CN1053673C - 负载催化剂体系、它的制备及其在烯烃聚合中的应用 - Google Patents

负载催化剂体系、它的制备及其在烯烃聚合中的应用 Download PDF

Info

Publication number: CN1053673C
Authority: CN; China
Prior art keywords: zirconium dichloride; indenyl; cyclopentadienyl; dimetylsilyl; methyl
Prior art date: 1993-02-12
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

Application number

CN94101358A

Other languages

English (en)

Chinese (zh)

Other versions

CN1096517A (zh

Inventor

M-J·布列克尼尔

B·巴赫曼

F·奥桑

K·阿尔伯逖

A·文特

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Hoechst AG

Original Assignee

Hoechst AG

Priority date (The priority date 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 date listed.)

1993-02-12

Filing date

1994-02-08

Publication date

2000-06-21

1994-02-08 Application filed by Hoechst AG filed Critical Hoechst AG

1994-12-21 Publication of CN1096517A publication Critical patent/CN1096517A/zh

2000-06-21 Application granted granted Critical

2000-06-21 Publication of CN1053673C publication Critical patent/CN1053673C/zh

2014-02-08 Anticipated expiration legal-status Critical

Status Expired - Fee Related legal-status Critical Current

Links

239000003054 catalyst Substances 0.000 title claims abstract description 66
238000002360 preparation method Methods 0.000 title claims abstract description 25
238000006116 polymerization reaction Methods 0.000 title claims description 24
150000001336 alkenes Chemical class 0.000 title description 4
238000000034 method Methods 0.000 claims abstract description 35
239000000725 suspension Substances 0.000 claims abstract description 33
239000000463 material Substances 0.000 claims abstract description 13
230000009471 action Effects 0.000 claims abstract description 7
VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 74
-1 fluorenyl zirconium dichlorides Chemical class 0.000 claims description 72
VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 59
239000007787 solid Substances 0.000 claims description 19
238000006243 chemical reaction Methods 0.000 claims description 18
ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 17
YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 16
UCIKZESDXASJNG-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 Chemical class [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 UCIKZESDXASJNG-UHFFFAOYSA-L 0.000 claims description 15
239000000843 powder Substances 0.000 claims description 15
JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
229910052726 zirconium Inorganic materials 0.000 claims description 11
IKMQPGOYCLXVSL-UHFFFAOYSA-L [Cl-].[Cl-].C1(C=CC=C1)[Zr+2]C1C2=CC=CC=C2C=2C=CC=CC1=2 Chemical compound [Cl-].[Cl-].C1(C=CC=C1)[Zr+2]C1C2=CC=CC=C2C=2C=CC=CC1=2 IKMQPGOYCLXVSL-UHFFFAOYSA-L 0.000 claims description 10
150000001925 cycloalkenes Chemical class 0.000 claims description 10
125000002619 bicyclic group Chemical group 0.000 claims description 9
ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 9
IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
150000001875 compounds Chemical class 0.000 claims description 8
DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 8
XJONFIGVOQMBIP-UHFFFAOYSA-L Cl[Zr](Cl)C1C=CC=C1 Chemical compound Cl[Zr](Cl)C1C=CC=C1 XJONFIGVOQMBIP-UHFFFAOYSA-L 0.000 claims description 7
125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
239000002904 solvent Substances 0.000 claims description 7
VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
229920000098 polyolefin Polymers 0.000 claims description 6
239000000741 silica gel Substances 0.000 claims description 6
229910002027 silica gel Inorganic materials 0.000 claims description 6
238000003756 stirring Methods 0.000 claims description 6
235000010290 biphenyl Nutrition 0.000 claims description 5
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 claims description 5
238000001914 filtration Methods 0.000 claims description 5
HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 5
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
NZDLIIBVQQCHBI-UHFFFAOYSA-L Cl[Zr]Cl.CC1=C[CH]C=C1 Chemical compound Cl[Zr]Cl.CC1=C[CH]C=C1 NZDLIIBVQQCHBI-UHFFFAOYSA-L 0.000 claims description 4
125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
239000002283 diesel fuel Substances 0.000 claims description 4
239000008187 granular material Substances 0.000 claims description 4
239000012442 inert solvent Substances 0.000 claims description 4
XFBYPTDICTYNBZ-UHFFFAOYSA-L CC1=C[C@@](C)([Zr](Cl)Cl)C=C1 Chemical compound CC1=C[C@@](C)([Zr](Cl)Cl)C=C1 XFBYPTDICTYNBZ-UHFFFAOYSA-L 0.000 claims description 3
SMATWXHZMRECKC-UHFFFAOYSA-L [Cl-].[Cl-].C1(C=CC=C1)[Hf+2]C1C2=CC=CC=C2C=2C=CC=CC1=2 Chemical compound [Cl-].[Cl-].C1(C=CC=C1)[Hf+2]C1C2=CC=CC=C2C=2C=CC=CC1=2 SMATWXHZMRECKC-UHFFFAOYSA-L 0.000 claims description 3
MVLVTGKWPHOVFO-UHFFFAOYSA-L [Cl-].[Cl-].[Zr+2].C=CC=CC Chemical compound [Cl-].[Cl-].[Zr+2].C=CC=CC MVLVTGKWPHOVFO-UHFFFAOYSA-L 0.000 claims description 3
230000004913 activation Effects 0.000 claims description 3
125000002015 acyclic group Chemical group 0.000 claims description 3
AIXAANGOTKPUOY-UHFFFAOYSA-N carbachol Chemical group [Cl-].C[N+](C)(C)CCOC(N)=O AIXAANGOTKPUOY-UHFFFAOYSA-N 0.000 claims description 3
239000012876 carrier material Substances 0.000 claims description 3
125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
229910052732 germanium Inorganic materials 0.000 claims description 3
GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
CISVRDKQPCPFQX-UHFFFAOYSA-N C(C1=CC=CC=C1)[Zr]CC1=CC=CC=C1.C=CC=CC Chemical compound C(C1=CC=CC=C1)[Zr]CC1=CC=CC=C1.C=CC=CC CISVRDKQPCPFQX-UHFFFAOYSA-N 0.000 claims description 2
JPSHILHGDRCOQO-UHFFFAOYSA-L C1=CC=C2C([Hf](Cl)Cl)C=CC2=C1 Chemical compound C1=CC=C2C([Hf](Cl)Cl)C=CC2=C1 JPSHILHGDRCOQO-UHFFFAOYSA-L 0.000 claims description 2
PRQXONWMWVCAEW-UHFFFAOYSA-L CCC1(C=CC=C1)[Zr](Cl)Cl Chemical compound CCC1(C=CC=C1)[Zr](Cl)Cl PRQXONWMWVCAEW-UHFFFAOYSA-L 0.000 claims description 2
ZBKJVVTWGPHNSC-UHFFFAOYSA-L Cl[Zr]Cl.C[C]1C(C)=C(C)C(C)=C1C Chemical compound Cl[Zr]Cl.C[C]1C(C)=C(C)C(C)=C1C ZBKJVVTWGPHNSC-UHFFFAOYSA-L 0.000 claims description 2
NKKALSOFYFMKGW-UHFFFAOYSA-L [Cl-].[Cl-].C(CCC)C1=CC=CC1[Zr+2] Chemical compound [Cl-].[Cl-].C(CCC)C1=CC=CC1[Zr+2] NKKALSOFYFMKGW-UHFFFAOYSA-L 0.000 claims description 2
QMUDOHCFQLGPLF-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC=CC1(C)[Zr++] Chemical compound [Cl-].[Cl-].CC1=CC=CC1(C)[Zr++] QMUDOHCFQLGPLF-UHFFFAOYSA-L 0.000 claims description 2
LJSGOOJPNHUWPL-UHFFFAOYSA-L [Cl-].[Cl-].[Zr++](C1C=Cc2ccccc12)C1c2ccccc2-c2ccccc12 Chemical compound [Cl-].[Cl-].[Zr++](C1C=Cc2ccccc12)C1c2ccccc2-c2ccccc12 LJSGOOJPNHUWPL-UHFFFAOYSA-L 0.000 claims description 2
FAJJYXYRMUZENM-UHFFFAOYSA-L [Cl-].[Cl-].[Zr++]C1c2ccccc2-c2ccccc12 Chemical compound [Cl-].[Cl-].[Zr++]C1c2ccccc2-c2ccccc12 FAJJYXYRMUZENM-UHFFFAOYSA-L 0.000 claims description 2
SZTWDTSJUBOWTK-UHFFFAOYSA-N [Zr].C1(=CC=CC=C1)C1=CC=CC=C1.C=CC=CC Chemical compound [Zr].C1(=CC=CC=C1)C1=CC=CC=C1.C=CC=CC SZTWDTSJUBOWTK-UHFFFAOYSA-N 0.000 claims description 2
238000013019 agitation Methods 0.000 claims description 2
238000009826 distribution Methods 0.000 claims description 2
TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
238000006884 silylation reaction Methods 0.000 claims description 2
125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
238000002425 crystallisation Methods 0.000 claims 1
230000008025 crystallization Effects 0.000 claims 1
238000000197 pyrolysis Methods 0.000 claims 1
238000001228 spectrum Methods 0.000 claims 1
230000008569 process Effects 0.000 abstract description 8
YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
239000004743 Polypropylene Substances 0.000 description 19
229920001155 polypropylene Polymers 0.000 description 19
230000000694 effects Effects 0.000 description 17
239000000243 solution Substances 0.000 description 14
238000012360 testing method Methods 0.000 description 14
VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
239000007789 gas Substances 0.000 description 10
239000000203 mixture Substances 0.000 description 8
QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 7
238000001816 cooling Methods 0.000 description 7
229920001577 copolymer Polymers 0.000 description 7
125000004122 cyclic group Chemical group 0.000 description 7
XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
229910052782 aluminium Inorganic materials 0.000 description 6
230000000052 comparative effect Effects 0.000 description 6
238000010438 heat treatment Methods 0.000 description 6
229920000642 polymer Polymers 0.000 description 6
239000000126 substance Substances 0.000 description 6
YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
229910004298 SiO 2 Inorganic materials 0.000 description 5
125000004429 atom Chemical group 0.000 description 5
239000012065 filter cake Substances 0.000 description 5
239000000706 filtrate Substances 0.000 description 5
239000000178 monomer Substances 0.000 description 5
239000002245 particle Substances 0.000 description 5
QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
238000009736 wetting Methods 0.000 description 5
125000003342 alkenyl group Chemical group 0.000 description 4
239000004411 aluminium Substances 0.000 description 4
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
229910052799 carbon Inorganic materials 0.000 description 4
230000007423 decrease Effects 0.000 description 4
229910052751 metal Inorganic materials 0.000 description 4
239000002184 metal Substances 0.000 description 4
230000000379 polymerizing effect Effects 0.000 description 4
239000011541 reaction mixture Substances 0.000 description 4
CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
239000005977 Ethylene Substances 0.000 description 3
238000004220 aggregation Methods 0.000 description 3
230000002776 aggregation Effects 0.000 description 3
229910052786 argon Inorganic materials 0.000 description 3
239000011521 glass Substances 0.000 description 3
229910052735 hafnium Inorganic materials 0.000 description 3
VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
239000011261 inert gas Substances 0.000 description 3
229910052757 nitrogen Inorganic materials 0.000 description 3
125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
238000010926 purge Methods 0.000 description 3
229920006395 saturated elastomer Polymers 0.000 description 3
125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 2
AGKZDUBMFACJPR-UHFFFAOYSA-L C12=CC=CC=C2C2=CC=CC=C2C1[Zr](Cl)(Cl)(=C(C)C)C1C=CC=C1 Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1[Zr](Cl)(Cl)(=C(C)C)C1C=CC=C1 AGKZDUBMFACJPR-UHFFFAOYSA-L 0.000 description 2
125000006374 C2-C10 alkenyl group Chemical group 0.000 description 2
239000004215 Carbon black (E152) Substances 0.000 description 2
ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
208000005156 Dehydration Diseases 0.000 description 2
TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
239000004698 Polyethylene Substances 0.000 description 2
125000000217 alkyl group Chemical group 0.000 description 2
230000033228 biological regulation Effects 0.000 description 2
239000000460 chlorine Substances 0.000 description 2
229910052801 chlorine Inorganic materials 0.000 description 2
239000011248 coating agent Substances 0.000 description 2
238000000576 coating method Methods 0.000 description 2
230000018044 dehydration Effects 0.000 description 2
238000006297 dehydration reaction Methods 0.000 description 2
125000005843 halogen group Chemical group 0.000 description 2
229930195733 hydrocarbon Natural products 0.000 description 2
150000002430 hydrocarbons Chemical class 0.000 description 2
239000007788 liquid Substances 0.000 description 2
238000002156 mixing Methods 0.000 description 2
238000012544 monitoring process Methods 0.000 description 2
125000005574 norbornylene group Chemical group 0.000 description 2
230000003287 optical effect Effects 0.000 description 2
229920000573 polyethylene Polymers 0.000 description 2
230000007115 recruitment Effects 0.000 description 2
229910052710 silicon Inorganic materials 0.000 description 2
239000010703 silicon Substances 0.000 description 2
230000007704 transition Effects 0.000 description 2
KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
XBBHYFLWNUTSGU-UHFFFAOYSA-L CC(C)=[Hf](Cl)(Cl)(C1C=CC=C1)C1c2ccccc2-c2ccccc12 Chemical compound CC(C)=[Hf](Cl)(Cl)(C1C=CC=C1)C1c2ccccc2-c2ccccc12 XBBHYFLWNUTSGU-UHFFFAOYSA-L 0.000 description 1
XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
238000010521 absorption reaction Methods 0.000 description 1
125000001931 aliphatic group Chemical group 0.000 description 1
125000005234 alkyl aluminium group Chemical group 0.000 description 1
238000003556 assay Methods 0.000 description 1
239000011324 bead Substances 0.000 description 1
230000008901 benefit Effects 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
150000001721 carbon Chemical group 0.000 description 1
230000003197 catalytic effect Effects 0.000 description 1
230000008859 change Effects 0.000 description 1
239000003795 chemical substances by application Substances 0.000 description 1
230000002596 correlated effect Effects 0.000 description 1
230000000875 corresponding effect Effects 0.000 description 1
238000005336 cracking Methods 0.000 description 1
125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
238000010790 dilution Methods 0.000 description 1
239000012895 dilution Substances 0.000 description 1
SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 1
125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
229920001038 ethylene copolymer Polymers 0.000 description 1
238000002474 experimental method Methods 0.000 description 1
125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
238000005227 gel permeation chromatography Methods 0.000 description 1
230000002650 habitual effect Effects 0.000 description 1
150000002366 halogen compounds Chemical class 0.000 description 1
239000001257 hydrogen Substances 0.000 description 1
229910052739 hydrogen Inorganic materials 0.000 description 1
238000011068 loading method Methods 0.000 description 1
229910001629 magnesium chloride Inorganic materials 0.000 description 1
238000002844 melting Methods 0.000 description 1
230000008018 melting Effects 0.000 description 1
CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
229910052758 niobium Inorganic materials 0.000 description 1
239000010955 niobium Substances 0.000 description 1
GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
238000012545 processing Methods 0.000 description 1
239000000047 product Substances 0.000 description 1
230000005855 radiation Effects 0.000 description 1
239000000376 reactant Substances 0.000 description 1
230000035484 reaction time Effects 0.000 description 1
238000003860 storage Methods 0.000 description 1
238000005728 strengthening Methods 0.000 description 1
229910052715 tantalum Inorganic materials 0.000 description 1
GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
229910052718 tin Inorganic materials 0.000 description 1
239000010936 titanium Substances 0.000 description 1
229910052719 titanium Inorganic materials 0.000 description 1
229910052720 vanadium Inorganic materials 0.000 description 1
GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
238000005406 washing Methods 0.000 description 1
230000003245 working effect Effects 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
- 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
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
- 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
- C08F4/65922—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 containing at least two cyclopentadienyl rings, fused or not
- 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
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/522—Radiant or wave energy activated
- 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)
Health & Medical Sciences (AREA)
Chemical Kinetics & Catalysis (AREA)
Medicinal Chemistry (AREA)
Polymers & Plastics (AREA)
Organic Chemistry (AREA)
Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

