US20030176606A1 - Process for the production of highly reactive polyisobutenes - Google Patents
Process for the production of highly reactive polyisobutenes Download PDFInfo
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- US20030176606A1 US20030176606A1 US10/385,556 US38555603A US2003176606A1 US 20030176606 A1 US20030176606 A1 US 20030176606A1 US 38555603 A US38555603 A US 38555603A US 2003176606 A1 US2003176606 A1 US 2003176606A1
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- United States
- Prior art keywords
- process according
- isobutene
- polymerization
- mol
- highly reactive
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- Abandoned
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- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 229920002367 Polyisobutene Polymers 0.000 title abstract description 31
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 51
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 150000003624 transition metals Chemical class 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 32
- 229920000642 polymer Polymers 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910015900 BF3 Inorganic materials 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000000336 imidazol-5-yl group Chemical group [H]N1C([H])=NC([H])=C1[*] 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- MBQWQUMAAHXKKG-UHFFFAOYSA-N BC1=C(F)C(F)=C(C)C(F)=C1F.BC1=C(F)C(F)=C(C)C(F)=C1F.BC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1.C.C.C.C.C/C=N\[Mn](/N=C\C)(/N=C/C)(/N=C/C)(/N=C/C)/N=C/C.C/C=N\[Mn](/N=C\C)(/N=C/C)(/N=C/C)(/N=C/C)/N=C/C.C/C=N\[Mn](/N=C\C)(/N=C\C)(/N=C/C)(/N=C/C)/N=C/C.C/C=N\[Ni](/N=C\C)(/N=C/C)/N=C/C.CC1=C(F)C(F)=C(BN2=CN(BC3=C(F)C(F)=C(F)C(F)=C3F)C=C2)C(F)=C1F Chemical compound BC1=C(F)C(F)=C(C)C(F)=C1F.BC1=C(F)C(F)=C(C)C(F)=C1F.BC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1.C.C.C.C.C/C=N\[Mn](/N=C\C)(/N=C/C)(/N=C/C)(/N=C/C)/N=C/C.C/C=N\[Mn](/N=C\C)(/N=C/C)(/N=C/C)(/N=C/C)/N=C/C.C/C=N\[Mn](/N=C\C)(/N=C\C)(/N=C/C)(/N=C/C)/N=C/C.C/C=N\[Ni](/N=C\C)(/N=C/C)/N=C/C.CC1=C(F)C(F)=C(BN2=CN(BC3=C(F)C(F)=C(F)C(F)=C3F)C=C2)C(F)=C1F MBQWQUMAAHXKKG-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- -1 cyclohexane Chemical class 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000010552 living cationic polymerization reaction Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000035899 viability Effects 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
- C08F10/10—Isobutene
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
- C08F110/10—Isobutene
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a process for the production of highly reactive polyisobutenes with a content of terminal vinylidene groupings of greater than 80 mol % and an average molecular weight of 500 to 10,000 Dalton by cationic polymerization of isobutene, in the liquid phase, in the presence of monomeric, solvent-stabilized transition metal complexes with weakly coordinating anions.
- Polyisobutenes with molecular weights of 500 to 5,000 Dalton are produced with the assistance of Lewis acid catalysts, such as aluminum chloride, aluminumalkyl chlorides or boron trifluoride and usually have less than 10 mol % of terminal double bonds (vinylidene groupings) and a molecular weight distribution (dispersity) of between 2 and 5.
- Lewis acid catalysts such as aluminum chloride, aluminumalkyl chlorides or boron trifluoride and usually have less than 10 mol % of terminal double bonds (vinylidene groupings) and a molecular weight distribution (dispersity) of between 2 and 5.
- terminal vinylidene groupings which react during adduct formation with maleic anhydride, whereas, depending upon their position, the double bonds located further within the macromolecules do not give rise to any or any distinctly lower conversion without the addition of halogens.
- the proportion of terminal vinylidene groupings in the molecule is an important quality criterion for this type of polyisobutene.
