WO2003076555A1 - Composition lubrifiante mixte - Google Patents

Composition lubrifiante mixte Download PDF

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Publication number
WO2003076555A1
WO2003076555A1 PCT/US2003/006558 US0306558W WO03076555A1 WO 2003076555 A1 WO2003076555 A1 WO 2003076555A1 US 0306558 W US0306558 W US 0306558W WO 03076555 A1 WO03076555 A1 WO 03076555A1
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Prior art keywords
blend
oil
group
ethylene
lubricant
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PCT/US2003/006558
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English (en)
Inventor
Margaret May-Som Wu
Jon Edmond Randolph Stanat
Kyle Douglas Lawrence
Richard T. Spissell
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Exxonmobil Research And Engineering Company
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Application filed by Exxonmobil Research And Engineering Company filed Critical Exxonmobil Research And Engineering Company
Priority to EP03711394A priority Critical patent/EP1490459A1/fr
Priority to AU2003213706A priority patent/AU2003213706B2/en
Priority to JP2003574762A priority patent/JP2005519184A/ja
Priority to CA002477331A priority patent/CA2477331A1/fr
Publication of WO2003076555A1 publication Critical patent/WO2003076555A1/fr
Priority to NO20044205A priority patent/NO20044205L/no

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    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic compounds
    • 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
    • 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
    • C10M2205/022—Ethene
    • 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
    • C10M2205/022—Ethene
    • C10M2205/0225—Ethene 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
    • C10M2205/024—Propene
    • 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
    • C10M2205/024—Propene
    • C10M2205/0245—Propene 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
    • C10M2205/026—Butene
    • 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
    • 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
    • C10M2205/10—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing cycloaliphatic monomers
    • 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
    • C10M2205/10—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing cycloaliphatic monomers
    • C10M2205/103—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing cycloaliphatic 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
    • C10M2205/17—Fisher Tropsch reaction products
    • 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
    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • 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
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/011—Cloud point
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/02—Reduction, e.g. hydrogenation
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention relates to lubricant fluid blends especially suitable as base stocks for lubricant compositions. More particularly the inventive relates to lubricant fluid blends based on hydroprocessed oils and copolymers made from ethylene with one or more alpha-olefins.
  • lubricant base stocks including most of API Group I to Group IV fluids, have viscosities at 100°C in the range of about 4 to about 6 cS.
  • PAOs high viscosity polyalphaolefin
  • PIB polyisobutylene
  • High viscosity PAOs have excellent viscometrics and low temperature properties; however, they are more expensive than PIB or bright stock. More- 03 06558
  • PAOs the availability of PAOs is limited to some extent due to the limited supply of the linear alpha olefins, such as 1-decene, used in preparing them.
  • one object of the present invention is to provide a blend of lubricant fluids having improved viscometrics when compared to blends containing PIB, bright stock or PAOs.
  • Another object is to provide lubricant fluid blends having improved shear stability when compared to blends containing PIB, bright stock or PAOs.
  • the present invention is directed toward a fluid blend suitable for use as a lube basestock comprising two major components: (A) a polymer made from ethylene with one or more alpha-olefins and containing not more than 50 wt% ethylene, the copolymer having a number average molecular weight from up 400 to 10,000 and having a molecular weight distribution (MWD) ⁇ 3 and (B) a polyalpha olefin or hydroprocessed oil having a VI greater than 80.