CN94101358A 1993-02-12 1994-02-08 负载催化剂体系、它的制备及其在烯烃聚合中的应用 Expired - Fee Related CN1053673C (zh)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DEP4304286.4		1993-02-12
DE4304286		1993-02-12

Publications (2)

Publication Number	Publication Date
CN1096517A CN1096517A (zh)	1994-12-21
CN1053673C true CN1053673C (zh)	2000-06-21

Family

ID=6480336

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
CN94101358A Expired - Fee Related CN1053673C (zh)	1993-02-12	1994-02-08	负载催化剂体系、它的制备及其在烯烃聚合中的应用

Country Status (7)

Country	Link
US (1)	US5719095A (2)
EP (1)	EP0615981B1 (2)
JP (1)	JP3425794B2 (2)
KR (1)	KR100312665B1 (2)
CN (1)	CN1053673C (2)
DE (1)	DE59405876D1 (2)
TW (1)	TW298593B (2)

Families Citing this family (71)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US6143686A (en) *	1994-08-03	2000-11-07	Exxon Chemical Patents, Inc.	Supported ionic catalyst compositions
US6043180A (en) *	1994-11-17	2000-03-28	The Dow Chemical Company	Supported catalyst component, supported catalyst, their preparation, and addition polymerization process
US6506866B2 (en) *	1994-11-17	2003-01-14	Dow Global Technologies Inc.	Ethylene copolymer compositions
CZ293261B6 (cs) *	1994-11-17	2004-03-17	The Dow Chemical Company	Nanesená katalytická komponenta, nanesený katalyzátor, způsob jejich přípravy a jejich použití
KR100405780B1 (ko) *	1996-04-22	2004-03-30	닛뽕폴리올레핀가부시키가이샤	폴리올레핀제조용촉매및폴리올레핀의제조방법
JPH10120716A (ja) *	1996-08-27	1998-05-12	Mitsui Chem Inc	予備重合固体状触媒、その調製方法およびオレフィンの不均一系重合方法
US5968864A (en) *	1996-12-20	1999-10-19	Fina Technology, Inc.	Catalyst efficiency for supported metallocene catalyst
US6245868B1 (en)	1998-05-29	2001-06-12	Univation Technologies	Catalyst delivery method, a catalyst feeder and their use in a polymerization process
US6562918B1 (en) *	1999-02-04	2003-05-13	Idemitsu Petrochemical Co., Ltd.	Olefin polymerization catalyst, method for producing the same and method for producing olefinic polymer
US7223822B2 (en)	2002-10-15	2007-05-29	Exxonmobil Chemical Patents Inc.	Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
BR0315341B1 (pt)	2002-10-15	2014-02-18		Adesivos compreendendo poliolefina.
BRPI0508173B1 (pt)	2004-03-17	2016-03-15	Dow Global Technologies Inc	copolímeros em multibloco, polímero, copolímero, um derivado funcional, mistura homogênea de polímero, processo para a preparação de um copolímero em multibloco contendo propileno e processo para preparar um copolímero em multibloco contendo 4-metil-1-penteno
EP2221329B1 (en)	2004-03-17	2014-11-26	Dow Global Technologies LLC	Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation
CN1934150A (zh)	2004-03-17	2007-03-21	陶氏环球技术公司	用于形成乙烯共聚物的包括穿梭剂的催化剂组合物
WO2005109099A1 (ja) *	2004-05-07	2005-11-17	Hitachi Chemical Dupont Microsystems Ltd.	ポジ型感光性樹脂組成物、パターンの製造方法及び電子部品
JP5188178B2 (ja)	2004-06-16	2013-04-24	ダウグローバルテクノロジーズエルエルシー	重合調整剤を選択するための技術
JP2008509277A (ja)	2004-08-09	2008-03-27	ダウグローバルテクノロジーズインコーポレイティド	ポリマーの製造のための担持ビス（ヒドロキシアリールアリールオキシ）触媒
WO2006049699A1 (en)	2004-10-29	2006-05-11	Exxonmobil Chemical Patents Inc	Catalyst compound containing divalent tridentate ligand
US8536268B2 (en)	2004-12-21	2013-09-17	Dow Global Technologies Llc	Polypropylene-based adhesive compositions
