US2091627A - Composition of matter and process - Google Patents
Composition of matter and process Download PDFInfo
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- US2091627A US2091627A US729699A US72969934A US2091627A US 2091627 A US2091627 A US 2091627A US 729699 A US729699 A US 729699A US 72969934 A US72969934 A US 72969934A US 2091627 A US2091627 A US 2091627A
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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
- 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
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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
- 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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- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
- C10M2201/042—Carbon; Graphite; Carbon black halogenated, i.e. graphite fluoride
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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
- 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
- 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
-
- 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
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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
- 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
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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
- 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
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- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
-
- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
-
- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
-
- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
-
- 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
- C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
-
- 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
Definitions
- This invention relates to a method for improving the viscosity-temperature characteristics of lubricating oils, and is concerned more particularly with a method for raising the so-called vis- 5 cosity index of lubricating oils which are essentially of a hydrocarbon nature for the purpose of improving their lubricant qualities.
- a lubricating oil As a lubricating oil is heated its viscosity decreases, but the rate at which the viscosity falls oil with rise in temperature of the oil varies with the nature of the oil.
- Highly parafiinic oils, such as Pennsylvania oils do not decrease in viscosity with rising temperature as rapidly as do naphthenic oils. In the manufacture of lubricating 1 oils, it is customary to rate the quality of oils by referring to their viscosity index.
- High grade oils which show a small change of viscosity with temperature are arbitrarily assigned a 100 V. I. (viscosity index) and oils having a large vis- 20 cosity-temperature coeflicient are given a value of 0 (zero) V. I. Viscosities are usually determined at 100 F. and 210 F. A mathematical relationship between the respective viscosities in Saybolt seconds at these two temperatures has 25 been found to exist which is characteristic of each type of oil, and which expressed as viscosity index indicates the suitability of ,a lubricating oil for various purposes. In automobile engines oils of high viscosity index are desirable so that 30 when the engine iscold, it can be more easily started, and when the engine is hot the oil does not lose too much of its body or lubricating qualities.
- the object of this invention is to provide a method by which the viscosity index of an oil can be raised to a relatively high value without detracting from its color, odor, stability towards oxidation or its lubricating properties, and by which an oil of better quality can be obtained.
- the above object is accomplished by incorporating with the lubricating oil a relatively small amount of a synthetic, oil-soluble, polymerized ester of the acrylic acid or vinyl ester series.
- This can be'done by either thoroughly mixing the' preformed oil-soluble polymerized ester with the oil, or else by mixing the oil with the unpolymerized ester, and then polymerizing said ester in the oil.
- the viscosity index of oils can be increased by adding thereto certain hydrocarbons, such as rubber, hydrogenated rubber, and hydrogenation products of polymers of oleflne hydrocarbons, or certain salts, such as aluminum or zinc stearates.
- certain hydrocarbons such as rubber, hydrogenated rubber, and hydrogenation products of polymers of oleflne hydrocarbons, or certain salts, such as aluminum or zinc stearates.
- these compounds are either readily oxidizable. (rubber) and rapidly deteriorate in the oil even when anti-oxidants are present, or else they are non-uniform compositions whose power of increasing the viscosity index is variable and in many cases relatively low compared to the substances used in the present process.
- Salts such as the zinc or aluminum stearates also give variable results and tend to become grainy and separate from the oil on storage or at low temperatures.
- polymers used in the present invention are colorless, non-odorous, nonautoxidizable materials the viscosity of which can be accurately and uniformly controlled.
- esters having the vinyl or substituted vinyl group are used; namely, esters of the formula wherein X is a hydrogen atom, an alkyl or aromatic hydrocarbon group, and Y is alpha-alkyl or alpha-aryl substitution products andmonohydric alcohols containing more than four carbon atoms such as the amyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, myricyl, cetyl, or
- octadecyl esters of acrylic acid, alpha-methalauric, palmitie, stearic, n-amyl-benzoic, mph-- thenic, hexahydrobenzoic, or of p-n-butyloxybutyric acid can be used.
