US3143513A - Lubricant composition - Google Patents

Lubricant composition Download PDF

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US3143513A
US3143513A US90197A US9019761A US3143513A US 3143513 A US3143513 A US 3143513A US 90197 A US90197 A US 90197A US 9019761 A US9019761 A US 9019761A US 3143513 A US3143513 A US 3143513A
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oil
vinyl
copolymer
polyethylene
ester
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US90197A
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Leslie B Day
Ronald C Watkins
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C10M143/02—Polyethylene
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of a saturated carboxylic or carbonic acid
    • C10M145/08—Vinyl esters of a saturated carboxylic or carbonic acid
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    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—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
    • C10M145/12—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 monocarboxylic
    • C10M145/14—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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—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
    • C10M145/16—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 polycarboxylic
    • 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
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C10M157/04—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
    • 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
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • 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
    • C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • C10M2209/062—Vinyl esters of saturated carboxylic or carbonic acids, e.g. vinyl acetate
    • 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
    • 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
    • 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
    • C10M2209/086—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 polycarboxylic, e.g. maleic acid
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/026—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrile group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/02—Macromolecular compounds obtained by reactions of monomers involving only carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a lubricating oil composition containing a mixture of two additives which synergistically lower the pour point of the lubricating oil.
  • the present invention therefore comprises an improved lubricating oil composition containing an oil-soluble polymer or copolymer derived from at least one unsaturated compound having at least one ester group, as hereinafter defined, together with an oil-soluble copolymer of polyethylene with an ester of vinyl alcohol and a C -C monocarboxylic acid.
  • the lubricating oils employed as the base oils may be of mineral origin or synthetic lubricating oils such as synthetic ester lubricants.
  • the oil-soluble polymer is hereby defined as a homopolymer of an unsaturated ester, or a copolymer of the unsaturated ester or esters with one or more copolymerisable compounds, such comonomers preferably containing polar groups selected from halogen-containing, nitrogencontaining, sulfur-containing, ester, carboxylic acid, anhydride or hydroxyl groups.
  • Two component cop0lymers Copolymers of vinyl acetate and fumaric acid esters, of vinyl acetate or acrylic acid esters with styrene, of cinnamic acid esters with acrylic or methacrylic acid esters, acrylic acid esters wi maleic anhydride, of vinyl acetate with aconitic acid esters, diiierent esters of fumaric acid that is, esters which have alkyl groups of different chain lengths, of nitriles or amides of unsaturated monobasic acids with methacrylic acid esters with nitriles of amides of unsaturated dibasic acids, of C C alcohol esters of unsaturated acids or esters of unsaturated alcohols with C C organic acids such as vinyl acetate with butyrolactams such as N-vinyl pyrrolidone, of vinyl esters and/or esters of unsaturated dicarboxylic acids with unsaturated urethanes, unsaturated ureas, N-viny
  • Three component c0p0lymers Copolymers of fumaric acid esters and vinyl acetate with maleic anhydride, partial esters of maleic acid or maleic hydrazide, or butyrolactams such as N-vinyl pyrrolidone.
  • c0polymers Four component c0polymers.-Copolyrners of a mixture of two difierent fumaric acid esters and vinyl acetate with maleic anhydride, or partial esters of maleic acid or butyrolactams such as N-vinyl pyrrolidone.