BRPI0609849B1 (pt)	2005-03-17	2017-05-09	Dow Global Technologies Inc	copolímero multibloco, processo de solução contínuo para preparar um copolímero multibloco, derivado funcionalizado, mistura polimérica homogênea e polímero
EP3424966B1 (en)	2005-03-17	2020-05-27	Dow Global Technologies Llc	Catalyst composition comprising shuttling agent for tactic/ atactic 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
EP1721913A1 (en) *	2005-05-09	2006-11-15	Total Petrochemicals Research Feluy	Microwave-promoted creation of catalytic species
JP5411502B2 (ja)	2005-09-15	2014-02-12	ダウグローバルテクノロジーズエルエルシー	重合性シャトリング剤による接触オレフィンブロック共重合体
AR058448A1 (es)	2005-09-15	2008-02-06	Dow Global Technologies Inc	Control de arquitectura del polimero y distribucoin de peso molecular va el agente de transferencia multi- centrado
US8153243B2 (en)	2005-12-09	2012-04-10	Dow Global Technologies Llc	Interpolymers suitable for multilayer films
AU2006329980A1 (en)	2005-12-16	2007-07-05	Dow Global Technologies Inc.	Polydentate heteroatom ligand containing metal complexes, catalysts and methods of making and using the same
EP1803747A1 (en)	2005-12-30	2007-07-04	Borealis Technology Oy	Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films
EP2024402B2 (en)	2006-05-17	2023-01-25	Dow Global Technologies LLC	High temperature solution polymerization process
US7879748B2 (en) *	2006-08-09	2011-02-01	Umicore Ag & Co. Kg	Method for producing a catalyst and the catalyst made therefrom
WO2008109628A1 (en)	2007-03-07	2008-09-12	Dow Global Technologies Inc.	Tethered supported transition metal complex
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
TW200932762A (en)	2007-10-22	2009-08-01	Univation Tech Llc	Polyethylene compositions having improved properties
ES2435568T3 (es)	2007-11-19	2013-12-20	Dow Global Technologies Llc	Copolímeros de propileno-alfa-olefina con ramificación de cadena larga
WO2010071798A1 (en)	2008-12-18	2010-06-24	Univation Technologies, Llc	Method for seed bed treatment for a polymerization reaction
WO2010102163A2 (en)	2009-03-06	2010-09-10	Dow Global Technologies Inc.	Catalysts, processes for making catalysts, processes for making polyolefin compositions and polyolefin compositions
WO2011016992A2 (en)	2009-07-29	2011-02-10	Dow Global Technologies Inc.	Polymeric chain transfer/shuttling agents
EP3243846B1 (en)	2009-07-29	2021-01-06	Dow Global Technologies LLC	Multi-headed chain shuttling agents and their use for the preparation of block copolymers
ES2446096T3 (es)	2009-10-19	2014-03-06	Sasol Technology (Proprietary) Limited	Oligomerización de compuestos olefínicos con formación de polímero reducida.
WO2011050565A1 (zh)	2009-10-26	2011-05-05	中国石油化工股份有限公司	负载型非茂金属催化剂、其制备方法及其应用
JP5523572B2 (ja)	2009-10-26	2014-06-18	中国石油化工股▲ふん▼有限公司	担持型非メタロセン触媒、その製造方法およびその使用
EP2500364B1 (en)	2009-11-13	2020-03-04	China Petroleum & Chemical Corporation	Supported non-metallocene catalyst preparation method and application thereof
US8952113B2 (en)	2009-11-13	2015-02-10	China Petroleum & Chemical Corp.	Supported nonmetallocene catalyst, preparation and use thereof
RU2430116C1 (ru) *	2010-01-29	2011-09-27	Закрытое Акционерное Общество "Сибур Холдинг"	Способ полимеризации и сополимеризации олефиновых олигомеров
RU2424055C1 (ru) *	2010-03-16	2011-07-20	Закрытое Акционерное Общество "Сибур Холдинг"	Способ получения каталитической системы полимеризации олефинов
