WO2001087996A2 - Catalyseur de polymerisation d'olefines et procede, polymere, derives de polymere, lubrifiants et carburants obtenus a partir de ces derniers - Google Patents

Catalyseur de polymerisation d'olefines et procede, polymere, derives de polymere, lubrifiants et carburants obtenus a partir de ces derniers Download PDF

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WO2001087996A2
WO2001087996A2 PCT/US2001/015532 US0115532W WO0187996A2 WO 2001087996 A2 WO2001087996 A2 WO 2001087996A2 US 0115532 W US0115532 W US 0115532W WO 0187996 A2 WO0187996 A2 WO 0187996A2
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hydrocarbyl
olefin
catalyst
polymer
group
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PCT/US2001/015532
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English (en)
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WO2001087996A3 (fr
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Saleem Al-Ahmad
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The Lubrizol Corporation
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Priority to CA002409110A priority Critical patent/CA2409110A1/fr
Priority to JP2001585213A priority patent/JP2003533562A/ja
Priority to US10/258,012 priority patent/US20040118035A1/en
Priority to AU2001261571A priority patent/AU2001261571A1/en
Priority to EP01935478A priority patent/EP1282652A2/fr
Publication of WO2001087996A2 publication Critical patent/WO2001087996A2/fr
Publication of WO2001087996A3 publication Critical patent/WO2001087996A3/fr

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    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

  • the present invention involves a novel catalyst to polymerize olefins or olefin-containing compounds, a polymerization process, a polymer, derivatives of the polymer, and lubricants and fuels that include the polymer or derivatives of the polymer.
  • the catalyst provides a route to a polyethylene having unique properties and utility in various commercial applications including as a performance additive or as an intermediate to performance additives for use in lubricants and fuels.
  • U.S. Patent 6,063,973 filed March 19, 1999 disclose highly branched polyethylene fluids having a molecular weight from about 300 to 30,000.
  • U.S. Patent 6,057,466 filed September 29, 1997 disclose catalysts from palladium and bidentate ligands complexed to the metal by heteroatoms for polymerizing ethylenically unsaturated compounds.
  • U.S. Patent 6,127,497 filed June 17, 1997 disclose a process for polymerizing olefins using a catalyst from a transition metal compound and a bidentate ligand.
  • U.S. Patent 6,174,975 filed January 13, 1998 disclose a process for polymerizing olefins using a catalyst from nickel compounds chelated with oxygen and nitrogen atoms.
  • ethylene is polymerized to a polymer having unique properties.
  • This ethylene polymer and derivatives thereof are useful in various areas of commerce.
  • the catalyst and process of the present invention are highly efficient in the amount of polymer produced per amount of catalyst and exceptionally durable in the retention of catalyst activity over time.
  • metal complexes and, optionally, an activating compound capable of reacting with the metal complex to form a catalyst are a catalyst for the polymerization of olefins or olefin-containing compounds.
  • the metal complexes are prepared by reacting a metal compound with a bidentate ligand.
  • the metal of the metal compound is selected from the group consisting of transition metals, boron, aluminum, germanium and tin.
  • the bidentate ligand has a nitrogen- coordinating group and a second coordinating group that is an oxygen, sulfur, selenium or tellurium group.
  • the bidentate ligand reacting with the metal compound to form a five-membered ring complex is selected from the group consisting of
  • Q is O, S, Se or Te
  • E, R, R 1 and R 2 are independently hydrogen, hydrocarbyl, cationic counterion or taken together to form a ring are hydrocarbylene, provided that E is hydrocarbyl or hydrocarbylene when Q is O
  • A is a divalent group that forms an aromatic ring and can include N, O and S atoms.
  • the bidentate ligand reacting with the metal compound to form a six- or seven-membered ring complex is selected from the group consisting of
  • Q is O, S, Se or Te
  • M is 1 or 2
  • E, R, R 1 and R 2 are independently hydrogen, hydrocarbyl, cationic counterion or taken together to form a ring are hydrocarbylene provided that E is hydrocarbyl or hydrocarbylene when Q is O
  • A is a divalent group that forms an aromatic ring and can include N, O and S atoms; and n is O or 1.
  • An embodiment of the present invention is the catalyst where the metal of the metal compound is cobalt, nickel, palladium or platinum and the bidentate ligand has a nitrogen-coordinating group and a second coordinating group that is a sulfur group.