- polyisobutene products are obtained, the polyisobutene components of which, i.e. the polyisobutene macromolecules, have a random molecular weight distribution of a greater or lesser width.
- the wider the molecular weight distribution of these polyisobutenes the greater the content thereof of polyisobutene macromolecules having relatively low or relatively high molecular weights, which are less suitable for the mentioned intended application.
- reactive polyisobutenes comprising up to 88 wt. % of terminal double bonds can be obtained by boron trifluoride-catalyzed polymerization of isobutene at temperatures of ⁇ 50 to +30° C. and residence times of less than 10 minutes. A value of no lower than 1.8 is found for the dispersity of the polyisobutenes produced in this manner.
- reaction temperatures of above 0° C. are disclosed in the above cited referenced and the Examples, therein only give rise to an elevated content of terminal double bonds of greater than 80% if temperatures of distinctly below 0° C. are used.
- U.S. Pat. No. 4,227,027 discloses boron trifluoride-catalyzed alkyl transfer reactions, wherein the catalysts are adducts of boron trifluoride and diols or polyols at temperatures of 40 to 120° C.
- the catalysts are adducts of boron trifluoride and diols or polyols at temperatures of 40 to 120° C.
- Another process for the production of highly reactive polyisobutenes involves living cationic polymerization of isobutene with subsequent dehydrochlorination, as is described, for example, in U.S. Pat. No. 5,340,881. This process yields up to 100% of terminal double bonds, but requires low temperatures and a complex solvent mixture, which unnecessarily complicates recycling of the unreacted starting materials.
- An object of the present invention was to develop an economic process, which operates at temperatures of above 0° C. and yields the described highly reactive polyisobutenes.
- the present invention provides a process for the production of highly reactive isobutene homo- and copolymers with a content of terminal vinylidene groupings of greater than 80 mol % and an average molecular weight of 500 to 10,000 Dalton, wherein isobutene or isobutene with copolymerizable monomers is/are polymerize in the presence of a transition metal catalyst of the general formula
- M is a metal from the 3rd to 12th periods of the periodic system of elements
- R 1 is a C 1 -C 8 alkyl group
- A is a weakly coordinating anion.
- Copolymerizable monomers which may be used in the process of the present invention, include, for example, isoprene and/or styrene.
- the process according to the present invention is preferably used to produce copolymers based on isobutene and isoprene, which have molecular weights from approximately 2,000 to 7,000 Dalton and have a content of incorporated isoprene of up to 60% (determined by nuclear magnetic resonance spectroscopy).
- the highly reactive polyisobutenes produced according to the process of the present invention preferably have a content of terminal vinylidene groupings of 95 to 100 mol % and an average molecular weight of 2,000 to 7,000 Dalton.
- the polyisoprenes according to the present invention are soluble in many organic solvents, such as chloroform, dichloromethane, hexane, heptane, cyclohexane, toluene or benzene or mixtures thereof.
- the process of the present invention is preferably performed in an inert organic solvent, wherein halogenated and halogen-free hydrocarbons, which may optionally be substituted by nitro groups, or mixtures thereof are used.
- halogenated and halogen-free hydrocarbons which may optionally be substituted by nitro groups, or mixtures thereof are used.
- Dichloromethane, chloroform, dichloroethane, tetrachloroethane, hexane or pentane, and cycloalkanes, such as cyclohexane, and aromatic hydrocarbons, such as toluene and benzene, are, for example, preferred.
- the quantity of solvent may be determined by routine experimentation.
- the concentration of the introduced monomers in the solvent used is preferably in the range from 0.01 to 10 mol/l, more preferably 0.1 to 2 mol/l.
- the transition metal catalysts of the above-stated general formula are those in which M is Mn, Ni, Cr or Zn and A contains anions of the formulae BF 4 ⁇ , SbX 6 ⁇ , PX 6 ⁇ and/or B(Ar) 4 ⁇ as well as B(Ar) 4 ⁇ anions bridged by cyclic groupings, wherein Ar denotes phenyl, which have 1 to 5 substituents, such as F, Cl or CF 3 .
