-26 | 2005-02-09 | 三井化学株式会社 | 烯烃聚合物、其制备方法和含它的模塑产品 |
DE60108619T2 (de) * | 2000-03-01 | 2006-05-11 | Shell Internationale Research Maatschappij B.V. | Selektive, katalytische und thermische funktionalisierung von sekundären oder aromatischen c-h bindungen in zyklischen kohlenwasserstoffen |
US6451937B1 (en) | 2000-03-01 | 2002-09-17 | Shell Oil Company | Selective, catalytic, thermal functionalization of primary C-H hydrocarbon bonds |
US6160029A (en) * | 2000-03-08 | 2000-12-12 | The Dow Chemical Company | Olefin polymer and α-olefin/vinyl or α-olefin/vinylidene interpolymer blend foams |
US6649671B2 (en) | 2000-03-13 | 2003-11-18 | Dow Global Technologies Inc. | Concrete and process to make same |
WO2001074920A1 (fr) | 2000-03-31 | 2001-10-11 | Mitsui Chemicals, Inc. | Procedes de production d'une composition de polyolefine |
WO2002002577A1 (en) | 2000-06-30 | 2002-01-10 | Dow Global Technology Inc. | Polycyclic, fused ring compounds, metal complexes and polymerization process |
US6806327B2 (en) | 2000-06-30 | 2004-10-19 | Dow Global Technologies Inc. | Substituted polycyclic, fused ring compounds, metal complexes and polymerization process |
JP2002020417A (ja) | 2000-07-04 | 2002-01-23 | Mitsui Chemicals Inc | オレフィンの重合方法 |
KR100443766B1 (ko) * | 2000-07-04 | 2004-08-09 | 미쓰이 가가쿠 가부시키가이샤 | 극성올레핀 공중합체의 제조방법 및 이 방법에 의하여얻어진 극성올레핀 공중합체 |
US6627573B2 (en) | 2000-07-20 | 2003-09-30 | The Dow Chemical Company | Expanded anionic compounds comprising hydroxyl or quiescent reactive functionality and catalyst activators therefrom |
BR0112607A (pt) | 2000-07-20 | 2003-06-10 | Dow Global Technologies Inc | Composições de espuma a partir de uma mescla de polìmeros aromáticos alquenìlicos e interpolìmeros aromáticos alfa-olefìnicos/vinìlicos ou vinilidênicos |
KR100467277B1 (ko) | 2000-07-26 | 2005-01-24 | 미쓰이 가가쿠 가부시키가이샤 | 분기형 폴리올레핀 및 그 제조방법 |
ES2276731T3 (es) * | 2000-09-07 | 2007-07-01 | Mitsui Chemicals, Inc. | Copolimero de olefina que contiene un grupo polar, procedimiento para preparar el mismo, composicion de resina termoplastica que contiene el copolimero y usos de los mismos. |
US6943133B2 (en) * | 2000-10-20 | 2005-09-13 | Univation Technologies, Llc | Diene functionalized catalyst supports and supported catalyst compositions |
KR100844062B1 (ko) | 2001-02-21 | 2008-07-07 | 미쓰이 가가쿠 가부시키가이샤 | 올레핀 중합용 촉매 및 이 촉매를 사용하는 올레핀중합체의 제조방법 |
WO2002068529A2 (en) * | 2001-02-27 | 2002-09-06 | Dow Global Technologies Inc. | Fabricated articles prepared from blends of substantially random ethylene/propylene/vinyl aromatic interpolymers with polypropylene |
EP1390417B1 (en) | 2001-04-12 | 2010-10-20 | ExxonMobil Chemical Patents Inc. | Process for polymerizing propylene and ethylene in solution |
US6943224B2 (en) | 2001-04-30 | 2005-09-13 | W. R. Grace & Co.-Conn. | Process for preparing supported transition metal catalyst systems and catalyst systems prepared thereby |
US6927261B2 (en) | 2001-04-30 | 2005-08-09 | W. R. Grace & Co.-Conn. | Method of making supported transition metal polymerization catalysts and compositions formed therefrom |
KR100893971B1 (ko) | 2001-04-30 | 2009-04-20 | 더블유.알. 그레이스 앤드 캄파니-콘. | 지지된 이중 전이금속 촉매 시스템 |
WO2002102859A2 (en) | 2001-04-30 | 2002-12-27 | W. R. Grace & Co.-Conn. | Coordination catalyst systems employing chromium support-agglomerate and method of their preparation |
KR100628620B1 (ko) | 2001-04-30 | 2006-09-26 | 더블유.알. 그레이스 앤드 캄파니-콘. | 이종 크롬 촉매 및 이를 사용하는 올레핀의 중합 방법 |
CN1518561A (zh) * | 2001-05-04 | 2004-08-04 | 通过使用金属络合物催化剂所制造的无规或嵌段共聚物或三元聚合物 | |
WO2002092610A1 (en) * | 2001-05-14 | 2002-11-21 | Dow Global Technologies Inc. | 3-aryl-substituted cyclopentadienyl metal complexes and polymerization process |
US6946531B2 (en) * | 2001-05-14 | 2005-09-20 | Dow Global Technologies Inc. | Low molecular weight ethylene interpolymers and polymerization process |
US7193024B2 (en) * | 2001-06-15 | 2007-03-20 | Dow Global Technology Inc. | Alpha-Olefin based branched polymer |
JP2004536871A (ja) * | 2001-07-23 | 2004-12-09 | ダウ グローバル テクノロジーズ インコーポレイティド | ルイス酸/酸付加体の塩、およびそれより得られる触媒活性化剤 |
US6953501B2 (en) | 2001-08-10 | 2005-10-11 | Inventions & Discoveries, Llc | Wood treatment composition and method of use |
MY139205A (en) | 2001-08-31 | 2009-08-28 | Pennzoil Quaker State Co | Synthesis of poly-alpha olefin and use thereof |
KR20050034609A (ko) * | 2001-10-12 | 2005-04-14 | 다우 글로벌 테크놀로지스 인크. | 금속 착물 조성물 및 폴리디엔을 제조하기 위한촉매로서의 이의 용도 |
US6927256B2 (en) * | 2001-11-06 | 2005-08-09 | Dow Global Technologies Inc. | Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agent |
JP2005508415A (ja) | 2001-11-06 | 2005-03-31 | ダウ グローバル テクノロジーズ インコーポレイティド | アイソタクチックプロピレンコポリマー類、その製法および用途 |
US6943215B2 (en) | 2001-11-06 | 2005-09-13 | Dow Global Technologies Inc. | Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers |
JP2005515277A (ja) | 2002-01-22 | 2005-05-26 | ダウ グローバル テクノロジーズ インコーポレーテッド | 高い溶融流動性をもつビニル芳香族ポリマー |