  • A a polymer made from ethylene with one or more alpha-olefins and containing not more than 50 wt% ethylene, the copolymer having a number average molecular weight from up 400 to 10,000 and having a molecular weight distribution (MWD) ⁇ 3
  • MWD molecular weight distribution
  • B a polyalpha olefin or hydroprocessed oil having a VI greater than 80.
  • a lubricating composition comprising the fluid blend and a lubricant additive package.
  • Figures 1 to 4 graphically compare the viscosity of lubricant base stock blends prepared from the copolymers of the invention with viscosities of blends employing polyisobutylene or bright stock.
  • component A in the fluid blend of the present invention is a copolymer made from ethylene with one or more alpha-olefins. Consequently, as used herein, the term copolymer encompass polymers containing 2, 3 or more different monomer moieties.
  • the copolymers in the blend of the invention have a number average molecular weight of from 400 to 10,000 and a MWD ⁇ 3. Importantly, the copolymer contains not more than 50 wt% ethylene.
  • the alpha-olefin moiety of the copolymer will be derived from at least one or more C3, C4 or higher alpha olefins.
  • Rj is a straight or branched chain alkyl radical comprising 1 to 18 carbon atoms and preferably 1 to 10 carbon atoms.
  • the branch is preferred to be at least two carbons away from the double bond.
  • the copolymers are prepared by copolymerizing a feed containing ethylene and one or more alpha olefins in the weight ratio of 60:40 to about 5:95 in the presence of a metallocene catalyst system.
  • Metallocene catalyst systems are well known in the art and mention is made of U.S. Patent 5,859,159, incorporated herein by reference, for a description of metallocene catalysts systems useful for producing the polymers from ethylene and one or more alpha-olefins suitable for the lubricant fluid blends of the present invention.
  • the polymer is produced by polymerizing a reaction mixture of ethylene and at least one additional alpha-olefin monomer in the presence of a metallocene catalyst system, preferably in solution.
  • a metallocene catalyst system preferably in solution.
  • hydrogen may be added to regulate the degree of polymerization or molecular weight, and to reduce the amount of unsaturation in the product. In such situations the amount of hydrogen typically will be 0.1 mole% to 50 mole% based on the amount of ethylene.
  • any known solvent effective for such polymerization can be used.
  • suitable solvents include hydrocarbon solvent such as aliphatic, cycloaliphatic and aromatic hydrocarbons.
  • the preferred solvents are propane, isobutane, pentane, isopentane, hexane, isohexane, heptane, isoheptane, Norpar, Isopar, benzene, toluene, xylene, alkylaromatic-containing solvents, or mixture of these solvents.
  • the polymerization reaction may be carried out in a continuous manner, such as in a continuous flow stirred tank reactor where feed is continuously introduced into the reactors and product removed therefrom.
  • the polymerization may be conducted in a batch reactor, preferably equipped with adequate agitation, to which the catalyst, solvent, and monomers are added to the reaction and left to polymerize therein for a time sufficient to produce the desired product.
  • Typical polymerization temperature for producing the copolymers useful herein are in the range of about 0°C to about 300°C and preferably 25 °C to 250°C at pressures of about 15 to 1500 psig, and preferably 50 to 1000 psig.
  • the conditions under which the polymerization is conducted will determine the degree of unsaturation in the resulting copolymer.
  • the degree of unsaturation of a polymer can be measured by bromine number. In the present invention it is preferred that the copolymer have a bromine number below 2 and more preferably in the range of 0 to 1.
  • the copolymer preferably is hydrogenated to provide a final product having a bromine number below 2.
  • the hydrogenation may be carried out in a batch mode or in continuous stir tank or in a continuous fixed bed operation, using typical hydrogenation catalysts.
  • the hydrogenation catalysts are nickel on kieselguhr catalyst, Raney Nickel catalyst, many commercial hydro-treating catalyst, such as nickel, cobalt, molybdenum or tungsten on silica, silica-alumina, alumina, zirconium support, etc., or supported Group VIIIB metals, such as platinum, palladium, ruthenium and rhodium.