- esters are employed in the form of their oil-soluble polymers which should be as free as possible of unpolymerized monomeric esters, since the presence of unsaturated or volatile compounds in the lubricating oils is objectionable.
- Unpoly-- 20 merized esters can be removed by heating the polymer or the mixture of lubricating oil and polymer in vacuo to a temperature suflioiently high to volatilize the monomeric ester, but preferably the polymerization should be carried out as completely as possible and the latter operation dispensed with.
- esters of acrylic acid or alpha-methacrylic acid and monohydric, saturated, primary aliphatic alcohols containing from 5 to 18 carbon atoms in the molecule are those derived from the straight chain, monohydric primary, saturated aliphatic alcohols containing 8 to 18 carbon atoms such as the normal octyl, lauryl, cetyl, or octadecyl esters. 40 These esters need not be pure, but may be pre pared from technical mixtures of the higher aliphatic alcohols such as are obtained commercially from the catalytic high pressure hydrogenation of fatty acids or their esters.
- any mixture of two or more polymers of the esters set forth herein can alsobe used. These may be simple mixtures of such polymers, or they may be co-polymers which can be preparedby polymerizing a. mixtureoi two or more of the- 80 monomeric esters.
- the polymers are prepared for use in the present process, preferably by heating the monomeric esters at 70100 C. in the presence of small amounts of polymerization-inducing catalysts ll such as peroxides-or ozonides. These are referred to as "heat polymerization products.- Other catalysts may, however, be used, such as anhydrous haiides of polyvalent or amphoteric metals,
- the polymers obtained were colorless or faintly yellow. They were each 70 dissolved in the oil in the concentrations shown bywarmingtoabout 100 C.andstirringuntila homogeneous clear solution was obtained.
- the polymers are more rubbery and viscousthan those made at the higher temperature (100 C.) with 1% of benzoylperoxide and give slightly higher rises-in viscosity index than the latter.
- Oil A was a Mid-Continent oil showing the following inspection:
- Example 1 If an oil of higher viscosity index than that shown in Example 1 is used, for instance, a Pennsylvania oil having a viscosity index of 80, smaller quantities oi. the polymerized ester are required to give an oil with a viscosity index of more than 100.
- lubricating oil as used herein is to be interpreted broadly as referring to natural or synthetic oils, essentially l5 hydrocarbons, possessing lubricating properties regardless of their actual viscosity, and'includes crude or refined petroleums, hydrogenated petroleum oils or hydrogenated cracked petroleum oils, high molecular oily hydrocarbons, such as are obtained by the polymerization of oleflnes or by the condensation of olefines with aromatic hydrocarbons.
- These lubricating oils can also contain other materials in solution or in suspension which are not necessarily hydrocarbons but which serve to give certain desirable properties in such oils, such as anti-oxidants, pour point depressors, or graphite.
- oils may also be used for the manufacture of other lubricants such as greases by incorporating in them the 3 soaps of lime, soda, potash, etc., as is customary in the preparation of lubricating greases.
- Oils treated by the hereindescribed process are particularly useful as gear oils, bearing oils, and cylinder oils in automotive engines. They may also be used as oils for hydraulic brakes, artillery recoil systems and similar equipment where rapid changes of viscosity with temperature are undesirable.
- An oil of improved viscosity-temperature coeflicient comprising a lubricating oil of relatively low viscosity index to which has been added a small quantity of an oil-soluble, viscous, heat polymerization product of an ester of alphamethacrylic acid and a monohydric saturated alcohol containing more than four carbon atoms.
- An oil of improved viscosity-temperature coefficient and increased viscosity index comprising a lubricating oil of relatively low viscosity index to which has been added from 0.1 to 6% by weight of an oil-soluble, viscous, heat polymerization product which is a member of the group consisting of the amyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, myricyl, cetyl and octadecyl esters of alpha-methacrylic acid.