- Cyclic bridges which may preferably be considered for B (Ar) 4 ⁇ anions, include imidazolyl bridges.
- R 1 preferably denotes C 1 -C 4 alkyl residues, such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl or tert.-butyl.
- More preferred transition metal catalysts include those of the following formulae:
- the transition metal catalysts are used in the process according to the present invention in a molar ratio of 1:15,000,000 to 1:10, preferably of 1:500,000 to 1:10,000, relative to the introduced quantities of monomers.
- the concentration of the introduced catalysts in the reaction mixture is in the range from 0.01 to 10 mmol/l, preferably 0.1 to 2 mmol/l.
- Polymerization is performed according to the present invention at temperatures of approximately 0 to 100° C., preferably from 20 to 60° C.
- transition metal catalysts useful according to the present invention are known per se and may be produced using known processes, as described, for example, in Wayne E. Buschmann, Joel S. Miller, Chem. Eur. J. 1998, 4(9), 1731-1737, and Bruce H. Lipshutz, Wayne Vaccaro, Bret Huft, Tetrahedron Letters 1986, 27(35), 4095-4098 and LaPointe, Robert E.; Roof, Gordon R.; Abboud, Khalil A.; Klosin, Jerzy. New Family of Weakly Coordinating Anions. Journal of the American Chemical Society (2000), 122(39), 9560-9561.
- Molecular weight Mn was determined by means of gel permeation chromatography in chloroform. Column: Waters Ultrastyragel®, pore size 10,000 and 100,000 ⁇ and Waters Styragel®, pore size 500 ⁇ , detection: differential refractometer (Waters R 401), calibration: polystyrene standards.
- Monomers gaseous at room temperature were advantageously dried by using columns packed with phosphorus pentoxide and finely divided potassium on aluminum oxide, while liquid monomers were dried by columns with aluminum oxide and distillation over sodium/aluminum oxide.
- Halogenated solvents such as for example dichloromethane, were dried with calcium hydride and distilled under inert gas.
- Aliphatic solvents such as for example hexane, were dried with sodium and distilled.
- the content of terminal vinylidene end groups is 100 mol % according to 1 H-NMR.
- the content of terminal vinylidene end groups is 100 mol % according to 1 H-NMR.
- Isothermal polymerization of isobutene was performed at 40° C. in a polymerization autoclave.
- the polymerization autoclave was heat treated and flooded with argon before the reaction.
- 93 mL of dichloromethane were then introduced and adjusted to a temperature of 40° C.
- Saturation proceeds at a stirring speed of 400 revolutions per minute, while polymerization was performed at a stirrer speed of 1,000 revolutions per minute.
- the content of terminal vinylidene end groups was 100 mol % according to 1 H-NMR.
Abstract
The present invention relates to a process for the production of highly reactive polyisobutenes with a content of terminal vinylidene groupings of greater than 80 mol % and an average molecular weight of 500 to 10,000 Dalton by cationic polymerization of isobutene or of isobutene and monomers copolymerizable with isobutene in the presence of solvent-stabilized transition metal complexes with weakly coordinated anions.
Description
- The present invention relates to a process for the production of highly reactive polyisobutenes with a content of terminal vinylidene groupings of greater than 80 mol % and an average molecular weight of 500 to 10,000 Dalton by cationic polymerization of isobutene, in the liquid phase, in the presence of monomeric, solvent-stabilized transition metal complexes with weakly coordinating anions.
- High molecular weight polyisobutenes with molecular weights up to several 100,000 Dalton have long been known and the production thereof is described, for example, in H. Güterbock: Polyisobutylen und Mischpolymerisate, pages 77 to 104, Springer, Berlin 1959.
- Polyisobutenes with molecular weights of 500 to 5,000 Dalton are produced with the assistance of Lewis acid catalysts, such as aluminum chloride, aluminumalkyl chlorides or boron trifluoride and usually have less than 10 mol % of terminal double bonds (vinylidene groupings) and a molecular weight distribution (dispersity) of between 2 and 5.