  • copolymer of polyethylene with an ester of vinyl alcohol and a C -C monocarboxylic acid is preferably derived from 230% by weight of the vinyl ester, particularly from 4-15 by weight of the vinyl ester.
  • the oil-soluble polyethylene copolymer may be added to the lubricating oil in the form of oil concentrates, the copolymer being present at concentrations of from 25% to 50% by weight in the concentrate.
  • the polyethylene When polyethylene is employed in the polyethylene copolymer used in the compositions of the present invention the polyethylene may be obtained by polymerising ethylene until the desired average molecular weight range is obtained; or by the degradation of high molecular weight polyethylene until the desired average molecular weight range is obtained.
  • the average molecular weight was determined by the cryoscopic method.
  • a preferred molecular weight range for polyethylene is from 800 to 6,000, a range of from 800 to 2,000 being particularly preferred.
  • Polyethylene as prepared by the known techniques consists of straight chain polymers and branched chain polymers, the applicants have discovered that it is particularly desirable to use polyethylene which contains branched chain polymers.
  • suitable polyethylene copolymers have a molecular weight from 1,200 to 1,400, dropping point from to 210 F., viscosity from 5 to 8.8 stokes at 210 F., and penetration at 77 F. of 8 to 12 mm./ 10.
  • a particularly preferred polyethylene copolymer has a molecular Weight of 1,300, dropping point of 204 F., viscosity of 7.34 stokes at 210 F., and penetration at 77 F. of 10 mm./ 10.
  • the lubricating oil compositions of the present invention when containing polyethylene copolymer, contain from 0.003 to 0.3 weight percent of the oil-soluble polyethylene copolymer, a range of 0.05 to 0.1 weight percent of the polyethylene copolymer being particularly preferred.
  • Example 1 A paraflinic mineral lubricating oil of Middle East origin having a VI. of 113 was employed as the base oil, a 40% oil solution a copolymer of n C -C1 alkyl fumarate acid esters and n C -C alkyl fumarate acid diester, vinyl acetate and maleic anhydride being the polymeric additive, the polyethylene copolymer being derived from polyethylene and 8% of vinyl acetate and having a molecular weight of 1300.
  • the pour points of the lubricating oil alone and with the additives singly and in com bination, are given below.
  • Base oil +15 Base oil+6.25% by wt. of the oil-solution of the polymeric additive Base oil+0.1% by wt. of polyethylene copolymer +15 Base oil+6.25% by wt. of the oil-solution of the polymeric additive, and 0.1% by wt. polyethylene copolymer 15
  • Example 2 Base oil +15 Base oil+6.25% by Wt. of the oil-solution of the polymeric additive 0 Base oil+0.1% by wt. of polyethylene copolymer +15 Base oil+6.25% by wt. of the oil-solution of polymeric additive, and 0.1% by wt. polyethylene copolymer 15
  • the pour points were determined by the method described in LR 15/55 Cloud and Pour Point Test.
  • Conventional lubricating oil additives such as antioxidants, extreme-pressure additives, detergent additives and viscosity index improving additives may also be added to the lubricating oil compositions of the present inven tion.
  • a lubricating composition comprising a major proportion of a mineral lubricating oil and a minor amount, suflicient to depress the pour point of said oil, of a mineral lubricating oil pour point depressant which is an oilsoluble copolymer of 1) ester of fumaric acid and C to C alcohol, (2) vinyl acetate, and (3) a material selected from the group consisting of maleic anhydride and N-vinyl pyrollidone; and an amount within the range of 0.003 to 0.3 wt. percent suflicient to further depress the pour point of said composition of an oil-soluble synergistically-acting copolymer of 70 to 98 wt. percent of poly- 4 ethylene having a molecular weight of from 800 to 6000 and to 2 wt. percent of an ester of vinyl alcohol and a C to C monocarboxylic acid.
  • a mineral lubricating oil pour point depressant which is an oilsoluble copolymer of 1) ester of fumaric acid and
  • composition according to claim 1 wherein said Wt. percent of said oil-soluble synergistically-acting copolymer is within the range of 0.05 to 0.1 Wt. percent, said molecular weight of said synergistically-acting copolymer is from 1200 to 1400, and said ester of vinyl alcohol and a C to C monocarboxylic acid is vinyl acetate.
  • composition according to claim 2 wherein said material is maleic anhydride.
  • composition according to claim 2 wherein said material is N-vinyl pyrollidone.