  • the hydrogenation conditions may range from room temperature to 300°C with hydrogen pressure from atmospheric pressure to 2000 psi for long enough residence time to reduce most or all of the unsaturation.
  • the unsaturation degree can be measured by bromine number of iodine index.
  • the bromine number of the finished product should be below 2. The lower the bromine number the better the oxidative stability. More preferably, the reaction temperature, pressure, residence time, catalyst loading all will be adjusted to achieve 0-1 bromine number.
  • the other major component, component B, in the fluid blend of the present invention is a polyalpha olefin or a hydroprocessed oil having a VI greater than 80.
  • oils are Group II and III oils, Fischer-Tropsch wax isomerates (as disclosed in US 6090989, US 6080301 or US 6008164) and Group IV synthetic polyalpha olefin fluids.
  • the amounts of efhylene- ⁇ -olefin copolymer and hydroprocessed oils in the blends of fluid the present invention are not critical and will depend on the intended use of the blend.
  • the amount of ethylene ⁇ -olefin copolymer will constitute from about 1 to about 95 wt% of the blend. Generally, it is prefer to be from 5 to 80%. If too small amount of the polymer is used, the blend will not have sufficient viscometrics. On the other hand, if too much of the polymer . is used, it maybe more costly or the blend viscosity may be too high for practical use.
  • the fluid blends of the present invention can be combined with selected lubricant additives to provide lubricant compositions.
  • Antifoaming Agents 0.01 - 0.1 0.001 - 0.01
  • Antiwear Agents 0.001 - 5 0.001 - 2
  • Friction Modifiers 0.01 - 3 0.01 - 1.5
  • additive concentrates comprising concentrated solutions or dispersions of the dispersant, together with one or more of the other additives to form an additive mixture, referred to herein as an additive package whereby several additives can be added simultaneously to the base stock to form the lubricating oil composition. Dissolution of the additive concentrate into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential.
  • the concentrate or additive-package will typically be formulated to contain the dispersant additive and optional additional additives in proper amounts to provide the desired concentration in the final formulation when the additive package is combined with a predetermined amount of the fluid blend of the invention.
  • composition of the invention may also include a co-base stock to enhance lubricant performance or to improve additive solubility in the basestock.
  • co-basestocks are selected from polar fluids useful as lubricants.
  • Examples of these fluids include many types of esters, alkyl- aromatics, and oil-soluble polyalkylene glycols.
  • Typical esters used in lubricant formulations include polyol esters, adipate esters, sibacate esters, phthalate esters, sterates, etc.
  • Typical alkylaromatics used in lube formulation include alkylated naphthalenes, alkylbenzenes, alkyltoluenes, detergent alkylate bottoms, etc.
  • Typical oil-soluble polyalkylene glycols include poly-propylene oxides, poly-butylene oxides, etc. Such fluids may be used in amounts of about 1 wt% to about 60 wt% although amounts of about 1 wt% to about 10 wt% are preferred.
  • This liquid product was further hydrogenated at 200°C, 1000 psi H2 pressure using 2 wt% nickel on Kieselguhr catalyst for 4 hours.
  • This polymer contains 28.6 wt% ethylene as measured by C13-NMR.
  • This polymer was prepared in a continuous mode of operation.
  • polymer grade ethylene, polymer grade 1-butene and polymer grade iso-butane solvent were charged into a 200 gallon reactor after purification through molecular sieve and treatment by injecting 50 ppm tri-t-butylaluminum.
  • the feed rates for ethylene, 1-butene and iso-butane were 12, 120 and 180 lb/hour, respectively.
  • a catalyst solution containing 5 x 10 g-mole/liter of dimethylsilylbis (4,5,6,7 tetrahydro-indenyl) zirconium dichloride and methyl- aluminoxane of 1/400 Zr/Al molar ratio in toluene, was charged into the reactor at 13.5 ml/minute.
  • the reactor temperature was maintained 89.4°C and 95.6°C, pressure 237-261 psi and average residence time 2 hours.
  • the crude reaction product was withdrawn form the reactor continuously and washed with 0.4 wt% sodium hydroxide solution followed with a water wash.
