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
  • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/14—Esterification
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• • 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
  • C10M2207/40—Fatty vegetable or animal oils
• • 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
  • C10M2207/40—Fatty vegetable or animal oils
  • C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
• • 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
  • 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
  • C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
• • 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
• • 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
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/015—Dispersions of solid lubricants
  • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
• • 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
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy
• • 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
  • C10N2070/02—Concentrating of additives
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/933—Detergent property or lubricant additive

Definitions

• Lubricating oil compositions containing a copolymer of (1) ethylene, (2) an alkyl ester of an unsaturated monocarboxylic acid and (3) a hydroxyalkylester of an unsaturated monocarboxylic acid exhibit excellent properties relative to thermal stability, viscosity index improvement and dispersant activity.
• This invention relates to novel lubricant compositions containing polymeric compounds which have dispersant properties and viscosity-improving characteristics. This invention further relates to novel polymeric compounds which are suitable for use as lubricant additives.
• a class of polymeric compounds has now been found which impart dispersant properties to a lubricating oil, improve the viscosity characteristics of the lubricating oil and in addition possess a very high thermal stability.
• These novel polymeric compounds are those which have been obtained by copolymerization of one or more olefins containing from 2-6 carbon atoms per molecule with one or more alkyl esters of unsaturated carboxylic acids and one or more esters of unsaturated carboxylic acids containing at least one free hydroxyl group located in the part of the molecule derived from the alcohol.
• the invention therefore relates to novel lubricant compositions containing one or more lubricants and polymeric compounds which have been obtained by copolymerization of one or more olefins containing 26 carbon atoms per molecule with one or more alkyl esters of unsaturated carboxylic acids and with one or more esters of unsaturated carboxylic acids containing at least one free hydroxyl group located in the part of the molecule derived from the alcohol.
• the preparation of the present polymers may be accomplished in two manners.
• the polymers may be pre 3,518,197 Patented June 30, 1970 "ice pared directly by copolymerization of a monomer mixture consisting of one or more olefins with 2-6 carbon atoms per molecule, one or more alkyl esters of unsaturated carboxylic acids and one or more esters of unsaturated carboxylic acids which contain at least one free hydroxyl group located in the part of the molecule derived from the alcohol.
• the polymers are preferably prepared by an indirect route comprising copolymerization of a monomer mixture consisting of one or more olefins having 2-6 carbon atoms per molecule, one or more unsaturated carboxylic acids and one or more alkyl esters of unsaturated carboxylic acids, followed by after-treatment of the acid copolymers so obtained in which the carboxyl groups are converted into COOR groups, in which R represents a monovalent alkyl radical containing at least one free hydroxyl group.
• the olefins suitable for use as monomers in the preparation of the present copolymers may be either monoolefins or diolefins. Mixtures of olefins may also be used. Examples of suitable monoolefins are ethylene, propylene, butene and pentene. Examples of suitable diolefins are, among others, butadiene, isoprene and dimethylbutadiene. Copolymers prepared with the aid of ethylene are preferred. Copolymers which have been prepared by copolymerization with diolefins may be used for the preparation of lubricant compositions as such or may be hydrogenated, thereby saturating at least part of the olefinically unsaturated bonds with hydrogen.
• alkyl esters of unsaturated carboxylic acids suitable for use as monomers in the preparation of the present copolymers may be either alkyl esters of unsaturated monobasic carboxylic acids or alkyl esters of unsaturated polybasic carboxylic acids. Mixtures of alkyl esters of unsaturated carboxylic acids can be used as Well. Examples of suitable alkyl esters of unsaturated monobasic carboxylic acids which may be mentioned are methyl methacrylate, isobutyl acrylate, lauryl methacrylate and stearyl methacrylate.
• alkyl esters of unsaturated 'polybasic carboxylic acids are diethyl maleate, dioctyl fumarate and di-(2-ethylhexyl)itaconate. Preference is given to polymers prepared with the aid of alkyl esters of monobasic carboxylic acids wherein the alkyl group contains 8 or more carbon atoms, in particular lauryl methacrylate or a mixture of lauryland stearyl methacrylate.
• esters of unsaturated carboxylic acids wherein the part of the molecule derived from the alcohol contains at least one free hydroxyl group maybe esters of both monobasic carboxylic acids and polybasic carboxylic acids. Mixtures of these esters are useful also.
