CN1076731C - 复合型限定几何构型金属茂催化剂、其制备及应用 - Google Patents
复合型限定几何构型金属茂催化剂、其制备及应用 Download PDFInfo
- Publication number
- CN1076731C CN1076731C CN96106466A CN96106466A CN1076731C CN 1076731 C CN1076731 C CN 1076731C CN 96106466 A CN96106466 A CN 96106466A CN 96106466 A CN96106466 A CN 96106466A CN 1076731 C CN1076731 C CN 1076731C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- silane
- preparation
- cyclopentadienyl
- lithium
- 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
- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 32
- 238000013329 compounding Methods 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 67
- -1 silylation Chemical group 0.000 claims description 34
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- 239000003446 ligand Substances 0.000 claims description 22
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 4
- 239000005864 Sulphur Chemical group 0.000 claims 2
- 229910052728 basic metal Inorganic materials 0.000 claims 2
- 150000003818 basic metals Chemical class 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 229910000765 intermetallic Inorganic materials 0.000 claims 2
- 125000003282 alkyl amino group Chemical group 0.000 claims 1
- 150000001354 dialkyl silanes Chemical class 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 238000006884 silylation reaction Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003426 co-catalyst Substances 0.000 abstract description 3
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 44
- 239000000243 solution Substances 0.000 description 41
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000005457 ice water Substances 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- PFGWJXLLXJLZCC-UHFFFAOYSA-N n-[dimethyl-(1,2,3,4-tetramethylcyclopenta-2,4-dien-1-yl)silyl]-2-methylpropan-2-amine Chemical compound CC1=CC(C)([Si](C)(C)NC(C)(C)C)C(C)=C1C PFGWJXLLXJLZCC-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 150000001335 aliphatic alkanes Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002516 radical scavenger Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- QJWCAWHRSWFNNM-UHFFFAOYSA-N chloro-dimethyl-(1,2,3,4-tetramethylcyclopenta-2,4-dien-1-yl)silane Chemical compound CC=1C(=C(C(C=1)(C)[Si](C)(C)Cl)C)C QJWCAWHRSWFNNM-UHFFFAOYSA-N 0.000 description 4
- ZAOSBIDKKLAWRE-UHFFFAOYSA-N CC[Si](CC)(C1C=CC2=CC=CC=C12)Cl Chemical compound CC[Si](CC)(C1C=CC2=CC=CC=C12)Cl ZAOSBIDKKLAWRE-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- HLZBYIVAMXUYBW-UHFFFAOYSA-N chloro-cyclopenta-2,4-dien-1-yl-dimethylsilane Chemical compound C[Si](C)(Cl)C1C=CC=C1 HLZBYIVAMXUYBW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- DBKDYYFPDRPMPE-UHFFFAOYSA-N lithium;cyclopenta-1,3-diene Chemical compound [Li+].C=1C=C[CH-]C=1 DBKDYYFPDRPMPE-UHFFFAOYSA-N 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VNPQQEYMXYCAEZ-UHFFFAOYSA-N 1,2,3,4-tetramethylcyclopenta-1,3-diene Chemical compound CC1=C(C)C(C)=C(C)C1 VNPQQEYMXYCAEZ-UHFFFAOYSA-N 0.000 description 2
- PXSCEAJMCLQOBY-UHFFFAOYSA-N 2,6,6-trimethyloxaluminane Chemical compound C[Al]1CCCC(C)(C)O1 PXSCEAJMCLQOBY-UHFFFAOYSA-N 0.000 description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- QINLGUWBWKUNQK-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+2].C(C)(C)(C)N[Si](C)(C)C1C=CC=C1 Chemical compound [Cl-].[Cl-].[Ti+2].C(C)(C)(C)N[Si](C)(C)C1C=CC=C1 QINLGUWBWKUNQK-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 125000003106 haloaryl 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
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- DWWZPYPYUFXZTL-UHFFFAOYSA-N lithium;2h-inden-2-ide Chemical compound [Li+].C1=CC=C2[CH-]C=CC2=C1 DWWZPYPYUFXZTL-UHFFFAOYSA-N 0.000 description 2
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Chemical group 0.000 description 2
- 239000011593 sulfur Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- CCRUDHGKDHTFNK-UHFFFAOYSA-N CC1=CC(C)([Na])C(C)=C1C Chemical compound CC1=CC(C)([Na])C(C)=C1C CCRUDHGKDHTFNK-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- JAHUCWAAGICQQB-UHFFFAOYSA-N N-[cyclopenta-2,4-dien-1-yl(dimethyl)silyl]-2-methylpropan-2-amine Chemical compound CC(C)(C)N[Si](C)(C)C1C=CC=C1 JAHUCWAAGICQQB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002009 alkene group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002355 alkine group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