US20040106739A1 (en) * | 2002-02-19 | 2004-06-03 | Cheung Yunwa Wilson | Blends of substantially random interpolymers with enhanced thermal performance |
AU2003216477A1 (en) * | 2002-03-14 | 2003-09-29 | Dow Global Technologies Inc. | Polycyclic, fused heteroring compounds, metal complexes and polymerization process |
JP4624679B2 (ja) * | 2002-03-14 | 2011-02-02 | ダウ グローバル テクノロジーズ インコーポレイティド | 置換インデニル金属錯体及び重合方法 |
EP2511305B1 (en) | 2002-09-27 | 2019-05-29 | Mitsui Chemicals, Inc. | Bridged metallocene compound for olefin polymerization and method of polymerizing olefin using the same |
US7795365B2 (en) | 2002-10-02 | 2010-09-14 | Dow Global Technologies Inc. | Liquid and gel-like low molecular weight ethylene polymers |
US7223822B2 (en) | 2002-10-15 | 2007-05-29 | Exxonmobil Chemical Patents Inc. | Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom |
CA2499951C (en) | 2002-10-15 | 2013-05-28 | Peijun Jiang | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
DE60322410D1 (de) | 2002-10-17 | 2008-09-04 | Dow Global Technologies Inc | Hochgefüllte polymerzusammensetzungen |
US7253132B2 (en) | 2002-10-23 | 2007-08-07 | Mitsui Chemicals, Inc. | Magnesium-containing carrier components and application thereof to olefin polymerization |
DE10251513A1 (de) * | 2002-11-04 | 2004-05-19 | Basf Ag | Übergangsmetallkatalysatoren für (Co)Polymerisation von olefinischen Monomeren |
ES2427626T3 (es) * | 2003-02-21 | 2013-10-31 | Styron Europe Gmbh | Procedimiento para homo- o copolimerización de olefinas conjugadas |
JP4742221B2 (ja) | 2003-03-21 | 2011-08-10 | ダウ グローバル テクノロジーズ エルエルシー | モルホロジー制御オレフィン重合プロセス |
US7084219B2 (en) * | 2003-03-25 | 2006-08-01 | Sumitomo Chemical Company, Limited | Contact product, and catalyst component and catalyst for addition polymerization, and process for producing addition polymer |
KR101004338B1 (ko) | 2003-03-28 | 2010-12-28 | 미쓰이 가가쿠 가부시키가이샤 | 프로필렌/1―부텐 공중합체, 폴리프로필렌 조성물 및 그 용도, 및 폴리프로필렌 복합 필름 |
FI20030610A0 (fi) * | 2003-04-22 | 2003-04-22 | Raisio Benecol Oy | Syötävä tuote |
US6927264B2 (en) * | 2003-05-28 | 2005-08-09 | Dow Global Technologies Inc. | Metal complexes and polymerization process using same |
JP4090389B2 (ja) * | 2003-06-10 | 2008-05-28 | 株式会社日立製作所 | 核磁気共鳴装置 |
ATE455832T1 (de) | 2003-08-19 | 2010-02-15 | Dow Global Technologies Inc | Interpolymere zur verwendung für schmelzklebstoffe und verfahren zu ihrer herstellung |
US20070073012A1 (en) * | 2005-09-28 | 2007-03-29 | Pannell Richard B | Method for seed bed treatment before a polymerization reaction |
US7985811B2 (en) * | 2004-01-02 | 2011-07-26 | Univation Technologies, Llc | Method for controlling sheeting in gas phase reactors |
US20050148742A1 (en) * | 2004-01-02 | 2005-07-07 | Hagerty Robert O. | Method for controlling sheeting in gas phase reactors |
DE602005017243D1 (de) | 2004-01-28 | 2009-12-03 | Idemitsu Kosan Co | Inpolymerisierung |
AU2005224257B2 (en) | 2004-03-17 | 2010-08-19 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for higher olefin multi-block copolymer formation |
RU2381240C2 (ru) | 2004-03-17 | 2010-02-10 | Дау Глобал Текнолоджиз Инк. | Состав катализатора, содержащий челночный агент, для формирования мульти-блок-сополимера этилена |
MXPA06010485A (es) | 2004-03-17 | 2006-12-19 | Dow Global Technologies Inc | Composicion catalizadora que comprende agente de enlace para la formacion de copolimeros de etileno. |
CN103102442B (zh) * | 2004-06-16 | 2016-01-20 | 陶氏环球技术有限责任公司 | 选择聚合改性剂的方法 |
WO2006004750A1 (en) * | 2004-06-28 | 2006-01-12 | Dow Global Technoligies Inc. | Adhesion promoters for multistrucural laminates |
WO2006020624A1 (en) * | 2004-08-09 | 2006-02-23 | Dow Global Technologies Inc. | Supported bis(hydroxyarylaryloxy) catalysts for manufacture of polymers |
KR20090027745A (ko) | 2004-08-27 | 2009-03-17 | 미쓰이 가가쿠 가부시키가이샤 | 올레핀 중합용 촉매 |
WO2006049857A1 (en) | 2004-10-28 | 2006-05-11 | Dow Global Technologies Inc. | Method of controlling a polymerization reactor |
KR20070085713A (ko) * | 2004-11-05 | 2007-08-27 | 다우 글로벌 테크놀로지스 인크. | 고용해성 페로세닐 화합물 |
EP1661921B1 (en) | 2004-11-26 | 2019-07-17 | Mitsui Chemicals, Inc. | Synthetic lubricating oil and lubricating oil composition thereof |
US20080038498A1 (en) * | 2004-12-22 | 2008-02-14 | Keita Itakura | Propylene Polymer, Composition Comprising the Polymer, and Molded Product Obtained Therefrom |
ZA200708784B (en) | 2005-03-17 | 2009-01-28 | Dow Global Technologies Inc | Catalyst composition comprising shuttling agent for tactic/atactic multi-block copolymer formation |
EP1861438B1 (en) * | 2005-03-17 | 2015-03-04 | Dow Global Technologies LLC | Catalyst composition comprising shuttling agent for regio-irregular multi-block copolymer formation |
US9410009B2 (en) | 2005-03-17 | 2016-08-09 | Dow Global Technologies Llc | Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation |
JP5438256B2 (ja) | 2006-11-17 | 2014-03-12 | 三井化学株式会社 | ポリプロピレン系樹脂フィルムおよびその用途 |
TWI391405B (zh) | 2005-05-18 | 2013-04-01 | Mitsui Chemicals Inc | 丙烯系聚合體、丙烯系聚合體組成物及該等之用途 |
JP5551360B2 (ja) | 2005-07-11 | 2014-07-16 | ダウ グローバル テクノロジーズ エルエルシー | シラングラフトオレフィンポリマー、それらから調製される組成物および物品、ならびにそれらの製造方法 |
WO2007035492A1 (en) | 2005-09-15 | 2007-03-29 | Dow Global Technologies Inc. | Catalytic olefin block copolymers via polymerizable shuttling agent |
WO2007035493A2 (en) * | 2005-09-15 | 2007-03-29 | Dow Global Technologies Inc. | Control of polymer architecture and molecular weight distribution via multi-centered shuttling agent |
US20070082998A1 (en) * | 2005-10-07 | 2007-04-12 | Mitsui Chemicals, Inc. | Process for producing injection molded product |
US20070225423A1 (en) * | 2005-10-07 | 2007-09-27 | Mitsui Chemicals, Inc. | Process for producing blow molded product by blow molding |
US20070080483A1 (en) * | 2005-10-07 | 2007-04-12 | Mitsui Chemicals, Inc. | Process for producing injection molded product |
US20070100056A1 (en) * | 2005-10-31 | 2007-05-03 | Mitsui Chemicals, Inc. | Process for producing thermoplastic resin composition |
US7605208B2 (en) * | 2005-10-31 | 2009-10-20 | Mitsui Chemicals, Inc. | Process for producing thermoplastic resin composition |
US8153243B2 (en) | 2005-12-09 | 2012-04-10 | Dow Global Technologies Llc | Interpolymers suitable for multilayer films |
EP1803747A1 (en) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films |
KR20080094722A (ko) * | 2006-02-15 | 2008-10-23 | 미쓰이 가가쿠 가부시키가이샤 | 에틸렌계 수지 및 그것으로 이루어지는 블로우 성형체 |
US20090036584A1 (en) * | 2006-02-15 | 2009-02-05 | Mitsui Chemicals, Inc. | Environmental Stress Cracking Resistance Improver, and Resin Composition With Improved Environmental Stress Cracking Resistance Properties Containing the Same |
US20090127751A1 (en) | 2006-03-10 | 2009-05-21 | Mitsui Chemicals, Inc. | Process for Producing Molded Product by Inflation Molding |
EP2006071B1 (en) | 2006-03-27 | 2012-02-22 | Mitsui Chemicals, Inc. | Process for producing shaped article by t-die molding |
JP2007261201A (ja) | 2006-03-29 | 2007-10-11 | Mitsui Chemicals Inc | ブロー成形による成形体の製造方法 |
WO2007114009A1 (ja) | 2006-03-30 | 2007-10-11 | Mitsui Chemicals, Inc. | 射出成形による成形体の製造方法 |
CN104725535A (zh) | 2006-05-17 | 2015-06-24 | 陶氏环球技术有限责任公司 | 高效溶液聚合法 |
CN109320664A (zh) | 2006-06-15 | 2019-02-12 | 陶氏环球技术有限责任公司 | 官能化烯烃共聚体、组合物和由其制成的制品及其制法 |
WO2008016059A1 (fr) | 2006-07-31 | 2008-02-07 | Mitsui Chemicals, Inc. | Film ou stratifié comprenant une résine d'éthylène ou une composition de résine d'éthylène |
US8101684B2 (en) | 2006-07-31 | 2012-01-24 | Mitsui Chemicals, Inc. | Thermoplastic resin composition for sealing solar cell, sheet for sealing solar cell and solar cell |
EP2075268B1 (en) | 2006-10-20 | 2015-07-08 | Mitsui Chemicals, Inc. | Copolymer, lubricating oil viscosity modifier, and lubricating oil composition |
US7863368B2 (en) * | 2006-11-17 | 2011-01-04 | Mitsui Chemicals, Inc. | Propylene resin composition, process for producing propylene resin composition, propylene polymer composition, shaped article produced of the propylene resin composition, and electric wire |
CN101541843B (zh) * | 2006-11-17 | 2011-05-04 | 三井化学株式会社 | 间规丙烯类聚合物的制造方法 |
KR101160383B1 (ko) | 2006-12-19 | 2012-06-27 | 미쓰이 가가쿠 가부시키가이샤 | 올레핀 중합용 고체상 촉매, 올레핀 중합 방법 및 상기 중합 방법에 의해 얻어지는 올레핀 중합체 입자 |
KR101128130B1 (ko) | 2007-01-16 | 2012-03-22 | 미쓰이 가가쿠 가부시키가이샤 | 중공 성형체용 에틸렌계 수지 조성물 및 그것으로 이루어지는 중공 성형체 |
ITMI20070878A1 (it) | 2007-05-02 | 2008-11-03 | Dow Global Technologies Inc | Processo per la polimerizzazine di polimeri tattici con l'uso di catalizzatori chirali |
ITMI20070877A1 (it) | 2007-05-02 | 2008-11-03 | Dow Global Technologies Inc | Processo per la produzione di copolimeri a blocchi multipli con l'utilizzo di solventi polari |
CN101679702B (zh) | 2007-06-14 | 2012-07-04 | 三井化学株式会社 | 热塑性弹性体组合物 |
JP5226973B2 (ja) | 2007-06-15 | 2013-07-03 | 三井化学株式会社 | エチレン系共重合体、該共重合体を含む組成物ならびにその用途 |
JP5126993B2 (ja) * | 2007-07-04 | 2013-01-23 | 三井化学株式会社 | 遷移金属錯体化合物、該化合物を含むオレフィン多量化用触媒および該触媒存在下で行うオレフィン多量体の製造方法 |
TW200932762A (en) | 2007-10-22 | 2009-08-01 | Univation Tech Llc | Polyethylene compositions having improved properties |
KR20100076056A (ko) | 2007-11-19 | 2010-07-05 | 미쓰이 가가쿠 가부시키가이샤 | 가교 메탈로센 화합물 및 그것을 사용한 올레핀 중합용 촉매, 및 상기 촉매를 사용하여 얻어지는 에틸렌계 중합체 |
ES2407121T3 (es) | 2007-12-18 | 2013-06-11 | Univation Technologies, Llc | Método para controlar la actividad de un catalizador bimodal durante una polimerización |
US8459525B2 (en) | 2008-02-14 | 2013-06-11 | Ethicon Endo-Sugery, Inc. | Motorized surgical cutting and fastening instrument having a magnetic drive train torque limiting device |
JP5473898B2 (ja) * | 2008-03-27 | 2014-04-16 | 三井化学株式会社 | 樹脂組成物およびその用途 |
EP2270089B1 (en) | 2008-03-31 | 2013-05-01 | Mitsui Chemicals, Inc. | Resin composition and meltable bag |