• esters are partial esters of polyvalent alcohols, such as glycol, glycerol, trimethylolpropane, pentaerythritol and p-dimethylolbenzene, with monobasic carboxylic acids, such as acrylic acid and methacrylic acid, or with polybasic carboxylic acids, such as maleic acid, fumaric acid and itaconic acid, in which partial esters part of the hydroxyl groups originally present in the polyvalent alcohols remain as such.
• esters are products of the reaction of cyclic ethers wherein the ring contains an oxygen atom and two or three carbon atoms, such as ethylene oxide and trimethylene oxide, with unsaturated monobasic carboxylic acids, such as acrylic acid and methacrylic acid, or with unsaturated polybasic carboxylic acids, such as maleic acid, fumaric acid and itaconic acid, in which reaction products the part of the molecule derived from the cyclic ether contains a free hydroxyl group.
• the preparation of the present copolymers takes place along the indirect route by copolymerization of a monomer mixture consisting of one or more olefins having 2-6 carbon atoms per molecule, one or more unsaturated carboxylic acids and one or more alkyl esters of unsaturated carboxylic acids followed by after-treatment of the copolymers so obtained, the unsaturated carboxylic acids may be either monobasic or polybasic carboxylic acids. Mixtures of unsaturated carboxylic acids may also be used. Examples of suitable unsaturated monobasic carboxylic acids are acrylic acid and methacrylic acid. Examples of appropriate unsaturated polybasic carboxylic acids are fumaric acid, maleic acid and itaconic acid. Preferred copolymers are those prepared by the indirect route using one or more unsaturated monocarboxylic acids. Particularly preferred are copolymers prepared using methacrylic acid.
• the after-treatment of the copolymers containing free carboxyl groups may be carried out in different ways. What is important is that the carboxyl groups are converted into -COOR groups, in which R represents a monovalent alkyl radical containing at least one free hydroxyl group.
• the copolymers containing free carboxyl groups may be caused to react with polyvalent alcohols such as glycol, glycerol, trimethylolpropane, pentaerythritol or p-dimethylolbenzene.
• the aftertreatment is preferably carried out by reacting the copolymers containing free carboxyl groups with cyclic ethers wherein the ring contains an oxygen atom and two or three carbon atoms, i.e., ethylene oxide and trimethylene oxide. Ethylene oxide is especially preferred.
• the copolymerization of olefins with unsaturated carboxylic acids and alkyl esters of unsaturated carboxylic acids is preferably carried out in solution in the presence of a free radical initiator, such as an azo compound or a peroxide.
• a free radical initiator such as an azo compound or a peroxide.
• the ratio in which the monomers are incorporated into a growing copolymer molecule depends on the reactivity of the monomers involved. If there are differences in reactivity, the molar ratio of the monomers in the mixture to be polymerized will be subject to considerable changes as the copolymerization proceeds, since the more reactive monomer is incorporated more rapidly. As a result, the composition of the copolymer also changes continually. As a general rule it may be said that, if in the polymerization of monomers which differ strongly in reactivity no special measures are taken, the products obtained are of an extremely heterogeneous composition.
• Associating substances which may be used are aliphatic compounds containing an oxygen atom attached to carbon, such as alcohols, ethers, ketones and carboxylic acids. Preference is given to lower aliphatic alcohols, such as methanol, ethanol, isopropanol and, in particular, to tert-butanol.
• the solvent in which the copolymerizations are carried out may be an aromatic solvent such as benzene, toluene or xylene, with benzene being preferred.
• the polymerizations may be conducted both batchwise and continuously. Continuous polymerization may take place in a tubular reactor or by continuously adding all reaction components in the ratio in which they are consumed in the process to a reaction mixture whose composition is kept homogeneous, for example by intensive stirring, while simultaneously discharging part of the reaction mixture.
• the after-treatment of the copolymers containing free carboxyl groups, in which the carboxyl groups are converted into COOR groups in which R represents a monovalent alkyl radical containing at least one free hydroxyl group, is preferably carried out with the aid of a cyclic ether, and in particular, ethylene oxide.
• This conversion may take place under the influence of a substance giving an alkaline reaction as a catalyst.
• Suitable substances giving an alkaline reaction are alkali metals, alkali metal oxides, alkali metal hydroxides, alkaline earth metals, alkaline earth metal oxides, alkaline earth metal hydroxides and organic compounds, such as trimethylamine, N-methylmorpholine, pyridine, quinoline and fl-picoline.
• a lithium compound is employed as a catalyst.
• suitable lithium compounds are lithium hydroxide, lithium hydride, lithium alkoxides, lithium carbonate and lithium acetate. Very favorable results may be obtained by using lithium hydroxide as a catalyst