- An oil of improved viscosity-temperature coefiicient comprising a lubricating oil of relatively low viscosity index to which has been added a small quantity of an oil-soluble, viscous, polymerization product 01 an ester of alpha-methacrylic acid and a monohydric saturated alcohol containing more than tour carbon atoms.
- An oil comprising a. lubricating oil to which has been added as a material for increasing the viscosity index, a small amount of a viscous, oilsoluble polymerization product of an ester having the formula wherein X" is an alkyl group and R is the radical of a monohydric saturated alcohol having more than 4 carbon atoms.
- a lubricating 011 containing as a material for increasing its viscosity index, a small amount of an oil-soluble polymer of an ester of alphamethacrylic acid and a primary, aliphatic, monohydric alcohol containing from 8 to 18 carbon atoms inclusive.
- An oil having lubricating properties containing, as a material for increasing its viscosity index, a small amount of an oil-soluble, viscous polymerization product of an ester 0! alphamethacrylic acid and lauryl alcohol.
- An oil having lubricating properties containing, as a material for increasing its viscosity index, a small amount or an oil-soluble, viscous polymerization product of an ester of alphamethacrylic acid and cetyl alcohol.
- An oil having lubricating properties containing, as a material for increasing its viscosity index, a small amount of an oil-soluble, viscous polymerization product of an ester of alphamethacrylic acid and octadecyl alcohol.
Description
Patented Aug. 31, 1937 2,091,021 COMPOSITION or mr'rsa AND raocsss Herman A. Bruson, Germantown, Philadelphia, Pa., minor to Biihm 8a Haas Company, Philadelphia, Pa.
No Drawing. Application June 8, 1934, Serial No. 729.699
10 Claims.
This invention relates to a method for improving the viscosity-temperature characteristics of lubricating oils, and is concerned more particularly with a method for raising the so-called vis- 5 cosity index of lubricating oils which are essentially of a hydrocarbon nature for the purpose of improving their lubricant qualities. As a lubricating oil is heated its viscosity decreases, but the rate at which the viscosity falls oil with rise in temperature of the oil varies with the nature of the oil. Highly parafiinic oils, such as Pennsylvania oils, do not decrease in viscosity with rising temperature as rapidly as do naphthenic oils. In the manufacture of lubricating 1 oils, it is customary to rate the quality of oils by referring to their viscosity index. High grade oils which show a small change of viscosity with temperature are arbitrarily assigned a 100 V. I. (viscosity index) and oils having a large vis- 20 cosity-temperature coeflicient are given a value of 0 (zero) V. I. Viscosities are usually determined at 100 F. and 210 F. A mathematical relationship between the respective viscosities in Saybolt seconds at these two temperatures has 25 been found to exist which is characteristic of each type of oil, and which expressed as viscosity index indicates the suitability of ,a lubricating oil for various purposes. In automobile engines oils of high viscosity index are desirable so that 30 when the engine iscold, it can be more easily started, and when the engine is hot the oil does not lose too much of its body or lubricating qualities.
The object of this invention is to provide a method by which the viscosity index of an oil can be raised to a relatively high value without detracting from its color, odor, stability towards oxidation or its lubricating properties, and by which an oil of better quality can be obtained.