WO2010021304A1 (ja) * | 2008-08-19 | 2010-02-25 | 三井化学株式会社 | 混合触媒によるオレフィン重合体の製造方法 |
EP2172490A1 (en) | 2008-10-03 | 2010-04-07 | Ineos Europe Limited | Controlled polymerisation process |
JP5789195B2 (ja) | 2008-12-08 | 2015-10-07 | シリコンバレー メディカル インスツルメンツ インコーポレイテッド | 画像誘導のためのカテーテルのシステム |
CN102421807B (zh) | 2009-03-06 | 2015-03-18 | 陶氏环球技术有限责任公司 | 催化剂、制备催化剂的方法、制备聚烯烃组合物的方法和聚烯烃组合物 |
SG174602A1 (en) | 2009-03-30 | 2011-11-28 | Mitsui Chemicals Inc | Copolymer of olefin and conjugated diene, and process for producing same |
SG175292A1 (en) | 2009-04-21 | 2011-11-28 | Mitsui Chemicals Inc | Method for producing olefin polymer |
JP2012529507A (ja) | 2009-06-11 | 2012-11-22 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | アルミノキサンの製造方法及びかくして製造されるアルミノキサンを含んでなる触媒 |
US8318874B2 (en) | 2009-06-26 | 2012-11-27 | Dow Global Technologies Llc | Process of selectively polymerizing ethylene and catalyst therefor |
CN102471352A (zh) | 2009-07-01 | 2012-05-23 | 三井化学株式会社 | 有机金属化合物及其制造方法 |
CN102471393B (zh) | 2009-07-29 | 2013-12-04 | 陶氏环球技术有限责任公司 | 多功能链穿梭剂 |
WO2011016992A2 (en) | 2009-07-29 | 2011-02-10 | Dow Global Technologies Inc. | Polymeric chain transfer/shuttling agents |
BR112012001948B1 (pt) | 2009-07-29 | 2019-08-20 | Dow Global Technologies Llc | Agente de translado de cadeia, processo para a polimerização de pelo menos um monômero polimerizável por adição, copolímero em multi-bloco e composição de catalisador |
US20110054122A1 (en) * | 2009-08-31 | 2011-03-03 | Jerzy Klosin | Catalyst and process for polymerizing an olefin and polyolefin prepared thereby |
KR101411182B1 (ko) | 2009-12-21 | 2014-06-23 | 미쓰이 가가쿠 가부시키가이샤 | 신디오택틱 α-올레핀 중합체의 제조방법 |
EP2357035A1 (en) | 2010-01-13 | 2011-08-17 | Ineos Europe Limited | Polymer powder storage and/or transport and/or degassing vessels |
KR101854480B1 (ko) | 2010-02-19 | 2018-05-03 | 다우 글로벌 테크놀로지스 엘엘씨 | 올레핀 단량체의 중합 방법 및 이를 위한 촉매 |
EP2536735B1 (en) | 2010-02-19 | 2018-08-01 | Dow Global Technologies LLC | Metal-ligand complexes and catalysts |
EP2383298A1 (en) | 2010-04-30 | 2011-11-02 | Ineos Europe Limited | Polymerization process |
EP2383301A1 (en) | 2010-04-30 | 2011-11-02 | Ineos Europe Limited | Polymerization process |
US20120135903A1 (en) | 2010-05-11 | 2012-05-31 | Mitsui Chemicals, Inc. | Lubricating oil composition |
KR101788892B1 (ko) | 2010-05-17 | 2017-11-15 | 다우 글로벌 테크놀로지스 엘엘씨 | 에틸렌의 선택적 중합 방법 및 그를 위한 촉매 |
SG187848A1 (en) | 2010-08-25 | 2013-03-28 | Dow Global Technologies Llc | Process for polymerizing a polymerizable olefin and catalyst therefor |
WO2012061706A1 (en) | 2010-11-04 | 2012-05-10 | Dow Global Technologies Llc | Double shuttling of polyolefin polymeryl chains |
US9464181B2 (en) | 2010-11-24 | 2016-10-11 | Exxonmobil Chemical Patents Inc. | High filler loaded polymer composition |
US9394381B2 (en) | 2010-11-29 | 2016-07-19 | Ineos Sales (Uk) Limited | Polymerisation control process |
EP2663400A4 (en) | 2011-01-14 | 2014-07-30 | Grace W R & Co | PROCESS FOR THE PREPARATION OF A MODIFIED METALLOCENE CATALYST, CATALYST THUS PRODUCED AND USE THEREOF |
WO2012103080A1 (en) | 2011-01-26 | 2012-08-02 | Dow Global Technologies Llc | Process for making a polyolefin-polysiloxane block copolymer |
US9296836B2 (en) | 2011-05-12 | 2016-03-29 | Dow Global Technologies Llc | Non-cyclopentadienyl-based chromium catalysts for olefin polymerization |
WO2012157709A1 (ja) | 2011-05-18 | 2012-11-22 | 三井化学株式会社 | プロピレン系共重合体、プロピレン系共重合体組成物、その成形体およびその発泡体、およびそれらの製造方法 |
US8383740B1 (en) | 2011-08-12 | 2013-02-26 | Ineos Usa Llc | Horizontal agitator |
WO2013056979A1 (en) | 2011-10-17 | 2013-04-25 | Ineos Europe Ag | Polymer degassing process control |
EP2799488B1 (en) | 2011-12-27 | 2016-07-20 | Mitsui Chemicals, Inc. | 4-methyl-1-pentene (co)polymer composition, and film and hollow molded body, each of which is formed from 4-methyl-1-pentene (co)polymer composition |
KR101612213B1 (ko) | 2011-12-28 | 2016-04-12 | 미쓰이 가가쿠 가부시키가이샤 | 에틸렌계 중합체 조성물 및 이로부터 얻어지는 성형체 |
WO2013101376A1 (en) | 2011-12-29 | 2013-07-04 | Dow Global Technologies Llc | Hyperbranched olefin oil-based dielectric fluid |
CN104024284B (zh) | 2011-12-29 | 2016-08-31 | 陶氏环球技术有限责任公司 | 低分子量的基于乙烯和α-烯烃的材料的制备方法 |
EP2829555B1 (en) | 2012-03-21 | 2018-05-16 | Mitsui Chemicals, Inc. | Method for producing olefin polymer |
JP5830600B2 (ja) | 2012-03-28 | 2015-12-09 | 三井化学株式会社 | 太陽電池封止材および太陽電池モジュール |
ES2620287T3 (es) | 2012-06-04 | 2017-06-28 | Sasol Olefins & Surfactants Gmbh | Complejos de guanidinato y su uso como catalizadores de polimerización de transferencia de cadenas |
US9458261B2 (en) | 2012-09-25 | 2016-10-04 | Mitsui Chemicals, Inc. | Transition metal compound, olefin polymerization catalyst, and olefin polymer production process |
JP5980339B2 (ja) | 2012-09-25 | 2016-08-31 | 三井化学株式会社 | オレフィン重合体の製造方法およびオレフィン重合体 |
KR101394943B1 (ko) | 2012-11-19 | 2014-05-14 | 대림산업 주식회사 | 에틸렌과 알파-올레핀의 공중합체 및 그 제조방법 |