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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)

Description

United States Patent 3,143,513 LUBRICANT COMPOSITION Leslie B. Day, Letcomhe Regis, Wantage, and Ronald C. Watkins, East Hendred, England, assignors to Esso Research and Engineering Company, a corporation of Deiaware No Drawing. Filed Feb. 20, 1961, Ser. No. 90,197 Claims priority, application Great Britain Feb. 26, 1960 4 Claims. (Cl. 252-515) The present invention relates to a lubricating oil composition containing a mixture of two additives which synergistically lower the pour point of the lubricating oil.
It is known that particular polymeric oil-soluble additives may lower the pour point of lubricating oils, such additives may also have other properties such as viscosity index (V.I.) improving and detergent properties. The applicants have discovered that if a copolymer of polyethylene with an ester of vinyl alcohol and a C -C monocarboxylic acid is employed in lubricating oils in conjunction with the oil-soluble polymers or copolymers as hereinafter defined there is an unexpected improvement in the pour point of the lubricating oil.
The present invention therefore comprises an improved lubricating oil composition containing an oil-soluble polymer or copolymer derived from at least one unsaturated compound having at least one ester group, as hereinafter defined, together with an oil-soluble copolymer of polyethylene with an ester of vinyl alcohol and a C -C monocarboxylic acid.
The lubricating oils employed as the base oils may be of mineral origin or synthetic lubricating oils such as synthetic ester lubricants.
The oil-soluble polymer is hereby defined as a homopolymer of an unsaturated ester, or a copolymer of the unsaturated ester or esters with one or more copolymerisable compounds, such comonomers preferably containing polar groups selected from halogen-containing, nitrogencontaining, sulfur-containing, ester, carboxylic acid, anhydride or hydroxyl groups.
A representative list of unsaturated polymers and copolymers as hereinbefore defined is given below. This list is not intended to be an exhaustive list of types of polymers that may be employed in the composition of the present invention but merely illustrative.
Ham0polymers.Polymers of acrylic acid esters and methacrylic acid esters.
Two component cop0lymers.Copolymers of vinyl acetate and fumaric acid esters, of vinyl acetate or acrylic acid esters with styrene, of cinnamic acid esters with acrylic or methacrylic acid esters, acrylic acid esters wi maleic anhydride, of vinyl acetate with aconitic acid esters, diiierent esters of fumaric acid that is, esters which have alkyl groups of different chain lengths, of nitriles or amides of unsaturated monobasic acids with methacrylic acid esters with nitriles of amides of unsaturated dibasic acids, of C C alcohol esters of unsaturated acids or esters of unsaturated alcohols with C C organic acids such as vinyl acetate with butyrolactams such as N-vinyl pyrrolidone, of vinyl esters and/or esters of unsaturated dicarboxylic acids with unsaturated urethanes, unsaturated ureas, N-vinyl-n-alkyl amides of aliphatic carboxylic acids, N-vinyl pyrazolones, N-vinyl morpholines, N-vinyl imidazolines, N-vinyl sultams or N-vinyl cyclic imides.
Three component c0p0lymers.Copolymers of fumaric acid esters and vinyl acetate with maleic anhydride, partial esters of maleic acid or maleic hydrazide, or butyrolactams such as N-vinyl pyrrolidone.
Four component c0polymers.-Copolyrners of a mixture of two difierent fumaric acid esters and vinyl acetate with maleic anhydride, or partial esters of maleic acid or butyrolactams such as N-vinyl pyrrolidone.
3,143,513 Patented Aug. 4, 1964 See The copolymer of polyethylene with an ester of vinyl alcohol and a C -C monocarboxylic acid is preferably derived from 230% by weight of the vinyl ester, particularly from 4-15 by weight of the vinyl ester.
The oil-soluble polyethylene copolymer may be added to the lubricating oil in the form of oil concentrates, the copolymer being present at concentrations of from 25% to 50% by weight in the concentrate.