• the reaction of the acid polymer with the cyclic ether is not conducted in the presence of a substance giving an alkaline reaction as a catalyst. Rather this catalyst is incorporated in the acid polymer beforehand. Incorporation of the catalyst in the acid polymer may take place by first combining one or more salts of substances giving an alkaline reaction with unsaturated carboxylic acids in the monomer mixture from which the acid polymer is prepared. The acid copolymer obtained by polymerization of this monomer mixture may then be reacted with a cyclic ether without using an additional catalyst. In this process, too, lithium salts are preferred.
• the reaction of the acid copolymer with the cyclic ether may take place at room temperature, but is preferably conducted at elevated temperatures between about and C. If the final product is liquid, the reaction may proceed without a solvent.
• the solvent if employed, may be either polar or non-polar.
• the polymer containing free carboxyl groups tends to form intramolecular hydrogen bridges, especially in a non-polar solvent, as a result of which the viscosity greatly increases.
• the reaction with the cyclic ether is therefore preferably carried out in the presence of a polar substance which prevents the formation of intramolecular hydrogen bridges.
• a low-boiling aliphatic alcohol is preferred.
• a very suitable medium for the reaction to be carried out is a mixture of a low-boiling aliphatic alcohol and an aromatic hydrocarbon such as benzene or toluene.
• the desired dispersant action and improvement of the viscometric properties is obtained when the quantity added is from 0.1 to 10 percent by weight and, in particular, when this copolymer. quantity is from 0.5 to 5 percent by weight of the lubri-
• the molecular weight of the copolymers according to eating oil composition. the invention may vary between wide limits.
• the lubricant comtion relates in particular to lubricant compositions conpositions according to the invention may also contain taining copolymers with a molecular weight (Mg) beother additives, such as antioxidants anti-corrosive tween 5,000 and 150,000, and in particular to lubricant agents, anti-foaming agents, agents to improve the lubricompositions containing copolymers with a molecular cating action and other substances which are usually weight between 15,000 and 100,000.
• Mg molecular weight
• the ratio of monoadded to lubricants. mers in the copolymer may also vary between wide limits.
• the invention relates in general to lubricant composimethacrylate and lauryl methacrylate and four copolytions containing polymeric compounds which have been mers of ethylene, methacrylic acid and lauryl methacryobtained by copolymerization of one or more olefins conlate (designated as polymers l-9) were prepared as taining from 26 carbon atoms per molecule with one f llows: A specified mixture of methacrylic esters methor more alkyl esters of. unsaturated carboxylic acids and acrylic acid, azodiisobutyronitrile, 300 g.
• the invention relates in particular to lubricant comthe autoclave at room temperature under a pressure of positions containing polymeric compounds which have up to 170 to 200 atm.
• the mixture was heated for been obtained by copolymerization of ethylene with one specified period, during which the pressure increased or more alkyl esters of C -C unsaturated monocarboxylic to 380-480 atm.
• the acids in which the alkyl group contains 8-20 carbon mixture was discharged and concentrated by partial atoms, and with one or more hydroxyalkyll, esters of evaporation of the solvent.
• the polymer was purified by C -C unsaturated monocarboxylic acids in which the precipitating three times in methanol. Finally the polymer hydroxyalkyl group contains 2-3 carbon atoms.
• the base oils suitable for the preparation of the lubricant compositions according to the invention may be mineral lubricating oils of varying viscosity, and also synthetic lubricating oils or lubricating oils containing fatty oils.
• the present lubricant additives may also be incorporated into lubricating greases.
• the invention is of particular importance in improving the quality of mineral lubricating oils or mixtures thereof.
• the polymeric compounds may be added to the lubricant as such or in the form of a concentrate obtained, by mixing the polymeric compounds with a small quantity of oil.
• the polymers of the present invention impart excellent dispersancy and viscos'ity index characteristics to lubricating oil as well as possessing excellent thermal stability.
• a lubricating oil composition comprising a major amount of a mineral lubricating oil and from 0.1 to 10% by weight of an oil soluble copolymer of ethylene with one or more C alkyl esters of C unsaturated monocarboxylic acids and with one or more C hydroxyalkyl esters of C unsaturated carboxylic acids said copolymer having a molecular weight between about 5,000 and 150,000.
• copolymer is a copolymer of ethylene, a member selected from the group consisting of lauryl methacrylate and stearyl methacrylate and mixtures thereof, and fl-hydroxyethyl methacrylate.
• copolymer is a copolymer of ethylene, lauryl methacrylate and p-hydroxyethyl methacrylate.

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

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• 1967
  • 1967-04-14 GB GB17198/67A patent/GB1112788A/en not_active Expired
• 1968
  • 1968-04-11 FR FR1559517D patent/FR1559517A/fr not_active Expired
  • 1968-04-11 BE BE713535D patent/BE713535A/xx unknown
  • 1968-04-11 NL NL6805167A patent/NL6805167A/xx unknown
  • 1968-04-11 DE DE19681770184 patent/DE1770184A1/de active Pending
  • 1968-04-12 US US721092A patent/US3518197A/en not_active Expired - Lifetime
• 1969
  • 1969-09-15 US US870777A patent/US3621004A/en not_active Expired - Lifetime

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