ES2731574T3 (es) | 2012-12-27 | 2019-11-18 | Dow Global Technologies Llc | Un proceso de polimerización para producir polímeros a base de etileno |
CN104884485B (zh) | 2012-12-27 | 2017-11-21 | 陶氏环球技术有限责任公司 | 用于产生乙烯类聚合物的聚合方法 |
BR112015015545B1 (pt) | 2012-12-27 | 2021-11-16 | Dow Global Technologies Llc | Processo para produzir um polímero a base de etileno |
JP6653173B2 (ja) | 2012-12-27 | 2020-02-26 | ダウ グローバル テクノロジーズ エルエルシー | エチレン系ポリマー |
BR112015015394B1 (pt) | 2012-12-27 | 2021-09-28 | Dow Global Technologies Llc | Procatalisador, sistema catalisador e processo de polimerização |
PT2960270T (pt) | 2013-02-20 | 2018-02-07 | Prime Polymer Co Ltd | Filme estirado biaxialmente, e composição de polímeto de tipo etileno |
JP6204973B2 (ja) | 2013-02-27 | 2017-09-27 | 三井化学株式会社 | オレフィン多量化用触媒および該触媒存在下で行うオレフィン多量体の製造方法 |
KR101699658B1 (ko) | 2013-03-12 | 2017-01-24 | 미쓰이 가가쿠 가부시키가이샤 | 올레핀 중합체의 제조방법 및 올레핀 중합용 촉매 |
ES2934177T3 (es) | 2013-06-28 | 2023-02-17 | Dow Global Technologies Llc | Control de peso molecular de poliolefinas usando catalizadores de bis-fenilfenoxilo halogenados |
JP6161716B2 (ja) | 2013-10-18 | 2017-07-12 | 三井化学株式会社 | エチレン・α−オレフィン共重合体を含有する接着剤 |
JP6549578B2 (ja) | 2013-12-19 | 2019-07-24 | ダウ グローバル テクノロジーズ エルエルシー | 金属−配位子錯体、それに由来するオレフィン重合触媒、及びその触媒を利用したオレフィン重合方法 |
CN109824809B (zh) | 2014-02-13 | 2022-06-28 | 三井化学株式会社 | 乙烯-α-烯烃-非共轭多烯共聚物及其用途 |
CA2936511C (en) | 2014-02-13 | 2019-06-11 | Mitsui Chemicals, Inc. | Process for producing ethylene/.alpha.-olefin copolymer |
WO2015122495A1 (ja) | 2014-02-14 | 2015-08-20 | 三井化学株式会社 | エチレン・α-オレフィン・非共役ポリエン共重合体、その製造方法ならびに用途 |
BR112016018907B1 (pt) | 2014-02-28 | 2021-07-06 | Mitsui Chemicals, Inc | método para a produção de um produto reticulado, artigo moldado laminado, copolímero de etileno (a) e composição de copolímero de etileno |
WO2015147215A1 (ja) | 2014-03-28 | 2015-10-01 | 三井化学株式会社 | エチレン/α-オレフィン共重合体および潤滑油 |
WO2015147186A1 (ja) | 2014-03-28 | 2015-10-01 | 三井化学株式会社 | オレフィン系樹脂およびその製造方法 |
KR101850233B1 (ko) | 2014-03-28 | 2018-04-18 | 미쓰이 가가쿠 가부시키가이샤 | 올레핀계 수지, 그의 제조 방법 및 프로필렌계 수지 조성물 |
US20170152377A1 (en) | 2014-06-26 | 2017-06-01 | Dow Global Technologies Llc | Breathable films and articles incorporating same |
EP3160742A1 (en) | 2014-06-26 | 2017-05-03 | Dow Global Technologies LLC | Cast films with improved toughness |
WO2015200743A1 (en) | 2014-06-26 | 2015-12-30 | Dow Global Technologies Llc | Blown films with improved toughness |
EP3160973B1 (en) | 2014-06-30 | 2020-04-08 | Dow Global Technologies LLC | Catalyst systems for olefin polymerization |
US10519260B2 (en) | 2014-06-30 | 2019-12-31 | Dow Global Technologies Llc | Polymerizations for olefin-based polymers |
SG11201700372SA (en) | 2014-07-24 | 2017-02-27 | Dow Global Technologies Llc | Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers |
JP6490086B2 (ja) | 2014-09-10 | 2019-03-27 | 三井化学株式会社 | 潤滑油組成物 |
SG11201701851XA (en) | 2014-09-11 | 2017-04-27 | Mitsui Chemicals Inc | Production method of olefin (co)polymer containing constituent unit derived from 1-butene |
SG11201703851UA (en) | 2014-11-25 | 2017-06-29 | Univation Tech Llc | Methods of controlling polyolefin melt index |
WO2016089935A1 (en) | 2014-12-04 | 2016-06-09 | Dow Global Technologies Llc | Five-coordinate bis-phenylphenoxy catalysts for the preparation of ethylene-based polymers |
WO2016093266A1 (ja) | 2014-12-09 | 2016-06-16 | 三井化学株式会社 | プロピレン系樹脂組成物 |
KR102533991B1 (ko) | 2014-12-31 | 2023-05-19 | 다우 글로벌 테크놀로지스 엘엘씨 | 폴리올레핀 조성물 및 그 제조방법 |
EP3653300A1 (en) | 2015-03-13 | 2020-05-20 | Dow Global Technologies LLC | Olefin oligomerization process with a catalyst comprising a chromium complex with a phosphacycle-containing ligand |
WO2016152710A1 (ja) | 2015-03-20 | 2016-09-29 | 三井化学株式会社 | 熱可塑性エラストマー組成物およびその製造方法 |
JP6439039B2 (ja) | 2015-03-20 | 2018-12-19 | 三井化学株式会社 | 熱可塑性エラストマー組成物、その用途、その製造方法、エチレン・α−オレフィン・非共役ポリエン共重合体およびその用途 |
WO2016158661A1 (ja) | 2015-03-31 | 2016-10-06 | 三井化学株式会社 | 樹脂組成物およびその用途 |
EP3093280A1 (en) | 2015-05-13 | 2016-11-16 | Sasol Performance Chemicals GmbH | Process for the oligomerisation of olefins by coordinative chain transfer polymerisation and catalyst synthesis |
US11041027B2 (en) | 2015-06-30 | 2021-06-22 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
EP3317312B1 (en) | 2015-06-30 | 2020-06-10 | Dow Global Technologies LLC | A polymerization process for producing ethylene based polymers |
KR102606500B1 (ko) | 2015-09-30 | 2023-11-28 | 다우 글로벌 테크놀로지스 엘엘씨 | 사슬 왕복에 유용한 다중-헤드 또는 이중-헤드 조성물 및 이를 제조하는 방법 |
WO2017058858A1 (en) | 2015-09-30 | 2017-04-06 | Dow Global Technologies Llc | A polymerization process for producing ethylene based polymers |
KR102646587B1 (ko) | 2015-09-30 | 2024-03-13 | 다우 글로벌 테크놀로지스 엘엘씨 | 전촉매 및 이를 사용한 중합 방법 |
JP6545813B2 (ja) | 2015-11-09 | 2019-07-17 | 三井化学株式会社 | 潤滑油用粘度調整剤、潤滑油用添加剤組成物および潤滑油組成物 |