  • Another embodiment of the present invention is a process for polymerizing olefins or olefin-containing compounds comprising contacting olefins or olefin- containing compounds under polymerization conditions with the catalyst of the present invention.
  • a further embodiment of the present invention is an olefin polymer prepared by the process of contacting an olefin or olefin-containing compound with the catalyst under polymerization conditions.
  • a still further embodiment of the present invention is a polyethylene polymer that has a number average molecular weight of less than 10,000, branching of about
  • inventions are dispersant and detergent derivatives from the olefin polymer of the present invention to include alkenylsuccinic acids and derivatives thereof, alkylphenols and derivatives thereof, and alkylarenes and derivatives thereof.
  • Additional embodiments of the invention are lubricant and fuel compositions that include the olefin polymer of the present invention, its dispersant derivatives or its detergent derivatives.
  • the catalyst of the present invention finds use in the polymerization of olefins or olefin-containing compounds.
  • Polymerization is defined herein to be the combining of two or more monomers of olefin or olefin-containing compound.
  • the polymerization can involve a single monomer to give homopolymers or a mixture of two or more monomers to give copolymers.
  • the olefins are acyclic or cyclic alkenes having a double bond or polyenes having two or more double bonds.
  • the olefins are preferably C 2 to C 50 alkenes, more preferably C 2 to C 20 alkenes and most preferably C 2 to C 2 o 1 -alkenes such as ethylene, propylene, 1-butene, isobutylene, 1-octene and 1-decene.
  • the olefin-containing compounds are compounds that have a polymerizable double bond in addition to one or more other functional groups.
  • Polymerizations using the catalyst of the present invention may involve homopolymers of an olefin or of an olefin-containing compound, or copolymers of a mixture of two or more olefins, of a mixture of two or more olefin-containing compounds, or of a mixture of one or more olefins and one or more olefin- containing compounds.
  • the catalyst of the present invention comprises a metal complex and, optionally, an activating compound capable of reacting with the metal complex to form the catalyst.
  • the metal complex is prepared by reacting a metal compound with a bidentate ligand.
  • the metal of the metal compound is selected from the group consisting of transition metals, boron, aluminum, germanium and tin. Especially preferred metals are cobalt, nickel, palladium and platinum.
  • metal compounds useful in forming metal complexes are NiBr 2 (l,2-dimethoxyethane), NiCl 2 (l ,2-dimethoxyethane), [Pd(CH 3 )(CH 3 CN)(l ,5-cyclooctadiene)]SbF 6 and CoCl 2 .
  • the bidentate ligand that reacts with the metal compound to form the metal complex, has a nitrogen-coordinating group and a second coordinating group that is an oxygen, sulfur, selenium or tellurium group. Especially preferred for the second coordinating group is a sulfur group.
  • the bidentate ligand that reacts with the metal compound to form a five- membered ring chelate metal complex is selected from the group consisting of
  • Q is O, S, Se or Te
  • E, R, R 1 and R 2 are independently hydrogen, hydrocarbyl, cationic counterion or taken together to form a ring are hydrocarbylene provided that E is hydrocarbyl or hydrocarbylene when Q is O
  • A is a divalent group that forms an aromatic ring and can include N, O and S atoms.
  • Hydrocarbyl and hydrocarbylene throughout this application are respectively univalent and divalent radicals of one or more carbon atoms that are predominately hydrocarbon in nature, but may have nonhydrocarbon substituent groups and may contain heteroatoms.
  • the bidentate ligand that reacts with the metal compound to form a six- or seven-membered ring chelate metal complex is selected from the group consisting of
  • Q is O, S, Se or Te
  • m is 1 or 2
  • E, R, R 1 and R 2 are independently hydrogen, hydrocarbyl, cationic counterion or taken together to form a ring are hydrocarbylene provided that E is hydrocarbyl or hydrocarbylene when Q is O
  • A is a divalent group that forms an aromatic ring and can include N, O and S atoms; and n is O or 1.
  • Instances of bidentate ligands and of metal complexes, prepared by reaction of these bidentate ligands with metal compounds, and their preparation are provided in the non-limiting examples listed below.
  • a mole ratio of metal compound to bidentate ligand of 1 : 1-2 may be used while a mole ratio of 1:1-1.5 is preferred.
