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
  • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
  • C10M143/12—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing conjugated diene
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/04—Reduction, e.g. hydrogenation
• • 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
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
• • 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
  • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
• • 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
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
• • 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
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/084—Acrylate; Methacrylate
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/086—Imides
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/28—Amides; Imides
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/046—Overbasedsulfonic acid salts
• • 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
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
• • 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
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • 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
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

• This invention relates to improved lubricating oils, particularly mineral lubricating oils, and processes of preparing the same.
• this invention relates ,to the addition of a small amount of a hydrogenated random butadiene-styrene copolymer to lubricating oils to produce formulations that are shear stable and have a high viscosity index (V.I.).
• this invention relates to hydrogenated random butadiene-styrene copolymers having defined amounts of butadiene and styrene which are blended with suitable mineral oils to increase the viscosity and improve the viscosity index.
• the viscosity of lubricating oils varies with the temperature. Many oils must be employed over a wide temperature range, e.g. F. to 300 F., and it is important that the oil not be too viscous at low temperatures nor too thin at high temperatures. Variation of the viscosity-temperature relationship of an oil is indicated by the well-known viscosity index value. The higher the viscosity index, the less the change in viscosity with change in temperature. Viscosity at 210 F. and at 100 F. is used to determine the viscosity index.
• an object of the present invention is to improve lubricating oils, and particularly the viscositytemperature relationships of mineral lubricating oils.
• Another object of this invention is to improve mineral and lubricating oils by adding specific hydrogenated random rubbery copolymers thereto.
• a further object of this invention is to provide new and improved mineral lubricating oils and methods for preparing the same.
• shear-stable, high V.I. lubricating oil formulations result from the inclusion of a small amount of a hydrogenated random butadienestyrene copolymer having a butadiene content of 30-44 weight percent.
• the additives of the invention are usually employed in an amount in the approximate range of 0.5 to 5 volume percent of the lubricating oil.
• the copolymers or additives of the present invention have a molecular weight in the approximate range of 25,- 000 to 125,000, a now preferred range being from about 30,000 to about 75,000.
• the copolymer can be one containing from about 30 to about 44 parts by weight butadiene per 100 parts by weight of total monomers.
• the values for butadiene content of the polymers are actually those for the butadiene in the monomers charge. However, these values are very close to those for the butadiene content of the polymers because essentially complete conversion was obtained in all polymer synthesis runs.
• the copolymers have a vinyl content before hydrogenation of less than 35 Weight percent. During hydrogenation, olefinic group hydrogenation is weight percent or more and phenyl group hydrogenation is 5 weight percent or less.
• the copolymers of the present invention can be prepared by any of the conventional techniques known in the art, such as those described in US. Pat. 2,975,160, R. P. Zelinski, issued Mar. 14, 1961.
• a mixture of butadiene and styrene monomers can be polymerized using butylh'thium as a catalyst and tetrahydrofuran as a randomizing agent.
• the hydrogenation can be carried out in any manner known in the art, such as by the process of U.S. Pat. 2,864,809, R. V. Jones et al., issued Dec. 16, 1958, or that of US. Pat. 3,113,986, D. S. Breslow et al., issued Dec. 10, 1963, or that of US.
• the copolymer can be hydrogenated over a reduced nickel-kieselguhr catalyst or over a nickel octoate-triethylaluminum catalyst system.
• the hydrogenated butadiene-styrene copolymers of the present invention are polymers which have been sufliciently hydrogenated to remove substantially all of the olefinic unsaturation, leaving only the aromatic (i.e., phenyl group) unsaturation.
• various mineral oils are employed. Generally, these are of petroleum origin and are complex mixtures of many hydrocarbon compounds.