EP3214124B2 (en) | 2016-03-02 | 2022-06-08 | Dow Global Technologies LLC | An ethylene/alpha-olefin copolymer composition, and articles comprising the same |
EP3214115B1 (en) | 2016-03-03 | 2018-10-03 | Dow Global Technologies LLC | Polyethylene composition, method of making the same, and films made therefrom |
EP3214211B1 (en) | 2016-03-03 | 2020-12-30 | Dow Global Technologies LLC | Artificial turfs and method of making the same |
EP3214116B1 (en) | 2016-03-03 | 2021-06-23 | Dow Global Technologies LLC | Breathable films and method of making the same |
KR102213323B1 (ko) | 2016-03-04 | 2021-02-05 | 미쓰이 가가쿠 가부시키가이샤 | 적층체 및 그의 용도 |
ES2919998T3 (es) | 2016-03-31 | 2022-07-29 | Dow Global Technologies Llc | Un catalizador de polimerización de olefinas |
WO2017173080A1 (en) | 2016-03-31 | 2017-10-05 | Dow Global Technologies Llc | Olefin polymerization catalyst systems and methods of use thereof |
ES2820365T3 (es) | 2016-03-31 | 2021-04-20 | Dow Global Technologies Llc | Sistemas catalíticos para la polimerización de olefinas y métodos de uso de los mismos |
US11492471B2 (en) | 2016-07-21 | 2022-11-08 | Mitsui Chemicals, Inc. | Polypropylene resin composition and monolayer and multilayer film |
EP3490999B1 (en) | 2016-07-29 | 2021-04-14 | Dow Global Technologies LLC | Synthesis of m-terphenyl pendant bis-ether ligands and metal complex and their use in olefin polymerization |
EP3519190B1 (en) | 2016-09-28 | 2020-09-23 | Dow Global Technologies Llc | Blown films with improved properties |
MX2019003242A (es) | 2016-09-30 | 2019-08-05 | Dow Global Technologies Llc | Resinas para usar como capas de union en peliculas multicapa y peliculas multicapa que las comprenden. |
KR102490785B1 (ko) | 2016-09-30 | 2023-01-20 | 다우 글로벌 테크놀로지스 엘엘씨 | 사슬 왕복에 유용한 캡핑된 다중- 또는 이중-헤드형 조성물 및 이의 제조 방법 |
KR102606000B1 (ko) | 2016-09-30 | 2023-11-27 | 다우 글로벌 테크놀로지스 엘엘씨 | 포스파구아니딘 4족 금속 올레핀 중합 촉매 |
CN109963888A (zh) | 2016-09-30 | 2019-07-02 | 陶氏环球技术有限责任公司 | 用于制备适用于链梭移的多头或双头组合物的方法 |
EP3519469B1 (en) | 2016-09-30 | 2020-07-29 | Dow Global Technologies LLC | Bis-ligated phosphaguanidine group iv metal complexes and olefin polymerization catalysts produced therefrom |
ES2866909T3 (es) | 2016-09-30 | 2021-10-20 | Dow Global Technologies Llc | Ligandos de bis-fosfaguanidina y poli-fosfaguanidina con metales del grupo IV y catalizadores producidos a partir de los mismos |
EP3519455B1 (en) | 2016-09-30 | 2024-04-10 | Dow Global Technologies Llc | Multi- or dual-headed compositions useful for chain shuttling and process to prepare the same |
ES2970349T3 (es) | 2016-10-18 | 2024-05-28 | Dow Global Technologies Llc | Composiciones y estructuras de fundas extensibles multicapa |
CN110072981B (zh) | 2017-01-16 | 2022-02-25 | 三井化学株式会社 | 汽车齿轮用润滑油组合物 |
JP6792650B2 (ja) | 2017-02-20 | 2020-11-25 | 三井化学株式会社 | 積層体 |
US11964447B2 (en) | 2017-02-20 | 2024-04-23 | Mitsui Chemicals, Inc. | Laminate |
CN110603271A (zh) | 2017-03-15 | 2019-12-20 | 陶氏环球技术有限责任公司 | 用于形成多嵌段共聚物的催化剂体系 |
EP3596141B1 (en) | 2017-03-15 | 2021-07-28 | Dow Global Technologies LLC | Catalyst system for multi-block copolymer formation |
US11897992B2 (en) | 2017-03-15 | 2024-02-13 | Dow Global Technologies Llc | Catalyst system for multi-block copolymer formation |
KR102631009B1 (ko) | 2017-03-15 | 2024-01-30 | 다우 글로벌 테크놀로지스 엘엘씨 | 다중-블록 공중합체 형성을 위한 촉매 시스템 |
BR112019019129A2 (pt) | 2017-03-15 | 2020-04-14 | Dow Global Technologies Llc | sistema catalisador para formação de copolímero de múltiplos blocos |
AR111718A1 (es) | 2017-04-19 | 2019-08-14 | Dow Global Technologies Llc | Estructuras de laminados y materiales de empaque flexibles que las incluyen |
AR112359A1 (es) | 2017-06-30 | 2019-10-23 | Dow Global Technologies Llc | Laminados de polietileno para usar en materiales de embalaje flexibles |
AR112245A1 (es) | 2017-06-30 | 2019-10-09 | Dow Global Technologies Llc | Laminados y películas de polietileno multicapa para usar en materiales de envasado flexibles |
KR20220110863A (ko) | 2017-07-06 | 2022-08-09 | 미쓰이 가가쿠 가부시키가이샤 | 올레핀 다량화용 촉매 및 그 촉매 존재하에서 행하는 올레핀 다량체의 제조 방법 |
EP3684850B1 (en) | 2017-09-22 | 2024-04-10 | Dow Global Technologies LLC | Thermoformed film compositions with enhanced toughness after thermoforming processes |
WO2019067280A1 (en) | 2017-09-29 | 2019-04-04 | Dow Global Technologies Llc | BIS-PHENYL-PHENOXY-POLYOLEFIN CATALYSTS HAVING ALKOXY OR AMIDO-TYPE LIGAND ON METAL FOR ENHANCED SOLUBILITY |
SG11202002720WA (en) | 2017-09-29 | 2020-04-29 | Dow Global Technologies Llc | Bis-phenyl-phenoxy polyolefin catalysts having two methylenetrialkylsilicon ligands on the metal for improved solubility |
ES2911503T3 (es) | 2017-09-29 | 2022-05-19 | Dow Global Technologies Llc | Catalizadores de bis-fenil-fenoxi-poliolefina que tienen un ligando de metilentrialquilsilicio en el metal para mejorar la solubilidad |
CN111868116B (zh) | 2018-03-20 | 2022-12-09 | 三井化学株式会社 | 乙烯-α-烯烃-非共轭多烯共聚物、其制造方法及用途 |
