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
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
• • 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
  • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
• • 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
  • C10M2209/082—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 monocarboxylic
• • 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
  • 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
  • C10M2223/041—Triaryl phosphates
• • 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—Semi-solids; 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

• This invention relates to improved lubricant compositions and to novel oil-soluble copolymers contained therein.
• the suitability of a lubricating oil for use in internal combustion engines is dependent, among other properties, on its pour point, viscosimetric behavior, and dispersant ability. Since most lubricating base stocks do not inherent-' ly possess these properties to the extent required for use in present day internal combustion engines, it is customary to addone or more additives to the lubricating medium to improve these characteristics.
• polymeric additives have been proposed in the literature which are capable of improving the pour point, viscosity index or dispersant ability of lubricating oils.
• a select few ofjthese polymeric materials can be classified as multi-functional additives, i.e., capable of improving more than one of these properties, and fewer still capable of simultaneously improving all three of the aforementioned characteristics.
• the present invention relates to such a class of polymeric additives, which because of their unique structural configuration, have been un' expectedly found to significantly reduce the pour points of lubricating oils and also improve their viscosity indices and dispersant properties.
• the high activity of these polymeric materials is attributed to a combination of their side chain length, molecular weight and polarity.
• lubricating compositions comprising a major amount of a lubricating oil and a minor amount, from 1 to 10% by weight, of an oil soluble copolymer of one or more alkyl esters of an alpha,
• polymers according to the invention are capable of depressing the-pour point of the lubricating oil to a much greater extent.
• Preferred polymers according to the invention are those in which the average number of carbon atoms of the CH -(CH groups present in the alkyl side chains, n being at least 9, is from 13.0 to 14.1.
• the molecular weight of therpresent polymers may vary within wide limits. Often polymers are selected with a molecular weight M, of at least 100,000 and at most 2,000,000, in particular polymers with a molecular weight M of at least 250,000 and at most'l,250,000.
• An important further aspect of polymeric lube oil additives is their resistance to degradation by shear in the engine. if polymeric lube oil additives haveinsufiicient shear stability, one of the consequences is that the viscosity of the lubricating oil composition in which they are incorporated diminishes during use of the composition in the engine. it has been found that the molecular weight of the present polymers plays an important part as far as their shear stability is concerned. Polymers according to the invention have ahigh shear stability, especially if their molecular weight M is below 750,000.
• the molar ratio of the units derived from the alkyl esters to those derived from the hydroxy alkyl esters may vary within wide limits. Generally, for every 10 units derived from alkyl esters, the copolymers should contain 0.25-5 units derived from .the monohydroxy alkyl esters. To assure satisfactory pourability of concentrates of the present polymers in oil, preference is given to polymers which for every 10 units derived from the alkyl esters fewer than 3' units are derived from the monohydroxy alkyl esters. The use of the present polymers with low polarity is not only preferred from the standpoint of better pourability, but also for another reason.
• the present copolymers can be prepared by two routes. It is possible to prepare these copolymers directly by copolymerization of a mixture of monomers consisting of one or more alkyl esters of unsaturated monocarboxylic acids and one or more monohydroxy alkyl esters of unsaturated monocarboxylic acids.
• the copolymers are preferably prepared via an indirect route by copolymerization of a mixture of monomers consisting of one or more unsaturated monocarboxylic acids and one or more alkyl esters of unsaturated monocarboxylic acids and after treatment of the acid copolymers, in which the carboxylic groups are converted'to COOR groups, in g which R represents a monohydroxy alkyl group.
• alkyl esters of monocarboxylic acids suitable for use as monomers in the preparation of the present copolymers should consist of at least mole percent of alkyl esters having an alkyl chain which contains a group, n being at least 9.- Moreover, these alkyl esters should have such a chain length and be present in the monomer mixture in such relative proportions that the average number of carbon atoms of the CH (CI-1;),,-- groups present in the alkyl chains, n being at least 9, is at least 12.5 and at most 14.3.
• alkyl esters of unsaturated monocarboxylic acids in which an unbranched saturated hydrocarbon chain with at least carbon atoms such as n-decyl, n-dodecyl, ntetradecyl, n-hexadecyl, and n-octadecyl esters of unsaturated monocarboxylic acids.
• Alkyl esters of unsaturated monocarboxylic acids in which a branched hydrocarbon chain occurs are also suitable provided this branched hydrocarbon chain contains a Cli -(Cl m group, in which n is at least 9.