  • the crystalline complex of Example 10 hereinbelow was prepared from NiBr 2 l,2-dimethoxyethane and a bidentate ligand having one N and one S coordinating group where the ligand was an imine formed by condensing 2,6-diisopropylaniline with 3-(methylthio)-2-butanone.
  • the complex of Example 10 was found by x-ray crystallography to be a distorted tetrahedral configuration around the Ni atom.
  • the activating compounds or cocatalysts are compounds that activate the metal complexes in any manner that allows catalytic polymerization to occur via insertion or coordination polymerization.
  • Examples of activating compounds include alkylaluminoxanes, organoaluminum compounds such as aluminum alkyls and alkylaluminum halides, aluminum halides, hydrocarbylborons, halogenated hydrocarbylborons such as fluorohydrocarbylboron compounds, acids of noncoordinating anions, acidic aluminas, acidic silicas, acidic clays, acidic zirconias and Lewis acids not already listed above.
  • Methylaluminoxane is a preferred activating compound.
  • the mole ratio of the metal complex to activating compound is 1:1-10,000, preferably 1:1-3,000 and more preferably 1:1-1,000.
  • the process of the present invention for polymerizing olefins or olefin- containing compounds involves contacting olefins or olefin-containing compounds under polymerizing conditions with the catalyst of the present invention.
  • the polymerization process may involve solution, slurry (or suspension) or gas phase processing conditions as described in WO 98/49208, the disclosure of which is incorporated herein by reference.
  • the polymerization process may involve supported catalysts that use inorganic solids or polymers for supports.
  • inorganic supports are silica, alumina, magnesia, titania, zirconia, clay and mixtures thereof. Formation of a supported catalyst is described in WO 98/49208, the disclosure of which is incorporated herein by reference.
  • the quantity of support material used may range from about 1 to 100,000 grams per gram of the complexed metal present in the catalyst.
  • the polymerization process may involve temperatures from -100°C to 250°C and pressures from atmospheric to 30,000 psig.
  • Solvents suitable for the polymerization process are those that are inert relative to the polymerization and thus allow the polymerization to proceed.
  • Preferred solvents are aliphatic and aromatic hydrocarbons such as methylene chloride and toluene.
  • the polymerization process is conducted for a period of time sufficient to form the polymer.
  • the catalyst and process for polymerization of this invention provide unique processing advantages in terms of productivity and durability.
  • the catalyst and process display a very high efficiency in producing polymer as measured by the yield ratio of amount of polymer produced per amount of complex used over the actual polymerization reaction. A yield ratio of 2800 has been observed in the examples hereinbelow.
  • An ethylene polymer of the present invention has a unique combination of properties which are a number average molecular weight (Mn) of less than 10,000 and branching of about 100 or more methyl-ended branches per 1,000 methylene carbon atoms and a reactivity with the acylating agent maleic anhydride of about 70% or greater.
  • the olefin polymer of this invention provides several advantages as a performance chemical and as an intermediate to performance chemicals for use in various applications of commerce. In general the olefin polymers provide a greater variety of performance chemicals.
  • the ethylene polymer and its derivatives have several advantages- a low cost and abundant source in ethylene, chlorine-free polymer and derivatives, and derivatives high in actives content.
  • a hydrocarbyl-substituted acylating agent of the present invention comprises the reaction product of the olefin polymer of this invention and an unsaturated carboxylic acid or a reactive equivalent thereof, glyoxylic acid or a reactive equivalent thereof, or a mixture of two or more thereof.
  • the olefin polymer can be the ethylene polymer of this invention.
  • the unsaturated carboxylic acid or reactive equivalent thereof includes maleic acid, maleic anhydride, acrylic acid, itaconic acid and fumaric acid.
  • Reactive equivalents of glyoxylic acid include hemiacetal glyoxylate esters.
  • a dispersant composition of the present invention comprises the reaction product of the hydrocarbyl-substituted acylating agent of this invention and a compound selected from the group consisting of an amine, an alcohol, an amino alcohol, a reactive metal compound or a mixture of two or more thereof.
  • the hydrocarbyl-substituted acylating agent can be derived from the olefin polymer of this invention to include the ethylene polymer.
  • the amine can be ammonia, a monoamine, a polyamine, or any organic compound having at least one reactive
  • the polyamine can be an alkylenediamine such as ethylenediamine or a polyalkylene- polyamine such as diethylenetriamine.