When polyethylene is employed in the polyethylene copolymer used in the compositions of the present invention the polyethylene may be obtained by polymerising ethylene until the desired average molecular weight range is obtained; or by the degradation of high molecular weight polyethylene until the desired average molecular weight range is obtained. As used in this specification the average molecular weight was determined by the cryoscopic method. A preferred molecular weight range for polyethylene is from 800 to 6,000, a range of from 800 to 2,000 being particularly preferred.
Polyethylene as prepared by the known techniques consists of straight chain polymers and branched chain polymers, the applicants have discovered that it is particularly desirable to use polyethylene which contains branched chain polymers. We have found that suitable polyethylene copolymers have a molecular weight from 1,200 to 1,400, dropping point from to 210 F., viscosity from 5 to 8.8 stokes at 210 F., and penetration at 77 F. of 8 to 12 mm./ 10. A particularly preferred polyethylene copolymer has a molecular Weight of 1,300, dropping point of 204 F., viscosity of 7.34 stokes at 210 F., and penetration at 77 F. of 10 mm./ 10.
It is preferred that the lubricating oil compositions of the present invention, when containing polyethylene copolymer, contain from 0.003 to 0.3 weight percent of the oil-soluble polyethylene copolymer, a range of 0.05 to 0.1 weight percent of the polyethylene copolymer being particularly preferred.
Example 1 A paraflinic mineral lubricating oil of Middle East origin having a VI. of 113 was employed as the base oil, a 40% oil solution a copolymer of n C -C1 alkyl fumarate acid esters and n C -C alkyl fumarate acid diester, vinyl acetate and maleic anhydride being the polymeric additive, the polyethylene copolymer being derived from polyethylene and 8% of vinyl acetate and having a molecular weight of 1300. The pour points of the lubricating oil alone and with the additives singly and in com bination, are given below.
Pour point, F.
Base oil +15 Base oil+6.25% by wt. of the oil-solution of the polymeric additive Base oil+0.1% by wt. of polyethylene copolymer +15 Base oil+6.25% by wt. of the oil-solution of the polymeric additive, and 0.1% by wt. polyethylene copolymer 15 Example 2 Base oil +15 Base oil+6.25% by Wt. of the oil-solution of the polymeric additive 0 Base oil+0.1% by wt. of polyethylene copolymer +15 Base oil+6.25% by wt. of the oil-solution of polymeric additive, and 0.1% by wt. polyethylene copolymer 15 In all the above examples the pour points were determined by the method described in LR 15/55 Cloud and Pour Point Test.
It will be seen in the examples that an unexpected drop in thepour point of the base oil is obtained when employing the two additives together in accordance with the present invention as compared to the pour points when the additives are used singly.
Conventional lubricating oil additives such as antioxidants, extreme-pressure additives, detergent additives and viscosity index improving additives may also be added to the lubricating oil compositions of the present inven tion.
What is claimed is:
l. A lubricating composition comprising a major proportion of a mineral lubricating oil and a minor amount, suflicient to depress the pour point of said oil, of a mineral lubricating oil pour point depressant which is an oilsoluble copolymer of 1) ester of fumaric acid and C to C alcohol, (2) vinyl acetate, and (3) a material selected from the group consisting of maleic anhydride and N-vinyl pyrollidone; and an amount within the range of 0.003 to 0.3 wt. percent suflicient to further depress the pour point of said composition of an oil-soluble synergistically-acting copolymer of 70 to 98 wt. percent of poly- 4 ethylene having a molecular weight of from 800 to 6000 and to 2 wt. percent of an ester of vinyl alcohol and a C to C monocarboxylic acid.
2. A composition according to claim 1, wherein said Wt. percent of said oil-soluble synergistically-acting copolymer is within the range of 0.05 to 0.1 Wt. percent, said molecular weight of said synergistically-acting copolymer is from 1200 to 1400, and said ester of vinyl alcohol and a C to C monocarboxylic acid is vinyl acetate.
3. A composition according to claim 2, wherein said material is maleic anhydride.
4. A composition according to claim 2, wherein said material is N-vinyl pyrollidone.
References Cited in the file of this patent UNITED STATES PATENTS 2,499,723 Cotfman et al Mar. 7, 1950 2,800,453 Bondi et a1. July 23, 1957 2,936,300 Tutwiler et al May 10, 1960 FOREIGN PATENTS 760,554 Great Britain Oct. 31, 1956 808,665 Great Britain Feb. 11, 1959