• the monomer mixture can contain other alkyl esters of unsaturated monocarboxylic acids such as alkyl esters with fewer than 10 carbon atoms in the alkyl chain or alkyl esters with 10 or more carbon atoms in the alkyl chain, in which, however, a CH,-(CH,) group, with n being at least 9, is absent.
• alkyl esters of unsaturated monocarboxylic acids such as alkyl esters with fewer than 10 carbon atoms in the alkyl chain or alkyl esters with 10 or more carbon atoms in the alkyl chain, in which, however, a CH,-(CH,) group, with n being at least 9, is absent.
• alkyl esters of unsaturated monocarboxylic acids such as alkyl esters with fewer than 10 carbon atoms in the alkyl chain or alkyl esters with 10 or more carbon atoms in the alkyl chain, in which, however, a CH,-(CH,) group, with
• the present copolymers can be conveniently prepared from a mixture of alkylmethacrylates which consists at least in part of alkylmethacryiates derived from alcohols obtained by a special hydroformulation process.
• the alcohols in question can be prepared by reacting oiefins with carbon monoxide and hydrogenin the presence of a complex catalyst which contains in the molecule a transition metal with an atomic number of 23 to 85 and at least one molecule of a biphyliic ligand which contains trivalent phosphorus,'arsine or antimony as catalyst.
• a .biphyiiic ligand is understood to mean a compound containing an element with an electron pair which is capable of forming a coordination bond with a metal atom and which element is at the same time capable of accepting electrons from the metal, as a result of which the stability of the complex is increased. Highly favorable results may be obtained by using a complex which contains cobalt, carbon monoxide and one or more phosphorus compounds.
• Unsaturated monocarboxylic acids which are particularly suitable for use in preparing alkyl ester and hydroxy alkyl ester monomers are those having 3 to 5 carbon atoms and alpha,beta-vinylidene unsaturation. Examples of such acids are acrylic acid, methacrylic acid, itaconic acid and crotonie acid. Esters of methacrylic acid have been found to be particularly advantageous in forming the copolymeric additives of the invention. 1
• the monohydroxy alkyl esters are generally formed from the aforementioned unsaturated monocarboxylic acids and dihydric alcohols oraiiphatic ethers.
• the monohydroxy alkyl group of the ester should contain from two to five carbon atoms.
• suitable monohydroxy alkyl ester monomers include partial esters of dihydric alcohols such as ethylene glycol with unsaturated monocarboxylic acids such as acrylic acid and methacryiic acid.
• esters further include reaction products of cyclic ethers which in addition to an oxygen atom contain two or three carbon atoms in the ring, such as ethylene oxide and trimethylene oxide with unsaturated monocarboxylic acids such as acrylic acid and methacryiic acid.
• copolymers of fl-hydroxycthyl methacrylate Preference is given to copolymers of fl-hydroxycthyl methacrylate. if the preparation of the present copolymers is effected via an indirect route, by copolymerization of a mixture of monomers consisting of one or more unsaturated monocnrboxyiic acids and by tiftertrcntmcnt of the copolymers thus obtained, it is preferred to use methacryiic acid as the unsaturated monocnrboxyiic acid.
• the aftertreatmcnt of the copolymers with free cnrboxyl groups as a result of which these groups are converted into -COOR groups, wherein R represents a monohydroxy alkyl group can be carried out in various ways.
• the after-treatment is preferably carried out by reacting the copolymers having free carboxyl groups with cyclic ethers which in addition to an oxygen atom contain two or three carbon atoms in the ring, such as ethylene oxide and trimethylene oxide, in particular ethylene oxide.
• the preparation of the acid copolymers is preferably carried out in solution in the presence of a radical initiator such as an azo compound or a peroxide.
• a radical initiator such as an azo compound or a peroxide.
• the relative proportion in which the monomers are incorporated into a growing copolymer molecule is dependent on the reactivity of the monomers in question. If these reactivities differ, the'molar ratio of the monomers in the mixture to be polymerized will change considerably as the copolymerization proceeds, since the more reactive monomer is incorporated more rapidly. The effect of this is that the composition of the copolymer likewise changes continually. In general, it may be said that if no special measures are taken in the polymerization of monomers which differ strongly in reactivity, products with an extremely heterogeneous composition are obtained.
• benzene for example, benzene, toluene, or xylene, in particular toi-' uene.
• the after-treatment of the copolymers with free carboxyl groups in which the carboxyl groups are converted into COOR groups wherein R represents a monohydroxy alkyl group is preferably'carried out by means of a cyclic ether, in particular ethylene oxide.
• This conversion can take place under the influence of a basic reacting substance as catalyst.
• suitable basic reacting substances include 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-methyl morpholine, pyridine, quinoiine and fl-picoline.
• a lithium compound is preferred to use a lithium compound as catalyst.
• suitable lithium compounds are, inter alia, lithium hydroxide, lithium hydride, lithium alkoxides, lithium carbonate, and lithium acetate. Very favorable results may be obtained by using lithium hydroxide as catalyst.