ES2543432T3 (es)	2010-11-30	2015-08-19	Univation Technologies, Llc	Composición de catalizador con características de flujo mejoradas y métodos de producir y utilizar la misma
MY161173A (en)	2010-11-30	2017-04-14	Univation Tech Llc	Processes for the polymerization of olefins with extracted metal carboxlate salts
US9637567B2 (en)	2011-05-13	2017-05-02	Univation Technologies, Llc	Spray-dried catalyst compositions and polymerization processes employing the same
KR102214265B1 (ko)	2013-01-14	2021-02-10	유니베이션 테크놀로지즈, 엘엘씨	증가된 생산성을 갖는 촉매 시스템의 제조 방법
WO2014120494A1 (en)	2013-01-30	2014-08-07	Univation Technologies, Llc	Processes for making catalyst compositions having improved flow
RU2658602C2 (ru)	2013-08-29	2018-06-22	Юнифай Гмбх Унд Ко. Кг	Поддержание аудиосвязи в перегруженном канале связи
US10069965B2 (en)	2013-08-29	2018-09-04	Unify Gmbh & Co. Kg	Maintaining audio communication in a congested communication channel
CN114957529A (zh)	2014-04-02	2022-08-30	尤尼威蒂恩技术有限责任公司	连续性组合物及其制备和使用方法
SG11201707037TA (en)	2015-03-10	2017-09-28	Univation Tech Llc	Spray dried catalyst compositions, methods for preparation and use in olefin polymerization processes
EP3285923B1 (en)	2015-04-20	2019-07-17	Univation Technologies, LLC	Bridged bi-aromatic ligands and olefin polymerization catalysts prepared therefrom
US10252967B2 (en)	2015-04-20	2019-04-09	Univation Technologies, Llc	Bridged bi-aromatic ligands and transition metal compounds prepared therefrom
CN107531840B (zh)	2015-04-27	2022-11-18	尤尼威蒂恩技术有限责任公司	具有改进流动特性的负载型催化剂组合物及其制备
EP3356374B1 (en)	2015-09-30	2025-09-24	Dow Global Technologies LLC	Multi- or dual-headed compositions useful for chain shuttling and process to prepare the same
EP4435013A3 (en)	2016-09-30	2024-12-25	Dow Global Technologies LLC	Process for preparing multi- or dual-headed compositions useful for chain shuttling
TWI756272B (zh)	2016-09-30	2022-03-01	美商陶氏全球科技有限責任公司	適用於鏈梭移之封端多頭或雙頭組合物及其製備方法
TW201840572A (zh)	2016-09-30	2018-11-16	美商陶氏全球科技有限責任公司	適用於鏈梭移之多頭或雙頭組合物及其製備方法
CN110498873A (zh) *	2018-05-17	2019-11-26	中国石油天然气股份有限公司	一种烷基铝氧烷的预处理方法、茂金属催化剂的制备方法及烯烃聚合方法
CA3125275A1 (en)	2018-12-28	2020-07-02	Dow Global Technologies Llc	Curable compositions comprising unsaturated polyolefins
US12180314B2 (en)	2018-12-28	2024-12-31	Dow Global Technologies Llc	Curable compositions comprising unsaturated polyolefins
KR102916971B1 (ko)	2018-12-28	2026-01-23	다우 글로벌 테크놀로지스 엘엘씨	텔레켈릭 폴리올레핀 및 이의 제조 방법
CN113498414A (zh)	2018-12-28	2021-10-12	陶氏环球技术有限责任公司	包括遥爪聚烯烃的可固化组合物
CN113412264B (zh)	2018-12-28	2024-06-25	陶氏环球技术有限责任公司	有机金属链转移剂
EP4448593A1 (en)	2021-12-16	2024-10-23	Chevron Phillips Chemical Company Lp	Modifications of sulfated bentonites and uses thereof in metallocene catalyst systems for olefin polymerization
CN115650286B (zh) *	2022-10-24	2024-06-21	浙江大学	一种rGO/MXene/TiO2/Fe2C多级异质结构多孔微球吸波材料的制备方法
CN117586439B (zh) *	2024-01-17	2024-03-26	营口风光新材料股份有限公司	一种复合型茂金属催化剂及其制备方法与应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
GB1530445A (en) *	1976-01-09	1978-11-01	British Petroleum Co	Polymerisation catalyst
EP0523416A2 (de) *	1991-06-28	1993-01-20	Hoechst Aktiengesellschaft	Katalysator und Verfahren zur Herstellung von hochmolekularen Polyolefinen