- A distinction is drawn between these conventional polyisobutenes and “highly reactive” polyisobutenes, which have an elevated content of terminal vinylidene groupings of greater than 60 mol %. Highly reactive polyisobutenes have a considerable market share and are used, for example, as an intermediate for the production of additives for lubricants and fuels, as described, for example, in DE-A 27 02 604. These additives are produced by initially producing polyisobutene/maleic anhydride adducts, in particular polyisobutenyl succinic anhydrides, by the reaction of predominantly terminal double bonds of the polyisobutene with maleic anhydride, which are then reacted with certain amines to yield the finished additive. Since it is mainly the terminal vinylidene groupings which react during adduct formation with maleic anhydride, whereas, depending upon their position, the double bonds located further within the macromolecules do not give rise to any or any distinctly lower conversion without the addition of halogens. The proportion of terminal vinylidene groupings in the molecule is an important quality criterion for this type of polyisobutene.
- Further quality criteria for polyisobutenes for the stated intended application are the average molecular weight and the molecular weight distribution, also known as dispersity, of the macromolecules contained in the polyisobutene. In general polyisobutenes with average molecular weights (Mn) of 500 to 5,000 Dalton are used as intermediates for the production of the mentioned lubricant and fuel additives.
- When isobutene is polymerized, polyisobutene products are obtained, the polyisobutene components of which, i.e. the polyisobutene macromolecules, have a random molecular weight distribution of a greater or lesser width. The wider the molecular weight distribution of these polyisobutenes, the greater the content thereof of polyisobutene macromolecules having relatively low or relatively high molecular weights, which are less suitable for the mentioned intended application.
- It is accordingly advantageous to produce highly reactive isobutenes having moderate molecular weights with the narrowest possible molecular weight distribution, in order to reduce the proportion of unwanted, relatively low or high molecular weight polyisobutenes in the resultant product and thus to improve the quality thereof.
- According to the teaching of DE-A 27 02 604, reactive polyisobutenes comprising up to 88 wt. % of terminal double bonds can be obtained by boron trifluoride-catalyzed polymerization of isobutene at temperatures of −50 to +30° C. and residence times of less than 10 minutes. A value of no lower than 1.8 is found for the dispersity of the polyisobutenes produced in this manner.
- Polyisobutenes with similarly high proportions of terminal double bonds, but with a narrower molecular weight distribution are obtainable if partially deactivated catalysts are used, such as for example complexes prepared from boron trifluoride, alcohols and/or ethers. Processes of this type are described, for example, in EP-A 145 235, U.S. Pat. No. 5,408,418 and WO 99/64482.
- While reaction temperatures of above 0° C. are disclosed in the above cited referenced and the Examples, therein only give rise to an elevated content of terminal double bonds of greater than 80% if temperatures of distinctly below 0° C. are used.
- It is apparently possible to produce polyisobutenes with a content of up to 95 mol % of terminal double bonds using the gas phase process of U.S. Pat. No. 3,166,546 and the process of U.S. Pat. No. 3,024,226, in which a boron trifluoride/sulfur dioxide gas mixture is used as the catalyst. These polyisobutenes are characterized on the basis of the results of infrared spectroscopy. However, investigation by13C nuclear magnetic resonance spectroscopy (13C NMR spectroscopy) of the polyisobutenes produced according to said processes revealed a content of at most 40 mol % of terminal double bonds.
- U.S. Pat. No. 4,227,027 discloses boron trifluoride-catalyzed alkyl transfer reactions, wherein the catalysts are adducts of boron trifluoride and diols or polyols at temperatures of 40 to 120° C. When this process was applied to the polymerization of isobutene using a boron trifluoride/1,2-butanediol adduct as catalyst, the only product to be obtained was diisobutylene. Polyisobutene was not formed.