• a variant of the alter-treatment described above is one in which contrary to the usual practice, the reaction of the acid copoiymcr'with the cyclic ether is not carried out in the presence of a basic reacting substance as catalyst, but instead this catalyst is incorporated into the acid polymer at the outset of the reaction.
• the incorporation of the catalyst into the acid polymer can be effected by including in the mixture of monomers from which the acid polymer is prepared; one or more salts of basic reacting substances and unsaturated monocarboxylic acids.
• the acid copolymer resulting from the polymerization of this mixture of monomers can subsequently be reacted with a cyclic ether without using any additional catalyst.
• preference is given to lithium salts.
• the reaction of the acid copolymer withthe cyclic ether can be carried out at room temperature, but is preferably carried out at an elevated temperature, for example at a temperature between 95 and 130 C. If the final product is liquid, the reaction can take place without the use of a solvent. If a solvent is used it can be either a polar or a non-polar solvent.
• Thepolymer with free carboxylic acid groups shows a tendency, especially in a non-polar solvent, to form intermolecular hydrogen bonds as a result of which the viscosity increases sharply. For this reason it is preferred to carry out the reaction with the cyclic ether in the presence of a polar substance which inhibits the formation of intermolecular hydrogen bonds.
• a low-boiling aliphatic alcohol is very convenient for this purpose.
• a highly suitable medium for carrying out the reaction is a mixtureof a low-boiling aliphatic alcohol and an aromatichydrocarbon.
• the lubricants in which the polymers according to this invention can be incorporated as additives may be mineral lubricating oils of varying viscosity, synthetic lubricating oils or lubricating oils containing fatty oils.
• the polymers can also be employed in greases.
• the present polymers are of special importance for the improvement of minear lubricating oils or mixtures thereof.
• the polymers can be added to the lubricant as such or in the form of a concentrate obtained for example by mixing the polymers with a minor quantity of oil.
• the concentration of the present polymers in the lubricants may vary within wide limits, for example from 0.1 to 10% by weight, more specifically 0.5 to 5% by weight.
• the lubricating compositions may contain other additives such as antioxidants, anti-foaming agents, anti-corrosive agents. means for improving the lubricating action and other substances which are generally added to lubricants.
• alkyl methacrylates were derived from an alcohol mixture prepared by reacting oletins having 11-14 carbon atoms with carbon monoxide and hydrogen in the presence of a complex which contained cobalt and organically bound trivalent phosphorus.
• n-C MA, n-CIflHA, n-C MA, 'n-C MA and 11- C MA alky1 methacrylates with an unbranched'satw rated alkyl chain having 10, l2, 14, 16 and 18 carbon atoms respectively.
• HEMA hydroxyethylmethacrylate
• the table also shows the molecular weight M of the polymers as well as the average number of carbon atoms of the groups CH -(Cl-lfl present in the alkyl side chains,wherein n is at least 9. This average number of carbon atoms is designated in the table with C TABLEI Molar composition 01' the copolymers 1'01.
• z 1'.- 10 11 10 is 470, 000 1:1. 7 z 112 10 11 10 111 200,000 13.;
• a commercial dispernnt a copolymer of alkyl methacrylates and N-vinyl pyrrolidone
• compositions of the invention also have good shear stability and have dispersant properties superior to those of a comparable commercial additive.
• a lubricant composition consisting essentially of a major amount of a lubricating oil and a minor amount, from 1 to 10% by weight, of an oil-soluble copolymer of one or more alkyl esters of a C alpha, beta-'vinylidene monocarboxylic acid and one or more monohydroxy C alkyl esters of C alpha, betavinylidene monocarboxylic acid; wherein at least mole percent of the alkyl esters have CH (CH,),, groups, n being at least 9, and the average number of carbon atoms of said groups is from of the units derived from alkyl esters to those derived from hydrosy alkyl esters is 10 to l-3.
• composition of claim 8 wherein the hydroxy- 4.
• composition of claim 2 wherein the average number of carbon atoms in the CH,--(CH,),,- groups, n being at least 9, is from 13.0 to 14.1.
• composition of claim 3 wherein the monocarboxylic acid used to form the alkyl and monohydroxy alkyl esters is selected from the group consisting of methacrylic acid, acrylic acid and mixtures thereof.
• composition of claim 1 wherein the lubricating oil is a mineral lubricating oil.
• alkyl ester is ap-hydroxyethyl ester.
• composition of claim 9 wherein the lubricating oil is a mineral lubricating oil.

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

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Cited By (9)

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• 0
  • NL NL134235D patent/NL134235C/xx active
• 1968
  • 1968-04-26 NL NL6805941A patent/NL6805941A/xx unknown
• 1969
  • 1969-04-17 US US817145A patent/US3598737A/en not_active Expired - Lifetime
  • 1969-04-24 CH CH627069A patent/CH540332A/de not_active IP Right Cessation
  • 1969-04-24 BR BR208332/69A patent/BR6908332D0/pt unknown
  • 1969-04-24 DE DE19691920971 patent/DE1920971A1/de active Pending
  • 1969-04-24 BE BE732022D patent/BE732022A/xx unknown
  • 1969-04-24 ES ES366410A patent/ES366410A1/es not_active Expired
  • 1969-04-24 FR FR6912996A patent/FR2007001A1/fr not_active Withdrawn
  • 1969-04-24 JP JP44031420A patent/JPS4823164B1/ja active Pending
  • 1969-04-24 GB GB21036/69A patent/GB1235961A/en not_active Expired

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