  • Alcohols include both monools and polyols having 1 to about 22 carbon atoms.
  • Amino alcohols can have 1 to about 50 carbon atoms and include amines having one or more hydroxy groups such as ethanolamine, diethanolamine and dialkylaminoalkanols such as dimethylaminoethanol and diethylammoethanol.
  • a hydrocarbyl-substituted phenol of the present invention comprises the reaction product of the olefin polymer of this invention and phenol.
  • the olefin polymer includes the ethylene polymer of this invention.
  • Hydrocarbyl-substituted phenols can serve as performance chemicals or as intermediates to performance chemicals. These alkylated phenols can be reacted with coupling agents such as formaldehyde, sulfur and glyoxylic acid to form oligomers of two or more phenolic units. These oligomers can serve as performance chemicals or as intermediates to performance chemicals such as nitrogen- or metal- containing detergents. Hydrocarbyl phenols can also be converted to salicylate derivatives which are useful in numerous applications.
  • a Mannich reaction product of the present invention comprises the reaction product of the hydrocarbyl-substituted phenol of this invention, an aldehyde, and an amine.
  • the hydrocarbyl-substituted phenol can be derived from the olefin polymer of this invention to include the ethylene polymer.
  • the aldehyde can have 1 to about 6 carbon atoms with formaldehyde, in one of its reagent forms such as formalin or paraformaldehyde, being a preferred aldehyde.
  • the amine can be ammonia, a monoamine, a polyamine, an alkanolamine or any organic compound having at least one reactive . N-H group capable of undergoing a Mannich reaction.
  • Monoamines can be primary or secondary amines having 1 to about 22 carbon atoms.
  • Polyamines can be alkylenediamines such as ethylenediamine and N,N-dimethylpropylenediamine or polyalkylenepolyamines such as diethylenetriamine.
  • Alkanolamines can be primary or secondary amines having 1 to about 22 carbon atoms and one or more hydroxy groups such as ethanolamine and diethanolamine.
  • Methods to prepare Mannich reaction products are well known in the art. Both U.S. Patent 5,876,468 and an example hereinbelow provide processing details for a Mannich reaction.
  • a hydrocarbyl-substituted aromatic hydrocarbon of the present invention comprises the reaction product of the olefin polymer of this invention and an aromatic hydrocarbon selected from the group consisting of benzene, toluene, xylenes and naphthalene.
  • the olefin polymer includes the ethylene polymer of this invention.
  • Methods to alkylate an aromatic hydrocarbon with an olefin polymer are well known in the art and generally employ an acid catalyst such as A1C1 or HF.
  • the alkylated aromatic hydrocarbon can serve as a base fluid, diluent or solvent in various applications and is also an intermediate to metal-containing detergents which find use in a multitude of commercial applications.
  • detergents involve sulfonation of the hydrocarbyl- substituted aromatic hydrocarbon using a reagent such as sulfur trioxide to form a sulfonic acid followed by its neutralization with an equivalent of or overbasing with more than an equivalent of a basic metal compound.
  • a reagent such as sulfur trioxide to form a sulfonic acid followed by its neutralization with an equivalent of or overbasing with more than an equivalent of a basic metal compound.
  • the olefin polymer, to include the ethylene polymer, of the present invention can be aminated to form a dispersant or ashless detergent which finds use in various applications.
  • the olefin polymer of this invention or its derivatives can be hydrogenated to provide greater stability for use as performance additives in fuels and lubricants or also as base stocks in the case of the hydrogenated polymers.
  • the olefin polymer to include the ethylene polymer, and its corresponding derivatives generally have utility as performance chemicals or additives in hydrocarbon fluids which include oils of lubricating viscosity, hydrocarbon fuels and petroleum crudes.
  • Ethylene polymers and their derivatives have excellent solubility in hydrocarbon fluids due to the high degree of branching of the polymer where solubility is defined to be at least 0.001 % by weight of a material being incorporated into the hydrocarbon fluid.
  • the olefin polymer and its derivatives can be added directly to a hydrocarbon fluid to form a hydrocarbon fluid composition or can be added to the hydrocarbon fluid as an additive concentrate.
  • An additive concentrate comprises the olefin polymer or a derivative of the olefin polymer and optionally a diluent.