- Another process for the production of highly reactive polyisobutenes involves living cationic polymerization of isobutene with subsequent dehydrochlorination, as is described, for example, in U.S. Pat. No. 5,340,881. This process yields up to 100% of terminal double bonds, but requires low temperatures and a complex solvent mixture, which unnecessarily complicates recycling of the unreacted starting materials.
- Accordingly, highly reactive polyisobutenes with an average molecular weight of 500 to 5,000 Dalton and a content of terminal vinylidene groupings of greater than 80 mol % are only obtained if temperatures of below 0° C. are used. Such cooling is associated with considerable costs, which reduce the economic viability of the process.
- An object of the present invention was to develop an economic process, which operates at temperatures of above 0° C. and yields the described highly reactive polyisobutenes.
- It has now been found that such a process may be achieved if monomeric, solvent-stabilized transition metal complexes with weakly coordinating anions are used as the catalysts.
- The present invention provides a process for the production of highly reactive isobutene homo- and copolymers with a content of terminal vinylidene groupings of greater than 80 mol % and an average molecular weight of 500 to 10,000 Dalton, wherein isobutene or isobutene with copolymerizable monomers is/are polymerize in the presence of a transition metal catalyst of the general formula
- [M(R1-CN)4-6] (A)2, in which
- M is a metal from the 3rd to 12th periods of the periodic system of elements,
- R1 is a C1-C8 alkyl group and
- A is a weakly coordinating anion.
- Copolymerizable monomers, which may be used in the process of the present invention, include, for example, isoprene and/or styrene. The process according to the present invention is preferably used to produce copolymers based on isobutene and isoprene, which have molecular weights from approximately 2,000 to 7,000 Dalton and have a content of incorporated isoprene of up to 60% (determined by nuclear magnetic resonance spectroscopy).
- The highly reactive polyisobutenes produced according to the process of the present invention preferably have a content of terminal vinylidene groupings of 95 to 100 mol % and an average molecular weight of 2,000 to 7,000 Dalton.
- The polyisoprenes according to the present invention are soluble in many organic solvents, such as chloroform, dichloromethane, hexane, heptane, cyclohexane, toluene or benzene or mixtures thereof.
- The process of the present invention is preferably performed in an inert organic solvent, wherein halogenated and halogen-free hydrocarbons, which may optionally be substituted by nitro groups, or mixtures thereof are used. Dichloromethane, chloroform, dichloroethane, tetrachloroethane, hexane or pentane, and cycloalkanes, such as cyclohexane, and aromatic hydrocarbons, such as toluene and benzene, are, for example, preferred. The quantity of solvent may be determined by routine experimentation. The concentration of the introduced monomers in the solvent used is preferably in the range from 0.01 to 10 mol/l, more preferably 0.1 to 2 mol/l.
- Preferably the transition metal catalysts of the above-stated general formula are those in which M is Mn, Ni, Cr or Zn and A contains anions of the formulae BF4 −, SbX6 −, PX6 − and/or B(Ar)4 − as well as B(Ar)4 − anions bridged by cyclic groupings, wherein Ar denotes phenyl, which have 1 to 5 substituents, such as F, Cl or CF3. Cyclic bridges, which may preferably be considered for B (Ar)4 − anions, include imidazolyl bridges.
- In the above general formula, R1 preferably denotes C1-C4 alkyl residues, such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl or tert.-butyl.
-
- The transition metal catalysts are used in the process according to the present invention in a molar ratio of 1:15,000,000 to 1:10, preferably of 1:500,000 to 1:10,000, relative to the introduced quantities of monomers. The concentration of the introduced catalysts in the reaction mixture is in the range from 0.01 to 10 mmol/l, preferably 0.1 to 2 mmol/l.
- Polymerization is performed according to the present invention at temperatures of approximately 0 to 100° C., preferably from 20 to 60° C.
- The transition metal catalysts useful according to the present invention are known per se and may be produced using known processes, as described, for example, in Wayne E. Buschmann, Joel S. Miller, Chem. Eur. J. 1998, 4(9), 1731-1737, and Bruce H. Lipshutz, Wayne Vaccaro, Bret Huft, Tetrahedron Letters 1986, 27(35), 4095-4098 and LaPointe, Robert E.; Roof, Gordon R.; Abboud, Khalil A.; Klosin, Jerzy. New Family of Weakly Coordinating Anions. Journal of the American Chemical Society (2000), 122(39), 9560-9561.