  • a viscous liquid product was obtained by devolitalization to remove iso-butane solvent, light stripping at 66°C/5 psig followed by deep stripping at 140°C/1 millitorr.
  • the residual viscous liquid was then hydro-finished at 200°C, 800-1200 psi H2 pressure with 2 wt% Ni-on-Kieselguhr catalyst for eight hours.
  • This polymer has Mn of 2374 and MWD of 1.88.
  • This polymer was prepared in a similar manner as in Example 3, except that the feed rates for ethylene, 1-butene and isobutane were 58, 120 and 283 lb/hour, and the reaction temperature was between 98.3°C and 101.1°C, pressure 290-300 psi and average residence time 1 hour.
  • This polymer has Mn of 2660 and MWD of 1.76.
  • ⁇ PIB H5O and H300 are trade names for polyisobutylene sold by BP Chemical Co. BP North America (chemicals), 150 W Warrenville Rd., N-3, Naperville, LL 60563 USA.
  • the 100 cS PAO is available from ExxonMobil Chemical Co at Edison, NJ.
  • Example 3 polymer and PIB H50 both have the similar 100°C viscosities
  • the blends from Example 3 have higher 100°C and 40°C viscosities than PIB at same weight percent ( Figures 1 and 2).
  • the thickening efficiency for Example 3 is also higher than PIB.
  • the Example 3 sample have better viscosity boosting effect than PIB of comparable viscosity.
  • the lube base fluids made from Example 3 and Group III base stocks have higher VI at similar 100°C viscosity, as shown in Figure 3. Similar trends were observed when compared to the blends with bright stock.
  • Examples 2 and 4 fluids both have much lower 100°C viscosities than PIB H300 (161 cS and 150 cS vs. 663 cS), the blends from Example 2 and 4 fluids have higher viscosities than those from PIB H300. At the same weight percent of blend stock, the thickening efficiencies of Example 2 and 4 fluids are higher than PIB H300. These data demonstrate that Example 2 and 4 fluids have better viscosity-boosting effect than PIB. Also, the VI of the blends from Example 3 and 5 fluids are higher than those from PIB H300 ( Figure 4).
  • the blends have a VI that is higher than the Group III base stock alone.
  • Blends were prepared from a Group II basestock with the Example 3 and 4 fluids and with PIB H50. The details and properties of the blends are given in Table 5.
  • the blending fluids of this invention (Blends 34 to 36) have comparable thickening efficiency as the best comparative example (Blend 38). At this comparable thickening efficiency, the copolymer blend of the invention (Blend 34 to 36) has better shear stability than that of the PIB blend 37.
  • a blend (blend no 38) is prepared using the Example 2 fluid, which has a much broader MWD (2.66) than the Example 3 and 4 polymers.
  • the polymer again has excellent thickening efficiency (Table 6), better than PIB H300.
  • this polymer still has better shear stability than PIB when tested in the D5621 method.
  • Blends 34 to 36 were prepared using polymers with MWD of 1.75 to 2.01. They have slightly better shear stability (0.2% viscosity loss) than the blend prepared by using polymer with MWD of 2.66 (blend 38 with 1.3% viscosity loss). Therefore, we conclude that blends containing polymer made from ethylene and alpha-olefins with narrower MWD are more desirable than blends made from ethylene and alpha-olefins with broader MWD.
  • Table 7 compares the shear stability of the blends made with Example 5 and Example 6 (blend 39 and 40) versus a blend made with commercial sample, Viscoplex 8-219 (available from RohMax USA, Inc) of comparable thickening efficiency in a Group III base stock. As the data showed that blends 39 and 40 have much better shear stability with only 1.3 and 1.6% viscosity loss as compared to the comparative blend 41 with 6% viscosity loss. TABLE 7
  • ethylene alpha-olefins copolymers were prepared similar to Example 3 except using different amounts of ethylene in the feed.
  • the polymers when blended with Group III base stocks are clear and bright and have excellent viscometrics as shown in Table 8. These example demonstrated that even with high ethylene content (44 wt%) and MWD of 2.3, blends of excellent properties can be obtained.
  • Example 3 Following the procedure of Example 3, except using higher ethylene feed rate, a copolymer sample containing 50.8 wt% ethylene was prepared.
  • This polymer has Mn of 2386, which is comparable to example 3. However, it has broader MWD of 2.81, instead of 1.88 as the Example 3 polymer.