Claims (1)

1. A LUBRICATING COMPOSITION COMPRISING A MAJOR PROPORTION OF A MINERAL LUBRICATING OIL AND A MINOR AMOUNT, SUFFICIENT TO DEPRESS THE POUR POINT OF SAID OIL, OF A MINERAL LUBRICATING OIL POUR POINT DEPRESSANT WHICH IS AN OILSOLUBLE COPOLYMER OF (1) ESTER OF FURMARIC ACID AND C8 TO C18 ALCOHOL, (2) VINYL ACETATE, AND (3) A MATERIAL SELECTED FROM THE GROUP CONSISTING OF MALEIC ANHYDRIDE AND N-VINYL PYROLLIDONE; AND AN AMOUNT WITHIN THE RANGE OF 0.003 TO 0.3 WT. PERCENT SUFFICIENT TO FURTHER DEPRESS THE POUR POINT OF SAID COMPOSITION OF AN OIL-SOLUBLE SYNERGISTICALLY-ACTING COPOLYMER OF 70 TO 98 WT. PERCENT OF POLYETHYLENE HAVING A MOLECULAR WEIGHT OF FROM 800 TO 6000 AND 30 TO 2 WT. PERCENT OF AN ESTER OF VINYL ALCOHOL AND A C1 TO C4 MONOCARBOYXLIC ACID.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3270032A (en) * 1963-07-25 1966-08-30 Air Prod & Chem Foam stabilizer oil
US3342788A (en) * 1960-03-22 1967-09-19 Exxon Research Engineering Co Additives
US3473901A (en) * 1963-02-08 1969-10-21 Rohm & Haas Fuel compositions
US5304315A (en) * 1992-04-15 1994-04-19 Exxon Chemical Patents Inc. Prevention of gel formation in two-cycle oils
US5371130A (en) * 1993-10-07 1994-12-06 The Lubrizol Corporation Polymer compositions of improved compatibility in oil
EP0673990A1 (en) * 1994-03-22 1995-09-27 Shell Internationale Researchmaatschappij B.V. Hydrocarbon oil compositions having improved cold flow properties

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2499723A (en) * 1947-07-28 1950-03-07 Du Pont Lubricants containing copolymers of ethylene and vinyl acetate
GB760554A (en) * 1953-05-18 1956-10-31 Bataafsche Petroleum Lubricating compositions and additives therefor
US2800453A (en) * 1955-11-18 1957-07-23 Shell Dev Liquid hydrocarbon compositions
GB808665A (en) * 1956-03-23 1959-02-11 Exxon Research Engineering Co Oils containing copolymers
US2936300A (en) * 1955-11-16 1960-05-10 Exxon Research Engineering Co Copolymers of vinyl acetate and fumarate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2499723A (en) * 1947-07-28 1950-03-07 Du Pont Lubricants containing copolymers of ethylene and vinyl acetate
GB760554A (en) * 1953-05-18 1956-10-31 Bataafsche Petroleum Lubricating compositions and additives therefor
US2936300A (en) * 1955-11-16 1960-05-10 Exxon Research Engineering Co Copolymers of vinyl acetate and fumarate
US2800453A (en) * 1955-11-18 1957-07-23 Shell Dev Liquid hydrocarbon compositions
GB808665A (en) * 1956-03-23 1959-02-11 Exxon Research Engineering Co Oils containing copolymers

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3342788A (en) * 1960-03-22 1967-09-19 Exxon Research Engineering Co Additives
US3473901A (en) * 1963-02-08 1969-10-21 Rohm & Haas Fuel compositions
US3270032A (en) * 1963-07-25 1966-08-30 Air Prod & Chem Foam stabilizer oil
US5304315A (en) * 1992-04-15 1994-04-19 Exxon Chemical Patents Inc. Prevention of gel formation in two-cycle oils
US5371130A (en) * 1993-10-07 1994-12-06 The Lubrizol Corporation Polymer compositions of improved compatibility in oil
EP0673990A1 (en) * 1994-03-22 1995-09-27 Shell Internationale Researchmaatschappij B.V. Hydrocarbon oil compositions having improved cold flow properties
US5585337A (en) * 1994-03-22 1996-12-17 Shell Oil Company Hydrocarbon oil compositions having improved cold flow properties

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