- The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
- Molecular weight Mn was determined by means of gel permeation chromatography in chloroform. Column: Waters Ultrastyragel®, pore size 10,000 and 100,000 Å and Waters Styragel®, pore size 500 Å, detection: differential refractometer (Waters R 401), calibration: polystyrene standards.
- Monomers gaseous at room temperature were advantageously dried by using columns packed with phosphorus pentoxide and finely divided potassium on aluminum oxide, while liquid monomers were dried by columns with aluminum oxide and distillation over sodium/aluminum oxide.
- Halogenated solvents, such as for example dichloromethane, were dried with calcium hydride and distilled under inert gas.
- Aliphatic solvents, such as for example hexane, were dried with sodium and distilled.
- The polymers were stabilized by addition of 2,2′-methylene-bis(4-methyl-6-tert-butylphenol) (Vulkanox®BKF, Bayer AG, Leverkusen).
- 12.80 mg of initiator [Mn(NCCH3)6][B(C6H3(CF3)2)4]2 (5.0·10−6 mol) were weighed out into a 38 ml autoclave under argon as protective gas and 20 ml of dry dichloromethane were added in a cooling bath at −40° C. 3 ml (1.988 g=0.0355 mol) of freshly condensed isobutene were added to the initiator solution. The isobutene was previously dried with a molecular sieve and potassium on activated carbon. The autoclaves were sealed and polymerization performed for 9 hours at 30° C. The solution remained colorless throughout the entire polymerization. After 9 hours, polymerization was terminated by addition of methanol and the polymer precipitated. A colorless, high viscosity polymer was obtained, which was dried to constant weight under a vacuum (50° C./0.1 mbar). 0.25 g of polymer (16.9% yield) with a molecular weight (Mn) of 9.0*103 Dalton (PDI=1.6) were obtained. The polymer can be stored in air and remains completely soluble.
- 12.43 mg of initiator [Mn(NCCH3)6][C3H3N2(B(C6F5)3)2]2 (5.0·10−6 mol) were weighed out into a 38 ml autoclave under argon as protective gas and 20 ml of dry dichloromethane were added in a cooling bath at −40° C. 3 ml (1.988 g=0.0355 mol) of freshly condensed isobutene were added to the initiator solution. The isobutene was previously dried with a molecular sieve and potassium on activated carbon. The autoclaves were sealed and polymerization performed for 16 hours at 30° C. and this solution too remained colorless throughout the entire polymerization. After the stated time, polymerization was terminated by addition of methanol and the polymer precipitated. A colorless, high viscosity polymer was obtained, which was dried to constant weight under a vacuum (50° C./0.1 mbar). 0.59 g of polymer (39% yield) were obtained with a molecular weight (Mn) of 6.4*103 Dalton (PDI=1.7). The polymer can be stored in air and remains completely soluble.
- The content of terminal vinylidene end groups is 100 mol % according to1H-NMR.
- 24.86 mg of initiator [Mn(NCCH3)6][C3H3N2(B(C6F5)3)2]2 (1.0·10−5 mol) were weighed out into a 38 ml autoclave under argon as protective gas and 20 ml of dry dichloromethane were added in a cooling bath at −40° C. 3 ml (1.988 g=0.0355 mol) of freshly condensed isobutene were added to the initiator solution. The isobutene was previously dried with a molecular sieve and potassium on activated carbon. The autoclaves were sealed and polymerization performed for 16 hours at 30° C. and this solution too remained colorless throughout the entire polymerization. After the stated time, polymerization was terminated by addition of methanol and the polymer precipitated. A colorless, high viscosity polymer was obtained, which was dried to constant weight under a vacuum (50° C./0.1 mbar). 0.69 g of polymer (45% yield) were obtained with a molecular weight (Mn) of 5.5*103 Dalton (PDI=1.8). The polymer can be stored in air and remains completely soluble.