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4564647A (en) *	1983-11-14	1986-01-14	Idemitsu Kosan Company Limited	Process for the production of polyethylene compositions
EP0314797B1 (en) *	1987-04-20	1997-07-02	Mitsui Petrochemical Industries, Ltd.	Olefin polymerization catalyst and process for polymerizing olefin
JP2538595B2 (ja) *	1987-05-13	1996-09-25	三井石油化学工業株式会社	オレフイン重合用固体触媒
FR2659337B1 (fr) *	1990-03-12	1992-06-05	Bp Chemicals Snc	Procede de preparation d'un catalyseur a base de zirconium, de titane et/ou de vanadium supporte sur du chlorure de magnesium, et utilisation du catalyseur dans la polymerisation des olefines.
EP0516458B2 (en) *	1991-05-31	2007-12-19	Mitsui Chemicals, Inc.	Olefin polymerization solid catalyst, olefin polymerization catalyst and olefin polymerization
TW337527B (en) *	1992-01-24	1998-08-01	Hoechst Ag	Catalyst for the polymerization of olefins, process for the preparation thereof, and use thereof
TW304963B (2) *	1992-01-27	1997-05-11	Hoechst Ag
FI112233B (fi) *	1992-04-01	2003-11-14	Basell Polyolefine Gmbh	Katalyytti olefiinipolymerointia varten, menetelmä sen valmistamiseksi ja sen käyttö
EP0578838A1 (en) *	1992-04-29	1994-01-19	Hoechst Aktiengesellschaft	Olefin polymerization catalyst, process for its preparation, and its use
TW369545B (en) *	1993-02-12	1999-09-11	Hoechst Ag	Process for preparing cycloolefin copolymers