CN112969726A (zh) | 2018-12-04 | 2021-06-15 | 三井化学株式会社 | 含有4-甲基-1-戊烯共聚物的树脂组合物及电容器用膜 |
WO2020140064A1 (en) | 2018-12-28 | 2020-07-02 | Dow Global Technologies Llc | Organometallic chain transfer agents |
JP2022516119A (ja) | 2018-12-28 | 2022-02-24 | ダウ グローバル テクノロジーズ エルエルシー | テレケリックポリオレフィンを含む硬化性組成物 |
KR20210121027A (ko) | 2018-12-28 | 2021-10-07 | 다우 글로벌 테크놀로지스 엘엘씨 | 불포화 폴리올레핀을 포함하는 경화성 조성물 |
KR20210121031A (ko) | 2018-12-28 | 2021-10-07 | 다우 글로벌 테크놀로지스 엘엘씨 | 불포화 폴리올레핀을 포함하는 경화성 조성물 |
SG11202107051UA (en) | 2018-12-28 | 2021-07-29 | Dow Global Technologies Llc | Telechelic polyolefins and processes for preparing the same |
EP3943543A4 (en) | 2019-03-19 | 2022-12-14 | Mitsui Chemicals, Inc. | PROPYLENE RESIN COMPOSITION, MOLDING AND PROPYLENE POLYMER |
EP3950898A4 (en) | 2019-03-26 | 2022-08-10 | Mitsui Chemicals, Inc. | COMPOSITION OF LUBRICANT OIL FOR AUTOMOTIVE TRANSMISSIONS AND METHOD OF PRODUCTION THEREOF |
EP3950901A4 (en) | 2019-03-26 | 2022-08-17 | Mitsui Chemicals, Inc. | LUBRICATING OIL COMPOSITIONLUBRICATING OIL COMPOSITION FOR INTERNAL COMBUSTION ENGINE, AND METHOD OF MAKING THE SAME |
EP3950902A4 (en) | 2019-03-26 | 2022-08-10 | Mitsui Chemicals, Inc. | LUBRICATION OIL COMPOSITION FOR AUTOMOTIVE GEAR FLUID AND METHOD OF MANUFACTURE THEREOF |
US20220169939A1 (en) | 2019-03-26 | 2022-06-02 | Mitsui Chemicals, Inc. | Lubricating oil and method for producing the same |
EP3950897A4 (en) | 2019-03-26 | 2022-08-10 | Mitsui Chemicals, Inc. | LUBRICATING OIL COMPOSITION FOR COMPRESSOR OIL, AND METHOD OF MAKING THE SAME |
EP3950892A4 (en) | 2019-03-26 | 2022-08-10 | Mitsui Chemicals, Inc. | FAT COMPOSITION AND PROCESS FOR PRODUCTION THEREOF |
US20220186133A1 (en) | 2019-03-26 | 2022-06-16 | Mitsui Chemicals, Inc. | Lubricating oil composition for industrial gears and method for producing the same |
WO2020194546A1 (ja) | 2019-03-26 | 2020-10-01 | 三井化学株式会社 | 内燃機関用潤滑油組成物およびその製造方法 |
EP3950895A4 (en) | 2019-03-26 | 2022-08-10 | Mitsui Chemicals, Inc. | LUBRICATION OIL COMPOSITION FOR HYDRAULIC OIL AND PROCESS FOR PRODUCTION THEREOF |
CN113574139A (zh) | 2019-03-26 | 2021-10-29 | 三井化学株式会社 | 润滑油组合物及其制造方法 |
EP3946938A1 (en) | 2019-03-26 | 2022-02-09 | Dow Global Technologies LLC | Multilayer films, laminates, and articles comprising multilayer films |
JP7297054B2 (ja) | 2019-03-29 | 2023-06-23 | 三井化学株式会社 | 樹脂組成物 |
WO2021025141A1 (ja) | 2019-08-08 | 2021-02-11 | 株式会社プライムポリマー | プロピレン系重合体組成物および成形体 |
US20220411659A1 (en) | 2019-10-07 | 2022-12-29 | Mitsui Chemicals, Inc. | ETHYLENE/alpha-OLEFIN COPOLYMER COMPOSITION AND APPLICATION THEREOF |
WO2021085225A1 (ja) | 2019-10-29 | 2021-05-06 | 三井化学株式会社 | エチレン系共重合体組成物およびその用途 |
US20230101204A1 (en) | 2020-01-30 | 2023-03-30 | Mitsui Chemicals, Inc. | Polyamide composition |
MX2022014745A (es) | 2020-05-27 | 2023-01-11 | Dow Global Technologies Llc | Formulaciones polimericas y tuberias de riego que incluyen formulaciones polimericas. |
JP2023534659A (ja) | 2020-07-17 | 2023-08-10 | ダウ グローバル テクノロジーズ エルエルシー | 拘束幾何プロ触媒のためのヒドロカルビル変性メチルアルミノキサン助触媒 |
CN116234836A (zh) | 2020-10-06 | 2023-06-06 | 三井化学株式会社 | 树脂组合物 |
US20230382929A1 (en) | 2020-10-15 | 2023-11-30 | Dow Global Technologies Llc | Olefin polymerization catalysts bearing a 6-amino-n-aryl azaindole ligand |
KR20230122111A (ko) | 2021-01-18 | 2023-08-22 | 미쓰이 가가쿠 가부시키가이샤 | 수분산체 조성물, 당해 수분산체 조성물의 제조 방법및 에틸렌·α-올레핀 공중합체 산변성물 |
EP4303238A1 (en) | 2021-03-05 | 2024-01-10 | Mitsui Chemicals, Inc. | Thermoplastic elastomer composition |
EP4316833A1 (en) | 2021-03-31 | 2024-02-07 | Mitsui Chemicals, Inc. | ETHYLENE-a-OLEFIN COPOLYMER, THERMOPLASTIC RESIN COMPOSITION, FILM, AND LAMINATE |
JPWO2022210844A1 (zh) | 2021-03-31 | 2022-10-06 | ||
US20240191068A1 (en) | 2021-03-31 | 2024-06-13 | Mitsui Chemicals, Inc. | Ethylene resin composition and shaped article |
US20240209124A1 (en) | 2021-04-30 | 2024-06-27 | Exxonmobil Chemical Patents Inc. | Processes for transitioning between different polymerization catalysts in a polymerization reactor |
JPWO2022244879A1 (zh) | 2021-05-20 | 2022-11-24 | ||
CN117337323A (zh) | 2021-07-20 | 2024-01-02 | 三井化学株式会社 | 润滑油用粘度调节剂及工作油用润滑油组合物 |
JPWO2023090308A1 (zh) | 2021-11-16 | 2023-05-25 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0780930B2 (ja) * | 1985-12-26 | 1995-08-30 | 三井石油化学工業株式会社 | α−オレフインの重合方法 |
US5153157A (en) * | 1987-01-30 | 1992-10-06 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
US5055438A (en) * | 1989-09-13 | 1991-10-08 | Exxon Chemical Patents, Inc. | Olefin polymerization catalysts |
US5096867A (en) * | 1990-06-04 | 1992-03-17 | Exxon Chemical Patents Inc. | Monocyclopentadienyl transition metal olefin polymerization catalysts |
IL85097A (en) | 1987-01-30 | 1992-02-16 | Exxon Chemical Patents Inc | Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes |
US4931417A (en) * | 1987-11-09 | 1990-06-05 | Chisso Corporation | Transition-metal compound having a bis-substituted-cyclopentadienyl ligand of bridged structure |