  • the diluent facilitates handling and transfer operations and can be an aliphatic solvent, aromatic solvent, mineral oil, synthetic fluid such as a poly (alpha-olefin) or carboxylate ester, an oil from a plant or animal source, and mixtures of two or more thereof.
  • synthetic fluid such as a poly (alpha-olefin) or carboxylate ester
  • an oil from a plant or animal source and mixtures of two or more thereof.
  • other known performance additives can be present in the additive concentrate or hydrocarbon fluid composition.
  • the hydrocarbon fluid composition or additive concentrate is usually prepared by mixing its components at ambient or elevated temperatures until the mixture is homogeneous.
  • a fuel composition of the present invention comprises a hydrocarbon fuel and the olefin polymer of this invention.
  • the hydrocarbon fuel includes gasoline and diesel fuel.
  • the olefin polymer includes the ethylene polymer of this invention and can function as a viscosity modifier.
  • a fuel composition comprises the hydrocarbon fuel and a derivative of the olefin polymer.
  • Derivatives of the olefin polymer as described above include the hydrocarbyl-substituted acylating agent and corresponding dispersant composition, the hydrocarbyl-substituted phenol, the Mannich reaction product, the hydrocarbyl- substituted aromatic hydrocarbon as well as its sulfonic acid and sulfonate detergent derivatives and the aminated olefin polymer.
  • Derivatives of the olefin polymer as described above also include salicylate, sulfur coupled, formaldehyde coupled and glyoxylic acid coupled derivatives of hydrocarbyl-substituted phenols.
  • a fuel composition comprises a hydrocarbon fuel, at least one component that is the olefin polymer of this invention or a derivative of the olefin polymer, and optionally water or an alcohol such as ethanol where the derivative can function as an emulsifier.
  • a lubricant composition of the present invention comprises a major amount of an oil of lubricating viscosity and the olefin polymer of this invention.
  • the oil of lubricating viscosity includes mineral oils, synthetic fluids such as poly (alpha- olefins) and carboxylate esters and alkylated benzenes, and oils from plants and animals.
  • the olefin polymer includes the ethylene polymer of this invention and can function as a viscosity modifier.
  • a lubricant composition comprises a major amount of the oil of lubricating viscosity and a derivative of the olefin polymer as listed above for fuel compositions.
  • a lubricant comprises an oil, at least one component that is the olefin polymer of this invention or a derivative thereof, and optionally water or an alcohol where the derivative can function as an emulsifier.
  • Metal complexes were prepared under nitrogen atmosphere using a glove box and Schlenk ware handling techniques.
  • Ligands la - le were prepared by the depicted reaction scheme below following the procedure of Example 5 for ligand le. Their corresponding nickel complexes Ua-IIe from NiBr 2 ' l,2-dimethoxyethane (NiBr 2 DME) were prepared following the procedure of Example 10 for Ni complex JJe.
  • the Pd complex IIIc from ligand Ic was prepared as detailed in Example 11.
  • a nickel complex Vc from ligand Ic was prepared in Example 12 from NiCl 2 -l,2-dimethoxyethane.
  • a mixture was prepared of 0.35g (1.3 mmol) N-(l-methylthio-2- propylidene)-2,6-diisopropylaniline Ic in 5 ml of acetonitrile and 5 ml of methylene chloride, and with stirring at room temperature 0.54g (1.07 mmol) of [Pd(CH 3 )(CH 3 CN)(l,5-cyclooctadiene)]SbF 6 (the complex is obtained by: 1) preparing Pd(CH3)Cl(l,5-cyclooctadiene) according to the method of Rulke et alii in Inorg.
  • Ligands If-JJi and Ij were prepared by the depicted reaction scheme below following the procedure of Examples 15a and 15 for ligand Hi.
  • Ligands Ii and fl were prepared by an alternate route in which the substituted aniline and chloroacetone were initially condensed followed by a second condensation of the aniline-chloroacetone condensate with the sodium mercaptide as detailed in Examples 18a and 18 for ligand Ik.
  • Corresponding Ni complexes ⁇ f-IJk from ligands If -Ik were prepared following the procedure of Example 10 for Ni complex He.
  • Pd complexes Illg and IUj from ligands Ig and Ij were prepared following the procedure of Example 11 for Pd complex LTJc.
  • Co complex IVg from ligand Ig was prepared as detailed in Example 27.