- The content of terminal vinylidene end groups is 100 mol % according to1H-NMR.
- Isothermal polymerization of isobutene was performed at 40° C. in a polymerization autoclave. The polymerization autoclave was heat treated and flooded with argon before the reaction. 93 mL of dichloromethane were then introduced and adjusted to a temperature of 40° C. As soon as the temperature has reached the desired value, isobutene (p(IB)=2 bar) was added under isothermal conditions until the solution was completely saturated. Saturation proceeds at a stirring speed of 400 revolutions per minute, while polymerization was performed at a stirrer speed of 1,000 revolutions per minute. The reaction began with the addition of 5 mL of a 2 mmolar solution of [Mn(NCCH3)6][B(C6H2(CF3)3)4]2 (n(I)=10 μmol) in dichloromethane. The initiator solution was injected into the monomer solution with overpressure and the injection system was post-rinsed with 2 mL of dichloromethane (V(CH2Cl2)total=100 mL). With the assistance of external and internal cooling (manual control), the temperature was held constant during the reaction. Consumed monomer was continuously replenished. After a reaction time of 16 h, no further polymerization occurred. Overpressure in the autoclave was vented while the mixture was slowly stirred and the polymer was then precipitated in an excess of methanol.
- Once the solvent evaporated, the polymer was dried to constant weight under a fine vacuum. It proved possible to obtain 67.0 g of polymer having a molar mass (Mn) determined by means of gel permeation chromatography of 2,100 Dalton (PDT=1.2).
- The content of terminal vinylidene end groups was 100 mol % according to1H-NMR.
- 12.43 mg portions of initiator [Mn(NCCH3)6][C3H3N2(B(C6F5)3)2]2 (5.0·10−6 mol) were weighed out into twelve 38 ml autoclaves under argon as protective gas and 20 ml of dry dichloromethane were added to each in a cooling bath at −40° C. The weighed out quantity of isoprene and isobutene was varied. The autoclaves were sealed and polymerization performed for 16 hours at 30° C. in a water bath. Once the polymer had been precipitated with methanol and stabilized with BKF (0.02 g per sample), the polymers were dried to constant weight under a fine vacuum (0.1 mbar/25° C.). Conversion was determined gravimetrically, while molar masses were determined by means of gel permeation chromatography. The quantity of incorporated isoprene was determined by means of nuclear magnetic resonance spectroscopy. The results are listed in Table 1.
TABLE 1 Copolymerization of isobutene/isoprene with Mn complexes IB:IP/mol % Conversion/% Mn · 10−3/Dalton mol % IB/IP polymer 100:0 32.9 6.4 0.0 98:2 6.6 5.6 1.5 96:4 14.9 5.9 2.3 94:6 6.2 4.8 2.3 92:8 19.9 4.5 3.6 90:10 6.2 2.8 7.7 80:20 2.3 3.3 6.0 70:30 1.8 2.8 not determinable 50:50 3.0 2.9 not determinable 30:70 6.1 2.9 not determinable 0:100 0.7 2.6 not determinable - All the polymers were completely soluble in toluene and colorless, high viscosity liquids.
- Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (11)
1. A process for the production of highly reactive isobutene homopolymers and copolymers with a content of terminal vinylidene groupings of greater than 80 mol % and an average molecular weight of 500 to 10,000 Dalton, comprising polymerizing an isobutene monomer or an isobutene and a copolymerizable monomer(s) in the presence of a transition metal catalyst of the general formula [M(R1-CN)4-6] (A)2, wherein
M is a metal from the 3rd to 12th periods of the periodic system of elements,
R1 is a C1-C8 alkyl group and
A is a weakly coordinating anion.