• the mineral oils are refined products such as are obtained by well-known refining processes, such as by hydrogenation, by polymerization, by dewaxing, etc.
• the oils have a Saybolt viscosity at F. in the range of about 60 to 5,000, and a Saybolt viscosity at 210 F. of about 30 to 250.
• the oils can be of paraflinic, naphthen-ic, or aromatic types, as wellas mixtures of one or more types.
• the additives of the invention have special advantages when employed with paraffinic types of oils such as are obtained by solvent extraction'of a suitable refinery stream.
• suitable lubricating compositions are available as commercial products, such as those used as motor oils, gear oils, automatic transmission oils, and the like.
• the lubri- 3 cating compositions can comprise one or more of other additives known to those skilled in the art, such as antioxidants, pour point depressants, dyes, detergents, etc.
• antioxidants such as antioxidants, pour point depressants, dyes, detergents, etc.
• these additives are metal petroleum sulfonates, zinc dialkyldithiophosphates, and alkyl succinimides.
• the lubricating composition should have a viscosity index of at least about 140.
• Example I A hydrogenated random 35/65 butadiene/styrene copolymer, whose preparation is described below, was compared with a methacrylate/N-vinylpyrrolidone copolymer (Acryloid 909) in the following premium motor oil formulations:
• the hydrogenated polymer used in this example was a solution-polymerized random butadiene-styrene copolymer having a molecular weight of about 50,000, and was prepared using the following recipe and conditions:
• essentially completely hydrogenated means that 95 weight percent or more of the olefinic groups are hydrogenated and 5 weight percent or less of the phenyl groups (when present) are hydrogenated.
• the polymers of the invention in this and succeeding examples all contained less than 35 weight percent vinyl unsaturation before hydrogenation.
• Example II An essentially completely hydrogenated random 35/65 butadiene/styrene copolymer, whose preparation is de- 4 scribed below, was compared with a commercial polymeric additive (Acryloid 909) in the following premium motor oil formulations:
• Example I the experimental formulation has about the same viscosity index as the commercial formulation and has considerably greater stability to the sonic shear test. These formulations were compared in a hour Caterpillar l-H engine test (Federal Test Method Standard #791A, Method 346), and the experimental formulation was found to give a cleaner engine, as indicated by inspection of the pistons at the end of the test. There was also less viscosity index dropoff during the test with the experimental formulation as indicated by viscosity measurements made at the conclusion of the test:
• the hydrogenated polymer used in this example was prepared using the same recipe used in preparing the polymer of Example I, and had the same molecular weight. Charge order was the same, except that the styrene was charged before the butadiene. Operating condition were the same. Unterminated product was hydrogenated in the same manner as in Example I, using the same amounts of catalyst. The only difference was that the reactor was held at about 395 F. for 2 hours instead of about 350 F. for 1.5 hours. Essentially completely hydrogenated product was recovered. About 0.5 gram of water was added to the recovered polymer solution and the mixture was stirred vigorously to coagulate the catalyst. Then 25 g.
• Example III A comparison was made between the viscosities and viscosity indexes (V.I.) obtained in a Mid-Continent SAE 10 stock with an essentially completely hydrogenated polybutadiene and an essentially completely hydrogenated random 35/65 butadiene/ styrene copolymer:
• the hydrogenated random copolymer provided about 6 times as much thickening effect as the hydrogenated polybutadiene.
• An extrapolation of the data for the two levels of hydrogenated polybutadiene indicates that about -weight percent hydrogenated polybutadiene would be required to obtain the 54.5 SUS viscosity obtained with 4 weight percent hydrogenated copolymer. This is obviously impractical, even if the hydrogenated polybutadiene were soluble in oil at that high concentration level. It is. also apparent that at the 4 weight percent level a, considerably greater increase in viscosity index is obtained with the hydrogenated copolymer than with the hydrogenated polybutadiene.
• the polybutadiene' used in this example was prepared in the same manner as described in Example I of US. Pat. 2,631,175, using 1.25 lb. of finely-divided sodium for each 100 lb. of butadiene. It had a molecular weight of about 2,000. It was hydrogenated in the following manher: g. of polymer dissolved in 400 ml. of cyclohexane was placed in a nitrogen fiushed reactor, followed by 0.059 g. of Ni (as nickel octoate) and 0.475 g. of triethylaluminum in 8.5 ml. of cyclohexane. The reactor was pressured to 50 p.s.i.g.
• the 35/ 65 butadiene/styrene copolymer was prepared and hydrogenated in the same manner as that used in Example I, and had the same molecular weight.