  • a complex JJh' from ligand Ih was prepared in Example 28 in which the product was also washed with diethyl ether and tetrahydrofuran in addition to the normal hexane washing.
  • Ligands Il-In were prepared by the depicted reaction scheme below from respectively benzaldehyde, 9-anthraldehyde and 2-(trifluoromethyl)benzaldehyde following the procedure of Example 29 for ligand II.
  • the corresponding Ni complexes Hl-IIn from ligands Il-In were prepared following the procedure of Example 10 for Ni complex lie.
  • Example 35 is representative of the general procedure for polymerizations of ethylene run at 5 psig.
  • Example 35 Ethylene polymerization using Complex Ila and methylaluminoxane.
  • the reactor was charged with a solution of 25 mg of Complex Ua in 50g of toluene.
  • the reactor was then cooled in an ice bath and charged with 2.6g of MAO (10% by weight of methylaluminoxane in toluene, available from Aldrich) under an ethylene atmosphere.
  • the cooling bath was removed, and the reaction mixture was stirred under 5-psig ethylene atmosphere, and soon became warm to the touch. After stirring for 1.5 hours, the reaction was quenched with aqueous MeOH/hydrochloric acid. Removal of toluene on a rotavap gave 2.1g of a colorless oil product.
  • Example 75 is representative of polymerizations of ethylene done with a palladium catalyst.
  • Example 75 Ethylene polymerization using Complex IIIc of example 11.
  • Table 1 of ethylene polymerizations provides instances of the catalyst, polymerization process and ethylene polymer of the present invention.
  • Examples 35-74 involved polymerizations done with a Ni catalyst, Examples 75-77 used a
  • Example 78 used a Co catalyst.
  • b The ethylene source was shut oft after the indicated time, and the reaction mixture was stirred overnight before quenching.
  • °Yield is polymer product obtained in grams.
  • dYield ratio is grams of polymer obtained per gram of complex.
  • eAnalysis by GCMS and H 1 MR indicated formation of a product that was a mixture of C4-C 40 olefins. 'Branching is the number of methyl-ended branches per 1,000 methylene carbons.
  • Examples 79 and 80 involve copolymerizations of the present invention.
  • Example 79 Copolymerization of ethylene and 1-octene using Complex lie and methylaluminoxane.
  • the reactor was charged with 75 mg (0.1545 mmol) of Complex He, 270g of toluene and 12.0g (107.1 mmol) of 1-octene.
  • 7.8g of MAO (13.4 mmol) was charged followed by a continuous supply of ethylene at 100 psig, and the reaction mixture was stirred for 7 hours while keeping the temperature at 25°C.
  • the ethylene supply was shut off, and stirring was continued overnight.
  • GCMS analysis of the reaction mixture indicated the presence of a mixture of C 8 -C 3 2 olefins.
  • the reaction mixture was quenched with hydrochloric acid in a water-methanol mixture.
  • the ratio of methyl H's to combined methylene and methine H's corresponds to 63 methyl- ended branches per 1,000 methylenes, while integration data for aliphatic H's and olefinic H's indicates a Mn of 714.
  • GCMS analysis run on the reaction mixture before quenching indicated the presence of a mixture of olefins that included C 5 , C , C 9 , C ⁇ and C 13 olefins, formed from the copolymerization of ethylene and propylene, although signal intensities were less for odd-numbered olefins relative to even-numbered olefins.
  • Examples 81 and 82 demonstrate the effect of temperature on catalyst activity and on molecular weight and branching of ethylene polymers.
  • Examples 83-86 of Table 2 show the effect of the mole ratio of the cocatalyst to the metal complex on polymerizations of ethylene.
  • aPolymerization of ethylene was done following the procedure of Example 82.
  • bAI/Ni is the mole ratio of methylaluminoxane to Ni complex He.
  • cT0F is turn over frequency of the catalyst measured as moles of ethylene consumed per mole of catalyst.
  • a Polyethylene was Example 66 from Table 1 having a Mn of 1792 and 117 methyl ended branches per 1000 methylenes.
  • bPolyethylene was a blend of several polymerizations using Ni complex llg where polymer blend had a Mn of 6830 and 120 methyl ended branches per 1000 methylenes.
  • cTreat rate was 5-10% by wt. polymer in a mineral oil having a viscosity of 5.85-5.88 cSt
  • Examples 94 and 95 are succinimide dispersant and Mannich detergent/dispersant derivatives of the polyethylene of the present invention.
  • the succinimide dispersant of Example 94 was found to be equivalent to better than standard dispersants derived from polyisobutylene in soot dispersancy testing.
  • Example 94 Preparation of Polyethylene Succinimide Dispersant
  • the alkenylsuccinic anhydride of Example 91 having a total acid number of 69, was diluted with oil to give a product having 50% diluent and heated to 100°C. Polyethylenepolyamine bottoms were added to the diluted anhydride at 100-110°C in a ratio of carbonyl to nitrogen of 6CO:5N. This mixture was heated to 150°C, held at 150°C for 4 hours, and then filtered to give a product having a 0.67% nitrogen content.

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  • Polymers & Plastics (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Abstract

L'invention se rapporte à un catalyseur et à un procédé associé pour la polymérisation d'oléfines ou de composés contenant des oléfines, à des polymères oléfiniques correspondants, à des dérivés de polymères oléfiniques et à des compositions de lubrifiant et de carburant comprenant lesdits polymères oléfiniques ou leurs dérivés. Le catalyseur de polymérisation est un complexe métallique et éventuellement un cocatalyseur, le complexe métallique étant formé à partir d'un ligand bidenté possédant un groupe de coordination azote et un second groupe de coordination choisi parmi les groupes tellurium et sélénium, oxygène et soufre et un composé métallique dans lequel le métal est un métal de transition, du bore, de l'aluminium, du germanium ou de l'étain. On forme des polymères d'éthylène hautement ramifiés et réactifs à partir du catalyseur et du procédé de l'invention. Les polymères d'éthylène et leurs dérivés sont utiles dans diverses applications, par exemple en tant qu'additifs de performance dans les lubrifiants et les carburants.
PCT/US2001/015532 2000-05-15 2001-05-15 Catalyseur de polymerisation d'olefines et procede, polymere, derives de polymere, lubrifiants et carburants obtenus a partir de ces derniers WO2001087996A2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002409110A CA2409110A1 (fr) 2000-05-15 2001-05-15 Catalyseur de polymerisation d'olefines et procede, polymere, derives de polymere, lubrifiants et carburants obtenus a partir de ces derniers
JP2001585213A JP2003533562A (ja) 2000-05-15 2001-05-15 オレフィン重合触媒およびオレフィン重合方法、ならびにそれらのポリマー、ポリマー誘導体、潤滑剤および燃料
US10/258,012 US20040118035A1 (en) 2001-05-15 2001-05-15 Olefin polymerization catalyst and process and polymer, polymer derivatives, lubricants and fuels thereof
AU2001261571A AU2001261571A1 (en) 2000-05-15 2001-05-15 Olefin polymerization catalyst and process and polymer, polymer derivatives, lubricants and fuels thereof
EP01935478A EP1282652A2 (fr) 2000-05-15 2001-05-15 Catalyseur de polymerisation d'olefines et procede, polymere, derives de polymere, lubrifiants et carburants obtenus a partir de ces derniers

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US7560523B2 (en) * 2005-08-25 2009-07-14 Cornell Research Foundation, Inc. Production of isotactic and regiorandom polypropylene based polymer and block copolymers
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Citations (1)

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WO1997002298A1 (fr) * 1995-06-30 1997-01-23 E.I. Du Pont De Nemours And Company Procede de polymerisation d'olefines

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997002298A1 (fr) * 1995-06-30 1997-01-23 E.I. Du Pont De Nemours And Company Procede de polymerisation d'olefines

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Derwent Publications Ltd., London, GB; Class A00, AN 1968-11617Q XP002189557 & JP 43 019024 B (MITSUI KAGAKU KOKYO KABUSHIKI KAISHA) *
LI, XIANG ET AL: "Olefinic substitution reaction catalyzed by sulfur-containing polymeric palladium complexes" J. MOL. CATAL. (1987), 39(1), 55-62, XP001059663 *
See also references of EP1282652A2 *

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EP1282652A2 (fr) 2003-02-12
JP2003533562A (ja) 2003-11-11
CA2409110A1 (fr) 2001-11-22
AU2001261571A1 (en) 2001-11-26
WO2001087996A3 (fr) 2002-08-15

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