2. The process according to claim 1 , wherein the polymerization is performed at a temperature from 0 to 100° C.
3. The process according to claim 2 , wherein the polymerization is performed at a temperature from 20 to 60° C.
4. The process according to claim 1 , wherein the copolymerizable monomer is isoprene, styrene or a mixture thereof.
5. The process according to claim 1 , wherein the polymerization is in the presence of an inert organic solvent.
6. The process according to claim 1 , wherein the catalyst is introduced in a molar ratio of 1:15,000,000 to 1:10, relative to the total amount of monomer.
7. The process according to claim 1 , wherein M is Mn, Ni, Cr or Zn.
8. The process according to claim 1 , wherein A comprises anions of the formulae BF4 −, SbX6 −, PX6 −, B(Ar)4 − or B(Ar)4 − anions bridged by cyclic groupings wherein Ar is a phenyl with 1 to 5 substituents.
9. The process according to claim 8 , wherein the substituent is Fl, Cl of CF3.
10. The process according to claim 1 , wherein R1 is a C1-C4 alkyl residue.
11. The process according to claim 11 , wherein R1 is methyl, ethyl, propyl, butyl, isobutyl or tert-butyl.
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GB202118103D0 (en) | 2021-12-14 | 2022-01-26 | Innospec Ltd | Fuel compositions |
GB202204084D0 (en) | 2022-03-23 | 2022-05-04 | Innospec Ltd | Compositions, methods and uses |
WO2023183460A1 (en) | 2022-03-23 | 2023-09-28 | Innospec Fuel Specialities Llc | Compositions, methods and uses |
GB202206069D0 (en) | 2022-04-26 | 2022-06-08 | Innospec Ltd | Use and method |
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GB2618101A (en) | 2022-04-26 | 2023-11-01 | Innospec Ltd | Use and method |
EP4279566A1 (en) | 2022-05-20 | 2023-11-22 | TotalEnergies OneTech | Compounds and compositions useful for scavenging hydrogen sulphide and sulfhydryl-containing compounds |
WO2024023490A1 (en) | 2022-07-26 | 2024-02-01 | Innospec Fuel Specialties Llc | Improvements in fuels |
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- 2003-03-03 DE DE50304702T patent/DE50304702D1/en not_active Expired - Lifetime
- 2003-03-11 US US10/385,556 patent/US20030176606A1/en not_active Abandoned
- 2003-03-12 CA CA002421688A patent/CA2421688A1/en not_active Abandoned
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- 2003-03-14 JP JP2003070662A patent/JP4541652B2/en not_active Expired - Fee Related
- 2003-03-14 RU RU2003106980/04A patent/RU2308462C2/en not_active IP Right Cessation
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Cited By (5)
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US9315752B2 (en) | 2007-09-27 | 2016-04-19 | Innospec Limited | Fuel compositions |
US11155655B2 (en) | 2018-03-21 | 2021-10-26 | Lg Chem, Ltd. | Organometal catalyst having cationic transition metal complex and borate-based bulky anion, method for preparing the same, and method for preparing oligomer using the same |
US11414504B2 (en) | 2018-03-21 | 2022-08-16 | Lg Chem, Ltd. | Method for preparing transition metal complex |
US11578152B2 (en) | 2018-04-05 | 2023-02-14 | Lg Chem, Ltd. | Cationic metal complex, organometal catalyst having borate-based bulky anion, method for preparing the same, and method for preparing oligomer or polymer using the same |
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Also Published As
Publication number | Publication date |
---|---|
DE10211418A1 (en) | 2003-09-25 |
US7291758B2 (en) | 2007-11-06 |
JP4541652B2 (en) | 2010-09-08 |
EP1344785A1 (en) | 2003-09-17 |
CN1445249A (en) | 2003-10-01 |
CN1276931C (en) | 2006-09-27 |
EP1344785B1 (en) | 2006-08-23 |
DE50304702D1 (en) | 2006-10-05 |
JP2003277428A (en) | 2003-10-02 |
CA2421688A1 (en) | 2003-09-15 |
RU2308462C2 (en) | 2007-10-20 |
US20060173227A1 (en) | 2006-08-03 |
HK1059445A1 (en) | 2004-07-02 |
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