主催化剂 | MAO用量g | Al/Timol/mol | 聚乙烯产量g | 催化剂活性克聚乙烯/mol Ti hr | 聚乙烯熔点℃ |
实施例1 | 3.5 | 159 | 43.6 | 1.1×105 | 137 |
实施例2 | 2.9 | 150 | 81.6 | 2.4×105 | 133 |
实施例3 | 2.9 | 150 | 25.0 | 7.5×104 | 135 |
实施例4 | 2.9 | 150 | 31.2 | 9.4×104 | 135 |
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN96106466A CN1076731C (zh) | 1996-08-12 | 1996-08-12 | 复合型限定几何构型金属茂催化剂、其制备及应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN96106466A CN1076731C (zh) | 1996-08-12 | 1996-08-12 | 复合型限定几何构型金属茂催化剂、其制备及应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1173502A CN1173502A (zh) | 1998-02-18 |
CN1076731C true CN1076731C (zh) | 2001-12-26 |
Family
ID=5119188
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN96106466A Expired - Fee Related CN1076731C (zh) | 1996-08-12 | 1996-08-12 | 复合型限定几何构型金属茂催化剂、其制备及应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1076731C (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100489125C (zh) * | 2004-06-24 | 2009-05-20 | 株洲硬质合金集团有限公司 | 一种铌的提纯方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10442921B2 (en) * | 2017-04-19 | 2019-10-15 | Nova Chemicals (International) S.A. | Means for increasing the molecular weight and decreasing the density employing mixed homogeneous catalyst formulations |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0426643A1 (en) * | 1989-10-30 | 1991-05-08 | Fina Research S.A. | Process for the preparation of metallocenes |
EP0582114A1 (en) * | 1992-08-03 | 1994-02-09 | Albemarle Corporation | Process for preparing metallocenes |
-
1996
- 1996-08-12 CN CN96106466A patent/CN1076731C/zh not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0426643A1 (en) * | 1989-10-30 | 1991-05-08 | Fina Research S.A. | Process for the preparation of metallocenes |
EP0582114A1 (en) * | 1992-08-03 | 1994-02-09 | Albemarle Corporation | Process for preparing metallocenes |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100489125C (zh) * | 2004-06-24 | 2009-05-20 | 株洲硬质合金集团有限公司 | 一种铌的提纯方法 |
Also Published As
Publication number | Publication date |
---|---|
CN1173502A (zh) | 1998-02-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1059448C (zh) | 一种用于生产间规聚烯烃的金属茂催化剂及其制备方法 | |
JP3275081B2 (ja) | 金属中心酸化による付加重合触媒の製造法 | |
US6218558B1 (en) | Transition metal compound, catalyst component for olefin polymerization and process for the preparation of α-olefin polymer | |
DE60226010T2 (de) | Mehrkerniger metallocenkatalysator | |
EP1752462B1 (en) | Siloxy substituted metallocene catalysts | |
JP3275211B2 (ja) | 付加重合触媒の製造方法 | |
JP3119305B2 (ja) | 触媒、これら触媒の製法、およびこれら触媒の使用法 | |
KR100282461B1 (ko) | 메탈로센 및 이의 제조 방법 | |
EP0427696A2 (en) | Process and catalyst for producing syndiotactic polymers | |
US6414162B1 (en) | Bimetallic catalysts for olefin polymerization | |
JP2004527608A (ja) | オレフィン重合触媒成分及び触媒システム、並びにそのような触媒システムを用いた重合プロセス | |
EP1784431A1 (en) | Supported metallocene catalyst, method of preparing the catalyst and method of preparing polyolefin using the catalyst | |
JP4482448B2 (ja) | 4−アリール−置換三環状インデニル誘導体含有第4族金属錯体 | |
CN1068330C (zh) | 金属茂化合物及其作为催化剂组分的应用 | |
JP2001122886A (ja) | 単一の炭素架橋したビスシクロペンタジエニル化合物及びこれのメタロセン錯体 | |
CN112745366B (zh) | 硅基桥联的茂金属化合物及其制备方法、应用 | |
CN1076731C (zh) | 复合型限定几何构型金属茂催化剂、其制备及应用 | |
JP3850048B2 (ja) | 有機遷移金属化合物およびそれを用いたポリオレフィンの製造方法 | |
CN1049439C (zh) | 负载型金属茂催化剂、其制备及应用 | |
CN1428355A (zh) | 一种双核茂金属化合物及其制备与在烯烃聚合中的应用 | |
US6194343B1 (en) | Bridged “tethered” metallocenes | |
CN1140720A (zh) | 间规选择性复合金属茂催化剂 | |
US6753436B2 (en) | Olefin polymerization catalysts | |
JP3946615B2 (ja) | オレフィン重合触媒用遷移金属化合物、オレフィン重合用触媒ならびにポリオレフィンの製造方法 | |
JP4055212B2 (ja) | 有機遷移金属錯体の製造方法 |
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 | ||
C56 | Change in the name or address of the patentee |
Owner name: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM & Free format text: FORMER NAME OR ADDRESS: CHINA PETRO-CHEMICAL CORP.; RESEARCH INST. OF PETROLEUM PROCESSING, SINOPEC |
|
CP01 | Change in the name or title of a patent holder |
Patentee after: China Petrochemical Group Corp. Patentee after: Chinese petrochemical industry Research Institute of Petro-Chemical Engineering of group company Patentee before: China Petrochemical Corporation Patentee before: Petroleum Chem. Indust. Sci. Inst., China Petro=chemical Corp. |
|
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20011226 Termination date: 20100812 |