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 |
US5064802A (en) * | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
US5066741A (en) * | 1990-03-22 | 1991-11-19 | The Dow Chemical Company | Process for preparation of syndiotactic vinyl aromatic polymers |
CA2024830A1 (en) * | 1989-09-29 | 1991-03-30 | Richard E. Campbell, Jr. | Process for preparation of syndiotactic vinyl aromatic polymers |
CA2027123C (en) * | 1989-10-30 | 2001-09-04 | Michael J. Elder | Metallocene catalysts for polymerization of olefins |
US5034034A (en) * | 1990-08-28 | 1991-07-23 | The Dow Chemical Company | Novel aryl carbonate cyanoaryl ether gas separation membranes |
-
1991
- 1991-06-20 JP JP3245282A patent/JP2545006B2/ja not_active Expired - Fee Related
- 1991-06-27 BR BR919102815A patent/BR9102815A/pt not_active IP Right Cessation
- 1991-07-01 MY MYPI91001193A patent/MY108636A/en unknown
- 1991-07-01 SG SG1996005482A patent/SG52523A1/en unknown
- 1991-07-01 ES ES95115577T patent/ES2267097T3/es not_active Expired - Lifetime
- 1991-07-01 EP EP95115577A patent/EP0698618B1/en not_active Expired - Lifetime
- 1991-07-01 EP EP91305955A patent/EP0468651B1/en not_active Expired - Lifetime
- 1991-07-01 DE DE69133543T patent/DE69133543T2/de not_active Expired - Fee Related
- 1991-07-01 DE DE69121813T patent/DE69121813T2/de not_active Expired - Fee Related
- 1991-07-01 ES ES91305955T patent/ES2091293T3/es not_active Expired - Lifetime
- 1991-07-02 NO NO912600A patent/NO180720C/no not_active IP Right Cessation
- 1991-07-02 MX MX9100063A patent/MX9100063A/es not_active IP Right Cessation
- 1991-07-02 ZA ZA915114A patent/ZA915114B/xx unknown
- 1991-07-02 KR KR1019910011149A patent/KR100203235B1/ko not_active IP Right Cessation
- 1991-07-02 CA CA002046075A patent/CA2046075C/en not_active Expired - Fee Related
- 1991-07-02 AU AU80145/91A patent/AU651599B2/en not_active Ceased
- 1991-07-02 CN CN91104485A patent/CN1032008C/zh not_active Expired - Fee Related
- 1991-07-02 FI FI913215A patent/FI105559B/fi not_active IP Right Cessation
- 1991-07-02 RU SU915001125A patent/RU2011652C1/ru not_active IP Right Cessation
-
1992
- 1992-06-09 US US07/896,732 patent/US5321106A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE69121813D1 (de) | 1996-10-10 |
DE69121813T2 (de) | 1997-04-03 |
DE69133543T2 (de) | 2007-08-16 |
MX9100063A (es) | 1992-02-28 |
FI913215A0 (fi) | 1991-07-02 |
BR9102815A (pt) | 1992-02-04 |
JP2545006B2 (ja) | 1996-10-16 |
AU651599B2 (en) | 1994-07-28 |
CA2046075A1 (en) | 1992-01-04 |
EP0468651A1 (en) | 1992-01-29 |
MY108636A (en) | 1996-10-31 |
EP0698618A2 (en) | 1996-02-28 |
FI913215A (fi) | 1992-01-04 |
FI105559B (fi) | 2000-09-15 |
SG52523A1 (en) | 1998-09-28 |
EP0698618B1 (en) | 2006-08-30 |
KR920002640A (ko) | 1992-02-28 |
ZA915114B (en) | 1993-03-31 |
ES2091293T3 (es) | 1996-11-01 |
EP0698618A3 (en) | 1997-02-12 |
AU8014591A (en) | 1992-01-09 |
CA2046075C (en) | 2002-06-04 |
CN1057845A (zh) | 1992-01-15 |
JPH04253711A (ja) | 1992-09-09 |
RU2011652C1 (ru) | 1994-04-30 |
NO180720B (no) | 1997-02-24 |
US5321106A (en) | 1994-06-14 |
NO180720C (no) | 1997-06-04 |
DE69133543D1 (de) | 2006-10-12 |
ES2267097T3 (es) | 2007-03-01 |
EP0468651B1 (en) | 1996-09-04 |
NO912600D0 (no) | 1991-07-02 |
KR100203235B1 (ko) | 1999-06-15 |
NO912600L (no) | 1992-01-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1032008C (zh) | 加聚催化剂的制备方法 | |
CN1028369C (zh) | 使用阳离子聚合催化剂的聚合方法 | |
KR100218559B1 (ko) | 금속 중심 산화반응에 의한 부가 중합반응 촉매의 제조방법 | |
CN1134467C (zh) | 剪切稀化的乙烯/α-烯烃共聚体及它们的制备 | |
KR100567505B1 (ko) | 사이클로펜타페난트레닐 금속 착체 및 중합 방법 | |
CN1044372C (zh) | 烯烃聚合催化剂的固体组份及其制备和该催化剂及其应用 | |
DE69426648T3 (de) | Verfahren zur herstellung von olefinpolymeren und katalysator zur olefinpolymerisation | |
CN1291204A (zh) | 用桥连的二茂铪化合物制备烯烃共聚物的聚合方法 | |
KR20100076056A (ko) | 가교 메탈로센 화합물 및 그것을 사용한 올레핀 중합용 촉매, 및 상기 촉매를 사용하여 얻어지는 에틸렌계 중합체 | |
CN1123795A (zh) | 催化剂组合物及其制备方法和应用方法 | |
EP2077269B1 (en) | Transition metal complexes, catalyst compositions containing the same, and methods for preparing ethylene polymers using the same | |
JPH10502342A (ja) | エチレン−α−オレフィンコポリマー製造触媒のためのモノシクロペンタジエニル金属化合物 | |
KR20200135420A (ko) | 규소-말단화된 유기-금속 화합물 및 이를 제조하는 방법 | |
CN1178949C (zh) | 作为聚合催化剂的环戊二烯基过渡金属配合物 | |
JPH05331324A (ja) | エチレン・α−オレフィン共重合体組成物 | |
CN1062733A (zh) | 杂环硼酸盐金属络合物及其用作配位聚合催化剂 | |
JPH10259212A (ja) | オレフィン(共)重合体の製造方法 | |
JP3262137B2 (ja) | エチレン系重合体の製造方法 | |
JP2002542348A (ja) | 遅延活性支持オレフィン重合触媒組成物、並びにその作成および使用方法 | |
JP3299275B2 (ja) | ポリオレフィンの製造方法 | |
JPH05132523A (ja) | 環状オレフイン系重合体の製造方法 | |
EP0614916A1 (en) | Process for producing polyolefin | |
JPH05331237A (ja) | エチレン系共重合体 | |
JPH05230134A (ja) | 分子量分布の広いポリオレフィンの製造方法 | |
JP3518772B2 (ja) | ポリオレフィンの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
OR01 | Other related matters | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |