EP3362539B1 - Synthetische schmierölzusammensetzungen - Google Patents

Synthetische schmierölzusammensetzungen Download PDF

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Publication number
EP3362539B1
EP3362539B1 EP16856034.0A EP16856034A EP3362539B1 EP 3362539 B1 EP3362539 B1 EP 3362539B1 EP 16856034 A EP16856034 A EP 16856034A EP 3362539 B1 EP3362539 B1 EP 3362539B1
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EP
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Prior art keywords
blend
base stock
lubricating base
polyolefins
cst
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English (en)
French (fr)
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EP3362539A1 (de
EP3362539C0 (de
EP3362539A4 (de
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Gregory S. HUTCHISON
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Phillips 66 Co
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Phillips 66 Co
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Priority claimed from PCT/US2016/056424 external-priority patent/WO2017066186A1/en
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Publication of EP3362539A4 publication Critical patent/EP3362539A4/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
    • C10M2205/223—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/12—Gas-turbines

Definitions

  • This invention relates to synthetic lubricating oil compositions.
  • Lubricating oils have been used in the past to lubricate the bearings of positive displacement compressors, to seal the rotors, and to cool the compressed gases.
  • Lubricating oils typically used in the industry comprise a mineral oil or synthetic oil as a base oil, and various additives for a particular purpose. Oxidation stability and varnish and deposit control are some of the important properties desirable in a lubricant for maximizing-the life of the lubricant, and hence, the life of the equipment, especially under the high temperature and pressure conditions created when operating turbines.
  • EP 0 796 908 A1 relates to synthetic lubricant compositions having good oxidation resistance, compatibility with petroleum lubricants, good corrosion resistance and hydrolytic stability, and being suitable for use in air compressors, turbines, hydraulics, gears, bearings, fuel engines, textile machinery and greases; said lubricant composition comprising a polyalkylene glycol compound in combination with an aromatic compound selected from the group consisting of alkylated aromatic lubricants and alkoxylated aromatic lubricants in an amount effective to improve the oxidation resistance of said polyalkylene glycol compound.
  • a lubricating base stock comprising an alkyl aromatic, a blend of additives, a blend of oil soluble polyalkylene glycols and a blend of polyolefins.
  • the blend of polyolefins comprises at least one metallocene polyolefin.
  • a lubricating base stock comprising an alkyl aromatic ranging from about 50 wt% to about 95 wt%, a blend of additives ranging from about 0.005 wt% to about 5 wt%, a blend of oil soluble polyalkylene glycols ranging from about 5 wt% to about 50 wt%, and a blend of polyalphaolefins ranging from about 10 wt% to about 20 wt%.
  • the blend of polyalphaolefins comprises at least two different types of polyalphaolefins comprising: at least one metallocene polyalphaolefin.
  • a method of manufacturing a lubricating base stock comprising the mixing of an alkyl aromatic, a blend of oil soluble polyalkylene glycols a blend of additives and a blend of polyolefins.
  • the blend of polyolefins comprise at least one metallocene polyolefin.
  • a method of manufacturing a lubricating base stock comprising the mixing of an alkyl aromatic ranging from about 50 wt% to about 95 wt%, a blend of additives ranging from about 0.005 wt% to about 5 wt%, a blend of oil soluble polyalkylene glycols ranging from about 5 wt% to about 50 wt%, and a blend of polyalphaolefins ranging from about 10 wt% to about 20 wt%.
  • the blend of polyalphaolefins comprises at least two different types of polyalphaolefins comprising: at least one metallocene polyalphaolefin.
  • the present embodiment describes a lubricating base stock comprising an alkyl aromatic, a blend of additives, and a blend of oil soluble polyalkylene glycols and a blend of polyolefins.
  • the blend of polyolefins comprises at least one metallocene polyolefin.
  • the alkyl aromatics used can have a kinematic viscosity at 40° C. of about 5 cSt to about 800 cSt, preferably from about 15 to about 500 cSt, and most preferably from about 15 cSt to about 220 cSt, and are selected from alkyl benzenes, alkyl naphthalenes, alkyl anthracenes, and alkyl phenanthrenes, or mixtures thereof.
  • Commercially available examples of such alkyl aromatics are RF 150 ® and RF 300 ® , available at Soltex, and Zerol 150 ® , Zerol 300 ® , and Zerol 500 ® , available at Shrieve Chemical.
  • the preferred alkyl aromatics are alkyl naphthalenes.
  • Commercially available examples of such alkyl naphthalenes are MCP 917 ® and MCP-968 ® , available at Mobil Chemical.
  • the alkyl aromatic is one formed from alkylating agents having from 1 to about 6 carbon atoms, preferably from 1 to about 12 carbon atoms, and most preferably from 1 to about 24 carbon atoms.
  • the alkyl aromatic used in the basestock is mono or di alkylated with an alkylating agent, forming an alkyl aromatic having one or more alkyl groups having from about 6 to about 30 carbons, and having a kinematic viscosity at 40° C. of about 15 cSt to about 500 cSt.
  • alkyl naphthalene is one that has been mono or di alkylated with an alkylating agent, and having from about 10 to about 20 carbon atoms and a kinematic viscosity at 40° C. of from about 15 cSt to about 220 cSt.
  • the lubricating basestock may also contain effective amounts of additives such as antioxidants, rust and corrosion inhibitors, antiwear, extreme pressure, demulsifiers, metal deactivators, lubricity additives, antiwear additives, or such additives as may be required.
  • additives such as tricresyl phosphate (TCP) available at Syn-O-Add, 8484 ® available at Akzo-Nobel, or triphenyl phosphorothionate (TPPT) available at Ciba Geigy.
  • the finished lubricant composition will contain the additive components in minor amounts sufficient to improve the performance characteristics and properties of the oil of lubricating viscosity or basestock blend, or to both the base oil and basestock blend.
  • the amounts of the respective components may vary in accordance with such factors as the type and characteristics of the base oil or basestock blend employed, the type and severity of the service conditions for which the finished product is intended, for example, for use in a positive displacement compressor, such as a rotary screw compressor, a reciprocating rotary vane, or scroll, and the specific performance properties desired in the finished product.
  • the lubricating composition consists essentially of a blend of (A) at least antioxidant and (B) at least one corrosion inhibitor, having excellent oxidation stability and thermal stability, and exhibiting excellent demulsibility and hydrolytic stability, particularly under high temperature and pressure conditions.
  • antioxidants examples include phenyl naphthyl amines (alpha and/or beta), diphenyl amines, including alkylated diphenyl amines.
  • phenyl naphthyl amines alpha and/or beta
  • diphenyl amines including alkylated diphenyl amines.
  • antioxidants are Irganox L-57 ® (available at Ciba Geigy, and Valube 81 ® (available at Vanderbilt Chemical).
  • Suitable antioxidants can also include phenolic antioxidants, aromatic amine antioxidants, sulfurized phenolic antioxidants, and organic phosphites, among others.
  • phenolic antioxidants examples include 2,6-di-tert-butylphenol, liquid mixtures of tertiary butylated phenols, 2,6-di-tert-butyl-4-methylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butyl-phenol), mixed methylene-bridged polyalkyl phenols, and 4,4'-thiobis(2-methyl-6-tert-butylphenol).
  • N,N'-Di-see-butyl-p-phenylenediamine, 4-isopropylaminodiphenyl amine, phenyl-alpha-naphthyl mine, phenyl-beta-naphthyl amine, and ring-alkylated diphenylamines serve as examples of aromatic amine antioxidants.
  • Available antioxidants that can be useful also include Ethanoxo ® 702 available at the Ethyl Corporation, Irganox ® L-135 and Irganox ® L-118, Irganox L-06 ® available at Ciba Geigy, and RC-7130 ® available at Rhein Chemie.
  • Suitable rust and corrosion inhibitors are neutral metal sulfonates such as calcium sulfonate, magnesium sulfonate, sodium sulfonate, barium dinonylnaphthalene sulfonate, and calcium petroleum sulfonate.
  • Other types of rust or corrosion inhibitors which may be used comprise monocarboxylic acids and polycarboxylic acids.
  • suitable monocarboxylic acids are oleic acids, octanoic acid, decanoic acid and dodecanoic acid.
  • Suitable polycarboxylic acids include dimer and trimer acids such as are produced from such acids as tall oil fatty acids, oleic acid, and linoleic acid.
  • carboxylic acid based, metal free materials such as hydroxy alkyl carboxylic esters.
  • Another useful type of rust inhibitor for use in the practice of this invention is comprised of the alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors such as, for example, tetrapropenylsuccinic acid, tetrapropenylsuccinic anhydride, tetradecenylsuccinic acid, tetradecenylsuccinic anhydride, hexadecenylsuccinic acid, hexadecenylsuccinic anhydride, and the like.
  • rust or corrosion inhibitors include ether amines; acid phosphates; amines; polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; imidazolines; and aminosuccinic acids or derivatives thereof. Mixtures of such rust or corrosion inhibitors can be used.
  • U.S. Pat. No. 5,773,393 is incorporated in its entirety herein for its disclosure regarding rust and corrosion inhibitor additives.
  • a commercially available example of a corrosion inhibitor is L-859 ® available at the Lubrizol Corporation.
  • suitable metal deactivators are complex organic nitrogen, oxygen and sulfur-containing compounds.
  • copper compounds such as substituted benzotriazole, alkyl or acyl substituted 5,5'-methylene-bis-benzotriazole, alkyl or acyl substituted 2,5-dimercaptothiazole, salts of salicylaminoguanidine, and quinizarin are useful.
  • Propylgallate is an example of a metal deactivator for magnesium
  • sebacic acid is an example of a deactivator for lead.
  • a commercially available example of a triazole metal deactivator is Irgamet 39 ® available at Ciba Geigy.
  • metal detergents examples include: sulfurized or unsulfurized alkyl or alkenyl phenates, alkyl or alkenyl aromatic sulfonates, sulfurized or unsulfurized metal salts of multi-hydroxy alkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy aromatic sulfonates, sulfurized or unsulfurized alkyl or alkenyl naphthenates, metal salts of alkanoic acids, metal salts of an alkyl or alkenyl multi-acid, metal salts of an alkyl salicylic acid, carboxylates, overbased detergents and chemical and physical mixtures thereof.
  • Examples ashless dispersants that can be used include: alkenyl succinimides, alkenyl succinimides modified with other organic compounds, and alkenyl succinimides modified with boric acid, alkenyl succinic ester.
  • oxidation inhibitors examples include: 4,4'-methylenebis (2,6-di-tertbutylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 4,4'-bis(2-methyl-6-tert-butylphenol), 2,2'-(methylene bis (4-methyl-6-tert-butyl-phenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-isopropylidenebis(2,6-di-tert-butyl phenol), 2,2'-methylenebis(4-methyl-6-nonylphenot), 2,2'-isobutylidene-bis(4,6-dimethylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,6-di-tert-butyl-4-methyl-phenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6
  • rust inhibitors examples include: nonionic polyoxyethylene surface active agents: polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol mono-oleate, polyethylene glycol monooleate, stearic acid and other fatty acids, dicarboxylic acids, metal soaps, fatty acid amine salts, metal salts of heavy sulfonic acid, partial carboxylic acid ester of polyhydric alcohol, and phosphoric ester.
  • nonionic polyoxyethylene surface active agents polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl
  • demulsifiers examples include: addition products of alkylphenol and ethylene oxide, polyoxyethylene alkyl ether, and polyoxyethylene sorbitan ester.
  • friction modifiers examples include: fatty alcohol, fatty acid, amine, borated ester, and other esters.
  • viscosity index improvers examples include: polymethacrylate type polymers, ethylenepropylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity index improvers.
  • pour point inhibitors examples include: polymethyl methacrylate.
  • foam inhibitors examples include: alkyl methacrylate polymers and dimethyl silicone polymers.
  • the polyolefin used in this embodiment can be any of a class of polymers produced from a simple olefin (general formula CnH2n) as a monomer.
  • Examples of polyolefins used can be oil soluble polyolefins or metallocene polyolefins, with the proviso that the blend of polyolefins used in the present invention comprise at least one metallocene polyolefin.
  • the specific type of polyolefins used are is polyalpha-olefins (PAO) or metallocene poly-alpha-olefins (mPAO), with the proviso that the blend of polyolefins used in the present invention comprise at least one metallocene polyolefin.
  • PAO polyalpha-olefins
  • mPAO metallocene poly-alpha-olefins
  • the PAO's can be chosen from any component from a conventional linear alpha-olefin (LAO) production facility or from refinery. It can be used alone to make homo-polymer or together with another LAO available from refinery or chemical plant, including propylene, 1-butene, 1-pentene, and the like, or with 1-hexene or 1-octene made from dedicated production facility.
  • LAO linear alpha-olefin
  • the alpha-olefins can be chosen from the alpha-olefins produced from Fischer-Trosch synthesis. For example, C3 to C16-alpha-olefins, more preferably linear alpha-olefins, are suitable to make homo-polymers.
  • C4 and C14-LAO; C6 and C16-LAO; C8, C10, C12-LAO; or C8 and C14-LAO; C6, C10, C14-LAO; C4 and C12-LAO, etc. are suitable to make co-polymers.
  • any of the PAOs produced herein preferably have a bromine number of 1.8 or less as measured by ASTM D 1159, preferably 1.7 or less, preferably 1.6 or less, preferably 1.5 or less, preferably 1.4 or less, preferably 1.3 or less, preferably 1.2 or less, preferably 1.1 or less, preferably 1.0 or less, preferably 0.5 or less, preferably 0.1 or less.
  • any of the PAOs produced herein are hydrogenated and have a bromine number of 1.8 or less as measured by ASTM D 1159, preferably 1.7 or less, preferably 1.6 or less, preferably 1.5 or less, preferably 1.4 or less, preferably 1.3 or less, preferably 1.2 or less, preferably 1.1 or less, preferably 1.0 or less, preferably 0.5 or less, preferably 0.1 or less.
  • any of the PAOs described herein may have monomer units represented by the formula, in addition to the all regular 1,2-connection.
  • j, k and m are each, independently, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22,
  • n is an integer from 1 to 350 (preferably 1 to 300, preferably 5 to 50) as measured by proton NMR.
  • any of the PAOs described herein preferably have an Mw (weight average molecular weight) of 100,000 or less, preferably between 100 and 80,000, preferably between 250 and 60,000, preferably between 280 and 50,000, preferably between 336 and 40,000 g/mol.
  • any of the PAOs described herein preferably have a Mn (number average molecular weight) of 50,000 or less, preferably between 200 and 40,000, preferably between 250 and 30,000, preferably between 500 and 20,000 g/mol.
  • Mw/Mn molecular weight distribution
  • any of the PAOs described herein preferably have an Mw/Mn of between 1 and 2.5, alternately between 1 and 3.5, depending on fluid viscosity.
  • the Mw, Mn and Mz are measured by GPC method using a column for medium to low molecular weight polymers, tetrahydrofuran as solvent and polystyrene as calibration standard, correlated with the fluid viscosity according to a power equation.
  • any PAO described herein may have a pour point of less than 0° C. (as measured by ASTM D 97), preferably less than -10° C., preferably less than -20° C., preferably less than -25° C., preferably less than -30° C., preferably less than -35° C., preferably less than -50°, preferably between -10 and -80° C., preferably between -15° C. and -70° C.
  • the PAO described herein may have a kinematic viscosity (at 40° C. as measured by ASTM D 445) from about 4 to about 50,000 cSt, preferably from about 5 cSt to about 30,000 cSt at 40° C., alternately from about 4 to about 100,000 cSt, preferably from about 6 cSt to about 50,000 cSt, preferably from about 10 cSt to about 30,000 cSt at 40° C.
  • any PAOs described herein may have a kinematic viscosity at 100° C. from about 1.5 to about 5,000 cSt, preferably from about 2 to about 3,000 cSt, preferably from about 3 cSt to about 1,000 cSt, more preferably from about 4 cSt to about 1,000 cSt, and yet more preferably from about 8 cSt to about 500 cSt as measured by ASTM D445.
  • the PAOs preferably have viscosities in the range of 2 to 500 cSt at 100° C. in one embodiment, and from 2 to 3000 cSt at 100° C. in another embodiment, and from 3.2 to 300 cSt in another embodiment.
  • the PAOs has a KV100 of less than 200 cSt.
  • any PAO described herein may have a kinematic viscosity at 100° C. from 3 to 10 cSt and a flash point of 150° C. or more, preferably 200° C. or more (as measured by ASTM D 56).
  • any PAO described herein may have a dielectric constant of 2.5 or less (1 kHz at 23° C. as determined by ASTM D 924).
  • any PAO described herein may have a specific gravity of 0.75 to 0.96 g/cm 3 , preferably 0.80 to 0.94 g/cm 3 .
  • any PAO described herein may have a viscosity index (VI) of 100 or more, preferably 120 or more, preferably 130 or more, alternately, form 120 to 450, alternately from 100 to 400, alternately from 120 to 380, alternately from 100 to 300, alternately from 140 to 380, alternately from 180 to 306, alternately from 252 to 306, alternately the viscosity index is at least about 165, alternately at least about 187, alternately at least about 200, alternately at least about 252.
  • VI viscosity index
  • Viscosity index is determined according to ASTM Method D 2270-93 [1998].
  • kinematic viscosity values reported for fluids herein are measured at 100° C. unless otherwise noted. Dynamic viscosity can then be obtained by multiplying the measured kinematic viscosity by the density of the liquid.
  • the mPAO used can be a co-polymer made from at least two alpha-olefins or more, or a homo-polymer made from a single alpha-olefin feed by a metallocene catalyst system.
  • This copolymer mPAO composition is made from at least two alpha-olefins of C3 to C30 range and having monomers randomly distributed in the polymers.
  • the average carbon number is at least 4.1.
  • Ethylene and propylene, if present in the feed, can be present in the amount of less than 50 wt % individually or preferably less than 50 wt % combined.
  • the copolymers can be isotactic, atactic, syndiotactic polymers or any other form of appropriate tacticity. These copolymers have useful lubricant properties including excellent VI, pour point, and low temperature viscometrics by themselves or as blend fluid with other lubricants or other polymers. Furthermore, these copolymers have narrow molecular weight distributions and excellent lubricating properties.
  • mPAO is made from the mixed feed LAOs comprising at least two and up to 26 different LAOs selected from C3 to C30 linear alpha-olefins.
  • the mixed feed LAO is obtained from an ethylene growth process using an aluminum catalyst or a metallocene catalyst.
  • the growth olefins comprise mostly C6 to C18-LAO. LAOs from other process can also be used.
  • This homo-polymer mPAO composition is made from single alpha-olefin choosing from C3 to C30 range, preferably C3 to C16, most preferably C3 to C14 or C3 to C12.
  • the homo-polymers of the invention can be isotactic, atactic, syndiotactic polymers or any other form of appropriate tacticity. Often the tacticity can be carefully tailored by the polymerization catalyst and polymerization reaction condition chosen or by the hydrogenation condition chosen.
  • These homo-polymers have useful lubricant properties including excellent VI, pour point, and low temperature viscometrics by themselves or as blend fluid with other lubricants or other polymers. Furthermore, these homo-polymers have narrow molecular weight distributions and excellent lubricating properties.
  • the activated metallocene catalyst can be simple metallocenes, substituted metallocenes or bridged metallocene catalysts activated or promoted by, for instance, methylaluminoxane (MAO) or a non-coordinating anion, such as N,N-dimethylanilinium tetrakis(perfluorophenyl)borate or other equivalent non-coordinating anion.
  • MAO methylaluminoxane
  • non-coordinating anion such as N,N-dimethylanilinium tetrakis(perfluorophenyl)borate or other equivalent non-coordinating anion.
  • OSP oil soluble polyalkylene glycols
  • OSP is defined as polyalkylene glycol's that can be miscible with common base oils.
  • OSP's are miscible with the alkyl aromatic chosen as part of the lubricating base stock.
  • polyalkylene glycol's that are miscible are those that typically have increased carbon to oxygen ratios.
  • butylene oxide is miscible in alkyl aromatics
  • tetrahydrofuran is more miscible than butylene oxide.
  • styrene oxide would be more miscible than tetrahydrofuran and other higher alpha olefin oxides would be more miscible than styrene oxide.
  • the polyalkylene glycol can have a number average molecular weight of about 200 to about 8000, preferably about 500 to 5000.
  • the polyalkylene glycol or derirative thereof can have a kinematic viscosity at 40° C. of about 15 to about 500 cSt, preferably of about 22 to about 500 cSt, more preferably of about 22 to about 370 cSt, and most preferably of about 22 to about 220 cSt.
  • the polyalkylene glycol represented by the following formula: Z--(--(CHR 1 --CHR 2 --O) n --R 3 ) m wherein Z is a residue of a non-amine initiator having from 1-8 active hydrogens, and R 1 and R 2 are independently H, or an alkyl.
  • the alkyl has from 1 to about 8 carbon atoms.
  • the alkyl is CH 3 or CH 2 CH 3 .
  • the integer n has a value from 8 to 25, preferably from 10 to 20.
  • R 3 is H, an alkyl having from about 1 about 30 carbons, preferably from about 1 to about 24 carbons, more preferably from about 1 to about 12 carbons, and most preferably from about 1 to about 6 carbons, or an acyl having from about 1 to about 30 carbons, preferably from about 1 to about 24 carbons, more preferably from about 1 to about 12, and most preferably from about 1 to about 6 carbons, and m is from 1 to 8.
  • R 1 is H or CH 3 when R 2 is CH 3
  • R 2 is H or CH 3 or CH 2 CH 3 when R 1 is H.
  • polyalkylene glycol's can be prepared in a number of ways, suitable examples are polyalkylene glycols prepared with initiators containing from 1-8 active hydrogens prepared from alkylene oxides having from 2 to about 12 carbons, including ethylene oxide, propylene oxide or butylene oxide. The oxides may be polymerized alone (homopolymers) or as mixtures (co- or tri-polymers).
  • Another suitable polyalkylene glycol is prepared from a non-amine initiator having 1-4 active hydrogens, and having a kinematic viscosity at 40° C. of about 22 to about 220 cSt.
  • the lubricating composition can comprise the alkyl aromatic in a weight % from about 5wt% to about 99wt%.
  • the alkyl aromatic can range from about 50wt% to about 90wt%, about 55wt% to about 80%, about 60wt% to about 80 wt%, or even from about 65 wt% to about 78wt%.
  • the lubricating composition can comprise the blend of additives in a weight % from about 0.005wt% to about 10wt%.
  • the blend of additives can range from about 0.5wt% to about 7wt%, about 0.5 wt% to about 5%, about 1wt% to about 5wt%, or even from about 1 wt% to about 2 wt%.
  • the lubricating composition can comprise oil soluble polyalkylene glycols or PAG's in a weight % from about 1wt% to about 99wt%.
  • the polyolefins or PAOs can range from about 5wt% to about 60wt%, about 5wt% to about 50%, about 20wt% to about 40wt%, or even from about 30wt% to about 40wt%.
  • the lubricating composition can comprise the blend of polyolefins or PAOs in a weight % from about 5wt% to about 99wt%.
  • the polyolefins or PAOs can range from about 2wt% to about 60wt%, about 5wt% to about 30%, about 10wt% to about 20wt%, or even from about 12wt% to about 18wt%.
  • the blend PAOs can also comprise a blend of mPAOs or a singular mPAO in an amount weight% amount ranging from about 0.25wt% to about 10wt% of the total lubricating composition.
  • the blend of mPAOs or the singular mPAO can range from about 0.5wt% to about 7wt%, about 1wt% to about 5wt%, about 1wt% to about 3wt%, about 0.5wt% to about 2wt%, or even from about 1wt% to about 2wt%.
  • the blend PAOs can also comprise a blend of conventional PAOs or a singular PAO in an amount weight% amount ranging from about 0.25wt% to about 50wt% of the total lubricating composition.
  • the blend of conventional PAOs or the singular PAO can range from about 0.5wt% to about 30wt%, about 1wt% to about 20wt%, about 5wt% to about 15wt%, about 1wt% to about 10wt%, or even from about 3wt% to about 10wt%.
  • Table 1 Material 1 2 3 4 5 6 7 8 Base oil A 35.98 Base oil B 63.18 PAO 99.4 Alkylated Naphthalene 99.4 89.4 79.4 69.4 59.4 OSP A 10 20 30 40 OSP B 99.4 Antioxidant A 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Pour Point depressant 0.2 Anti-foam 0.04 Table 2 Material 9 10 11 12 13 14 15 16 Alkylated Naphthalene 89.45 79.45 88.98 78.98 OSP A 10 20 10 20 OSP B 99.45 98.95 98.45 94.95 Antioxidant B 0.25 0.5 0.75 1.0 0.25 0.25 0.5 0.5 0.5 Antioxidant C 0.25 0.5 0.75 1.0 0.25 0.25 0.5 0.5 Corrosion Inhibitor 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05
  • MPC tests show the ability to control varnish and are typically below 15.
  • the industry rating scale for the MPC tests is 0-15 normal (new oil value), 15-30 monitor (slight potential to form varnish), 30-40 abnormal (increased tendency to form varnish), and >40 critical(high tendency to form varnish).
  • Table 4 Test 1 2 3 4 5 6 7 8 cSt @ 40°C 32.15 31.15 27.48 29.37 31.21 33.23 35.36 30.32 cSt @ 100°C 5.46 6.10 4.67 5 5.35 5.71 6.1 5.78 Viscosity Index 105 147 84 94 104 112 119 136 Acid Number (new) 0.09 0.09 0.09 0.13 0.12 0.1 0.08 0.16 MPC (new) ⁇ 0.5 0.7 0.7 0.7 0.7 0.6 0.6 0.5 RPVOT, Avg.
  • the lubricating composition was then subjected to a long term oxidation test where four different complete temperature cycles lasting a total of 672 hours with a cycle being a minimum temperature of 60°C for 96 hours and a maximum temperature of 150°C for 72 hours were done.
  • the tests run on the lubricating composition after the long term oxidation test was % change of the kinetic viscosity test, acid number increase, % oil loss, MPC, and RPVOT retention %.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (15)

  1. Schmierbasisflüssigkeit, umfassend:
    a) einen Alkylaromaten;
    b) eine Mischung von Zusatzstoffen;
    c) eine Mischung von öllöslichen Polyalkylenglykolen; und
    d) eine Mischung von Polyolefinen,
    wobei die Mischung von Polyolefinen mindestens ein Metallocen-Polyolefin umfasst und
    wobei die Menge an öllöslichen Polyalkylenglykolen im Bereich von 5 Gew.-% bis 50 Gew.-% liegt.
  2. Schmierbasisflüssigkeit nach Anspruch 1, wobei die Menge an Alkylaromat im Bereich von 50 Gew.-% bis 95 Gew.-% liegt.
  3. Schmierbasisflüssigkeit nach Anspruch 1, wobei die Menge an Zusatzstoffen im Bereich von 0,005 Gew.-% bis 5 Gew.-% liegt.
  4. Schmierbasisflüssigkeit nach Anspruch 1, wobei die Menge an Polyolefinen im Bereich von 10 Gew.-% bis 20 Gew.-% liegt.
  5. Schmierbasisflüssigkeit nach Anspruch 1, wobei der Alkylaromat eine oder mehrere Alkylgruppen von 6 bis 30 Kohlenstoffatomen aufweist.
  6. Schmierbasisflüssigkeit nach Anspruch 1, wobei die Zusatzstoffe aus der Gruppe ausgewählt sind, die im Wesentlichen aus Folgenden besteht: Antioxidantien, Korrosionsinhibitoren, Rostinhibitoren, Verschleißschutzmitteln, Hochdruckmitteln, Demulgatoren und Antischaummitteln.
  7. Schmierbasisflüssigkeit nach Anspruch 1, wobei die Schmierbasisflüssigkeit als ein Turbinenöl verwendet wird; oder
    wobei die Mischung von Polyolefinen mindestens drei verschiedene Arten von Polyolefinen umfasst.
  8. Schmierbasisflüssigkeit nach Anspruch 1, wobei die Mischung von Polyolefinen mindestens ein öllösliches Polyolefin und mindestens ein Metallocen-Polyolefin umfasst.
  9. Schmierbasisflüssigkeit nach Anspruch 1, wobei die Schmierbasisflüssigkeit Folgendes umfasst:
    a) einen Alkylaromaten im Bereich von 50 Gew.-% bis 95 Gew.-%;
    b) eine Mischung von Zusatzstoffen im Bereich von 0,005 Gew.-% bis 5 Gew.-%;
    c) eine Mischung von öllöslichen Polyalkylenglykolen von 5 Gew.-% bis 50 Gew.-%; und
    d) eine Mischung von Polyalphaolefinen im Bereich von 10 Gew.-% bis 20 Gew.-%,
    wobei die Mischung von Polyalphaolefinen mindestens zwei verschiedene Arten von Polyalphaolefinen umfasst, die Folgendes umfassen: mindestens ein Metallocen-Polyalphaolefin.
  10. Verfahren zum Herstellen einer Schmierbasisflüssigkeit, umfassend das Vermischen von:
    a) einem Alkylaromaten;
    b) einer Mischung von Zusatzstoffen;
    c) einer Mischung von öllöslichen Polyalkylenglykolen; und
    d) einer Mischung von Polyolefinen,
    wobei die Mischung von Polyolefinen mindestens ein Metallocen-Polyolefin umfasst.
  11. Verfahren nach Anspruch 10, wobei die Menge an Alkylaromat im Bereich von 50 Gew.-% bis 95 Gew.-% liegt oder wobei die Menge an Zusatzstoffen im Bereich von 0,005 Gew.-% bis 5 Gew.-% liegt.
  12. Verfahren nach Anspruch 10, wobei die Menge an Polyolefinen im Bereich von 10 Gew.-% bis 20 Gew.-% liegt; oder
    wobei die Menge an öllöslichen Polyalkylenglykolen im Bereich von 5 Gew.-% bis 50 Gew.-% liegt.
  13. Verfahren nach Anspruch 10, wobei der Alkylaromat eine oder mehrere Alkylgruppen von 6 bis 30 Kohlenstoffatomen aufweist.
  14. Verfahren nach Anspruch 10, wobei die Schmierbasisflüssigkeit als ein Turbinenöl verwendet wird.
  15. Verfahren nach Anspruch 10, wobei das Verfahren Herstellen einer Schmierbasisflüssigkeit umfasst, umfassend das Vermischen von:
    a) einem Alkylaromaten im Bereich von 50 Gew.-% bis 95 Gew.-%;
    b) einer Mischung von Zusatzstoffen im Bereich von 0,005 Gew.-% bis 5 Gew.-%;
    c) einer Mischung von öllöslichen Polyalkylenglykolen von 5 Gew.-% bis 50 Gew.-%; und
    d) einer Mischung von Polyalphaolefinen im Bereich von 10 Gew.-% bis 20 Gew.-%,
    wobei die Mischung von Polyalphaolefinen mindestens zwei verschiedene Arten von Polyalphaolefinen umfasst, die Folgendes umfassen: mindestens ein Metallocen-Polyalphaolefin.
EP16856034.0A 2015-10-15 2016-10-11 Synthetische schmierölzusammensetzungen Active EP3362539B1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5431835A (en) * 1992-02-18 1995-07-11 Idemitsu Kosan Co., Ltd. Lubricant refrigerant comprising composition containing fluorohydrocarbon
EP0796908A1 (de) * 1996-02-20 1997-09-24 Unilever N.V. Oxidationsbeständiges Schmiermittel
US6127324A (en) * 1999-02-19 2000-10-03 The Lubrizol Corporation Lubricating composition containing a blend of a polyalkylene glycol and an alkyl aromatic and process of lubricating
EP2456845B2 (de) * 2009-07-23 2020-03-25 Dow Global Technologies LLC Polyalkylenglykole als schmiermittelzusätze für gruppe i-iv-kohlenwasserstofföle
WO2013066702A2 (en) * 2011-11-01 2013-05-10 Dow Global Technologies Llc Oil soluble polyalkylene glycol lubricant compositions

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