1994
- 1994-02-04 TW TW083100946A patent/TW298593B/zh active
- 1994-02-07 EP EP94101797A patent/EP0615981B1/de not_active Expired - Lifetime
- 1994-02-07 DE DE59405876T patent/DE59405876D1/de not_active Expired - Fee Related
- 1994-02-08 CN CN94101358A patent/CN1053673C/zh not_active Expired - Fee Related
- 1994-02-10 JP JP01652694A patent/JP3425794B2/ja not_active Expired - Fee Related
- 1994-02-10 US US08/196,285 patent/US5719095A/en not_active Expired - Fee Related
- 1994-02-12 KR KR1019940002491A patent/KR100312665B1/ko not_active Expired - Fee Related

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
GB1530445A (en) *	1976-01-09	1978-11-01	British Petroleum Co	Polymerisation catalyst
EP0523416A2 (de) *	1991-06-28	1993-01-20	Hoechst Aktiengesellschaft	Katalysator und Verfahren zur Herstellung von hochmolekularen Polyolefinen

Also Published As

Publication number	Publication date
CN1096517A (zh)	1994-12-21
DE59405876D1 (de)	1998-06-10
JPH072920A (ja)	1995-01-06
US5719095A (en)	1998-02-17
EP0615981A3 (de)	1994-11-17
EP0615981A2 (de)	1994-09-21
EP0615981B1 (de)	1998-05-06
TW298593B (2)	1997-02-21
JP3425794B2 (ja)	2003-07-14
KR100312665B1 (ko)	2001-12-28

Legal Events

Date	Code	Title
1994-12-21	C06	Publication
1994-12-21	PB01	Publication
1996-05-22	C10	Entry into substantive examination
1996-05-22	SE01	Entry into force of request for substantive examination
2000-06-21	C14	Grant of patent or utility model
2000-06-21	GR01	Patent grant
2003-04-09	C19	Lapse of patent right due to non-payment of the annual fee
2003-04-09	CF01	Termination of patent right due to non-payment of annual fee

Publication	Publication Date	Title
CN1096517A (zh)	1994-12-21	负载催化剂体系、它的制备及其在烯烃聚合中的应用
CN1149231C (zh)	2004-05-12	负载型烯烃聚合催化剂组合物的制备方法、所制得的催化剂及用途
CN1176093C (zh)	2004-11-17	双环戊二烯基二烯配合物
CN1068332C (zh)	2001-07-11	金属茂化合物
CN1116314C (zh)	2003-07-30	烯烃聚合的催化剂及方法
CN1231502C (zh)	2005-12-14	多核茂金属催化剂
CN1142190C (zh)	2004-03-17	高活性负载型催化剂组合物
CN1113899C (zh)	2003-07-09	用于烯烃聚合的催化剂及方法
CN1878805A (zh)	2006-12-13	用于制备多相丙烯共聚物的多步法
CN1181386A (zh)	1998-05-13	金属茂
CN1105674A (zh)	1995-07-26	乙烯聚合物的制备方法以及由乙烯聚合物制得的产物
CN1366528A (zh)	2002-08-28	可用作烯烃聚合的助催化剂的有机金属化合物
CN1211996A (zh)	1999-03-24	载体催化剂体系
CN1270595A (zh)	2000-10-18	改性铝氧烷催化剂活化剂
CN1910207A (zh)	2007-02-07	载体茂金属催化剂、制备该催化剂的方法以及使用该催化剂制备聚烯烃的方法
CN100339403C (zh)	2007-09-26	用于烯烃聚合的卤代催化剂体系
CN1109061A (zh)	1995-09-27	金属茂化合物
CN1131954A (zh)	1996-09-25	乙烯共聚物，乙烯基聚合物制备方法及所用的催化剂体系
CN1249760A (zh)	2000-04-05	用于金属茂化合物的新活化剂体系
CN1103069A (zh)	1995-05-31	载体型烯烃聚合催化剂
CN1805977A (zh)	2006-07-19	采用金属茂催化剂体系的聚合方法
CN1019579B (zh)	1992-12-23	制备烯烃聚合催化剂的方法
CN1101051A (zh)	1995-04-05	环烯烃共聚物的制备方法
CN1127524C (zh)	2003-11-12	载体上的催化剂组分、载体上的催化剂、它们的制备方法和加聚方法
CN1123796A (zh)	1996-06-05	无定形丙烯聚合物的制备方法