Abstract

La présente invention concerne un mélange liquide à utiliser en tant qu'huile de base lubrifiante. Ce mélange comprend deux principaux composants : (A) un copolymère produit à partir d'éthylène avec une ou plusieurs alpha oléfines, le copolymère (i) ayant une teneur en éthylène inférieure ou égale à 50 % en poids; (ii) présentant un poids moléculaire moyen en nombre qui va de 400 à 10 000; et (iii) une répartition de poids moléculaire < 3; et (B) un liquide à base de polyalphaoléfine ou une huile hydrotraitée présentant un VI supérieur à 80.
PCT/US2003/006558 2002-03-05 2003-03-04 Composition lubrifiante mixte WO2003076555A1 (fr)

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EP03711394A EP1490459A1 (fr) 2002-03-05 2003-03-04 Composition lubrifiante mixte
AU2003213706A AU2003213706B2 (en) 2002-03-05 2003-03-04 Lubricant blend composition
JP2003574762A JP2005519184A (ja) 2002-03-05 2003-03-04 潤滑油混合組成物
CA002477331A CA2477331A1 (fr) 2002-03-05 2003-03-04 Composition lubrifiante mixte
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US10/367,245 US20030236177A1 (en) 2002-03-05 2003-02-14 Novel lubricant blend composition

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WO2014158533A1 (fr) * 2013-03-14 2014-10-02 Exxonmobil Research And Engineering Company Composition lubrifiante pour une grande résistance à l'usure
WO2022212431A1 (fr) * 2021-04-01 2022-10-06 The Lubrizol Corporation Lubrifiants destinés à être utilisés dans des systèmes de compression de vapeur

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JP2008531813A (ja) * 2005-03-03 2008-08-14 シェブロン ユー．エス．エー． インコーポレイテッド ポリαオレフィン及びフィッシャー−トロプシュ誘導潤滑基油潤滑油ブレンド
JP2008531834A (ja) * 2005-03-03 2008-08-14 シェブロン ユー．エス．エー． インコーポレイテッド ポリαオレフィン及びフィッシャー−トロプシュ誘導潤滑基油潤滑油ブレンド
WO2007012969A1 (fr) * 2005-07-29 2007-02-01 Toyota Jidosha Kabushiki Kaisha Composition d'huile pour engrenages
EP1752520A1 (fr) * 2005-07-29 2007-02-14 TonenGeneral Sekiyu Kabushiki Kaisha Compositions d'huile pour engrenages
CN101233218A (zh) * 2005-07-29 2008-07-30 丰田自动车株式会社 齿轮油组合物
CN104498140A (zh) * 2005-07-29 2015-04-08 丰田自动车株式会社 齿轮油组合物
US8669215B2 (en) 2008-12-05 2014-03-11 Croda International Plc Gear oil additive
WO2011011656A3 (fr) * 2009-07-23 2011-03-17 Dow Global Technologies Inc. Polyalkylène glycols utiles comme additifs lubrifiants pour des huiles hydrocarbonées des groupes i-iv
CN102471720A (zh) * 2009-07-23 2012-05-23 陶氏环球技术有限责任公司 可用作i-iv类烃油用润滑剂添加剂的聚亚烷基二醇
US8969271B2 (en) 2009-07-23 2015-03-03 Dow Global Technologies Llc Polyakylene glycols useful as lubricant additives for groups I-IV hydrocarbon oils
WO2014158533A1 (fr) * 2013-03-14 2014-10-02 Exxonmobil Research And Engineering Company Composition lubrifiante pour une grande résistance à l'usure
WO2022212431A1 (fr) * 2021-04-01 2022-10-06 The Lubrizol Corporation Lubrifiants destinés à être utilisés dans des systèmes de compression de vapeur

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CA2477331A1 (fr) 2003-09-18
US20030236177A1 (en) 2003-12-25
US20050250657A1 (en) 2005-11-10
NO20044205L (no) 2004-12-06
EP1490459A1 (fr) 2004-12-29
JP2005519184A (ja) 2005-06-30
AU2003213706B2 (en) 2008-06-19

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