• Example IV Unsuccessful attempts were made to prepare a 4 weight percent solution of a hydrogenated polybutadiene, whose preparation is described below, in a Mid-Continent SAE 10 stock. Following these tests a test was made'in which 0.5 weight percent of the hydrogenated polymer was dissolved in the 10 stock by heating and stirring for one hour at 295 F. Even at this level, precipitation occurred on cooling. Viscosity data for the cooled, centrifuged material and for the 10 stock are:
• the hydrogenated polybutadiene used in this example was prepared by hydrogenation of a polybutadiene having a molecular weight of about 50,000, which was prepared using the following recipe:
• Example V An essentially completely hydrogenated random 41/59 butadiene/ styrene copolymer, whose preparation is described below, was compared with a commercial polymeric additive (Acryloid 909) in the following premium motor 011 formulations:
• the charge order was as indicated, with a 3-minute nitrogen purge following solvent addition to the reactor, and 10 minutes stirring following tetrahydrofuran addition while the temperature was raised to 122 F.
• the reaction period was 2 hours.
• the unterminated polymer solution was hydrogenated 2 hours at 225 p.s.i.g. and 275 F. using 7.8 millimoles of nickel octoate per 100 parts of rubber by weight and a triethylaluminum to nickel mol ratio of 3 to 1.
• Essentially completely hydrogenated polymer was recovered by the technique described in Example III.
• the polymer had a vinyl content before hydrogenation of 22.5 weight percent, and had a molecular weight of about 75,000.
• Example VI A blend of 2.6 weight percent hydrogenated 50/50 butadiene/ styrene block copolymer, whose preparation is described below, in a Mid-Continent SAE 10 stock had the following properties:
• the block butadiene/styrene copolymer used in the tests of this example was prepared using the following recipe:
• the charge order was as indicated, and the styrene was allowed to polymerize for 1.5 hours at 122 F. before addition of the tetrahydrofuran and butadiene, after which reaction was continued for 3 hours at 122 F.
• the unterminated polymer solution was hydrogenated 0.5 hour at 400 p.s.i.g. and 350 F. using 6.5 millimoles of nickel octoate per 100 parts of rubber by weight and a triethylaluminum to nickel mol ratio of 4.1 to 1. Essentially completely hydrogenated polymer was recovered by the technique described in Example III. The polymer had a molecular weight of 25,000.
• Example VII Additional runs were conducted varying the butadi ene/styrene ratio in the hydrogenated random copolymer which was blended with lubricating oil and the resulting products evaluated.
• the data presented in the table below were obtained in an elfort to provide products having a balance of properties and a minimum V.I. of 140 along with complete polymer solubility.
• the lubricating oil formulation used in these tests was:
• Shear-stable, high V.I. mineral lubricating oil compositions having a minimum V.I. of about 140 comprising a mineral lubricating oil containing a viscosity improving amount of a soluble hydrogenated random butadiene-styrene copolymer dissolved therein, said copolymer having a bntadiene content of 30-44 weight percent and the remainder being styrene and a molecular weight ranging from 25,000 to 125,000.
• a composition according to claim 1 wherein the hydrogenated random bntadiene-styrene copolymer has a molecular weight in the range 25,000-125,000, a vinyl content before hydrogenation of less than 35 weight percent, an olefinic group hydrogenation of weight per cent or more, and a phenyl group hydrogenation of 5 weight percent or less.
• a composition according to claim 1 wherein said copolymer has a molecular weight in the range 30,000- 75,000.
• composition according to claim 1 wherein the mineral lubricating oil has a viscosity at 210 F. in the range of 30 to 250 SUS.
• composition according to claim 1 wherein said copolymer is prepared by copolymerization with a butyllithium catalyst and the hydrogenation is effective to remove substantially all of olefinic unsaturation.

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• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Lubricants (AREA)

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Cited By (43)

Families Citing this family (6)

• 1967
  • 1967-11-30 US US686825A patent/US3554911A/en not_active Expired - Lifetime
• 1968
  • 1968-11-11 ES ES360071A patent/ES360071A1/es not_active Expired
  • 1968-11-25 DK DK574868AA patent/DK139033B/da not_active IP Right Cessation
  • 1968-11-26 NO NO4710/68A patent/NO122492B/no unknown
  • 1968-11-28 DE DE19681811516 patent/DE1811516A1/de active Pending
  • 1968-11-28 FR FR1604282D patent/FR1604282A/fr not_active Expired
  • 1968-11-28 JP JP43086695A patent/JPS4839203B1/ja active Pending
  • 1968-11-28 NL NL6817031A patent/NL137863C/xx active
  • 1968-11-29 BE BE724661D patent/BE724661A/xx not_active IP Right Cessation
  • 1968-11-29 GB GB56797/68A patent/GB1223500A/en not_active Expired
  • 1968-11-29 SE SE16300/68D patent/SE346326B/xx unknown

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