The above object is accomplished by incorporating with the lubricating oil a relatively small amount of a synthetic, oil-soluble, polymerized ester of the acrylic acid or vinyl ester series. This can be'done by either thoroughly mixing the' preformed oil-soluble polymerized ester with the oil, or else by mixing the oil with the unpolymerized ester, and then polymerizing said ester in the oil. The amount of the poly merized ester which should be present in the oil ing oil used; the degree of viscosity index rise which is desired, and to a certain extent with the individual polymerized ester which is used. since these oil-soluble polymerized esters are very varies somewhat with the nature of the lubrlcat-- powerful increasers orv the'viscosity index, only small amounts are required; quantities as low as 0.1% on the weight of the oil being eifective, and, as an upper limit, 6% on the weight of the oil being extremely powerful in this respect. In general 0.6-2% on the weight of the lubricating oil gives satisfactory results;
It is known that the viscosity index of oils can be increased by adding thereto certain hydrocarbons, such as rubber, hydrogenated rubber, and hydrogenation products of polymers of oleflne hydrocarbons, or certain salts, such as aluminum or zinc stearates. These compounds are either readily oxidizable. (rubber) and rapidly deteriorate in the oil even when anti-oxidants are present, or else they are non-uniform compositions whose power of increasing the viscosity index is variable and in many cases relatively low compared to the substances used in the present process. Salts such as the zinc or aluminum stearates also give variable results and tend to become grainy and separate from the oil on storage or at low temperatures.
In contrast thereto the polymers used in the present invention are colorless, non-odorous, nonautoxidizable materials the viscosity of which can be accurately and uniformly controlled.
Moreover, when added to lubricating oils they also have the advantage of acting as pour point depressors.
For the purpose of this invention, the oilsoluble polymerization products of esters having the vinyl or substituted vinyl group, according to the following general formula, are used; namely, esters of the formula wherein X is a hydrogen atom, an alkyl or aromatic hydrocarbon group, and Y is alpha-alkyl or alpha-aryl substitution products andmonohydric alcohols containing more than four carbon atoms such as the amyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, myricyl, cetyl, or
octadecyl esters of acrylic acid, alpha-methalauric, palmitie, stearic, n-amyl-benzoic, mph-- thenic, hexahydrobenzoic, or of p-n-butyloxybutyric acid can be used.
These esters are employed in the form of their oil-soluble polymers which should be as free as possible of unpolymerized monomeric esters, since the presence of unsaturated or volatile compounds in the lubricating oils is objectionable. Unpoly-- 20 merized esters can be removed by heating the polymer or the mixture of lubricating oil and polymer in vacuo to a temperature suflioiently high to volatilize the monomeric ester, but preferably the polymerization should be carried out as completely as possible and the latter operation dispensed with.
The most eifective polymers for the present P pose, from the point of view of availability, cost, and power of increasing the viscosity index of oils, are the polymerized esters of acrylic acid or alpha-methacrylic acid and monohydric, saturated, primary aliphatic alcohols containing from 5 to 18 carbon atoms in the molecule. The esters possessing the highest solubility and stability in oils and giving the highest viscosity index are those derived from the straight chain, monohydric primary, saturated aliphatic alcohols containing 8 to 18 carbon atoms such as the normal octyl, lauryl, cetyl, or octadecyl esters. 40 These esters need not be pure, but may be pre pared from technical mixtures of the higher aliphatic alcohols such as are obtained commercially from the catalytic high pressure hydrogenation of fatty acids or their esters.
5 Any mixture of two or more polymers of the esters set forth herein can alsobe used. These may be simple mixtures of such polymers, or they may be co-polymers which can be preparedby polymerizing a. mixtureoi two or more of the- 80 monomeric esters.
The polymers are prepared for use in the present process, preferably by heating the monomeric esters at 70100 C. in the presence of small amounts of polymerization-inducing catalysts ll such as peroxides-or ozonides. These are referred to as "heat polymerization products.- Other catalysts may, however, be used, such as anhydrous haiides of polyvalent or amphoteric metals,
according to the known art of polymerizing vinyl U compounds. 1
Iii the following examples the polymers used were prepared by heating the monomeric esters at 100 C. for 15hours in the presence of 0.5% by weight of benzoyl peroxide and, if necessary,
05 removing any unchanged monomeric ester by V careiullyheating the product in high vacuo (0.5-1
mm.) toa temperature just above the boiling point of the monomer. The polymers obtained were colorless or faintly yellow. They were each 70 dissolved in the oil in the concentrations shown bywarmingtoabout 100 C.andstirringuntila homogeneous clear solution was obtained.
By using 0.1% of benzoyl peroxide on the weight of the monomeric wter and polymerizing 7 at 75 C. for 24-48 hours, the polymers are more rubbery and viscousthan those made at the higher temperature (100 C.) with 1% of benzoylperoxide and give slightly higher rises-in viscosity index than the latter.
Viscosities were determined at 100 F. and 210 F. and the viscosity index calculated according to standard methods, (see The Oil and Gas Journal, -March 31, 1932, pp. 92, 93, 169). The f01' lowing table shows the efiect of various polymerized esters of acrylic acid, etc., on the viscosity and viscosity index of lubricating oils.
Oil A was a Mid-Continent oil showing the following inspection:
Gravity A. P. I 25.0
Saybolt vis./100 F 219 Saybolt via/210 F 45. Viscosity index 63 Flash point F 400 Fire point do 460 Pour point ...d
' Example 1 Viscosity" Polymcrised star added t cos] 1 90" At2l0 mac:
Original oil (A) (Mid-Continent p0 0. m 219 45. 63 Cetyl-alpha-methnerylate l. 00 282 51 U5 D0 1.32 33) 54.9 104 Do 200 357 57.9 111 n-Amyl-alpha-methauylats- 1. 1K) 219 49. 4 100 D0 0. 60 2&3 47. 1 S0 p-Hexyl-alpha-nnthacrylata- 0. 60 253 48. 2 78 D0 1. Z) 251 49. 5 87 D0 2(1) 210 51.1 98 n-Octyl-alpha-methacrylato 0.00 246 48.1 85 Do 1.20 281 51 5 100 I n Lauryl-alpha-methauylatm 0. 60 258 4s. 9 85 Vinyl laurato 0. 50 270 49. 5 85 (Jo-polymer of equal weights cetyl-alphalate and lanryl-alpha-methacrylate 1. 20 260 50 98 n-Oetyl-aaylato l. 33 31 l. 1 5i. 6 107 200 330 56 110 0. 50 252 48. 5 81 on the weight olthe oil. Vmcosity is in Saybolt seconds.
Saybolt vigmosity Yiscosity index msec.,50.9see 100 (oi Upon adding 1.3% by weight of n-octadecylalpha-methacrylate polymer, the oil showed the following properties:
Saybolt vis. at'100 F sec 355.7 Saybolt vis. at 210 F do 60.5 Viscosity in 122' -(b) The addition of 0.7% by weight of polymerized lauryl acrylate to the above oil gave an oil having a. osity index of 113.
(c) 1% by weight of polymerized cetyl-alphamethacrylate .was added to a Pennsylvania oil having a pour point of +35.,F. The pour point of themixture was +15 F. V
' It will be seen from the above table that the addition of about 1% of the polymers on the weight of the oil raises the viscosity index about 30 points. The addition of 4% "of any of the above polymers on the 'weightof the-above oil approximately doubles the original viscosity in- Instead of the above tabulated esters, any of the other polymerized esters enumerated herein can similarly be used, the above, tabulated results being simply typical of the whole group of compounds.
If an oil of higher viscosity index than that shown in Example 1 is used, for instance, a Pennsylvania oil having a viscosity index of 80, smaller quantities oi. the polymerized ester are required to give an oil with a viscosity index of more than 100.
It is understood that the term lubricating oil as used herein is to be interpreted broadly as referring to natural or synthetic oils, essentially l5 hydrocarbons, possessing lubricating properties regardless of their actual viscosity, and'includes crude or refined petroleums, hydrogenated petroleum oils or hydrogenated cracked petroleum oils, high molecular oily hydrocarbons, such as are obtained by the polymerization of oleflnes or by the condensation of olefines with aromatic hydrocarbons. These lubricating oils can also contain other materials in solution or in suspension which are not necessarily hydrocarbons but which serve to give certain desirable properties in such oils, such as anti-oxidants, pour point depressors, or graphite. These oils may also be used for the manufacture of other lubricants such as greases by incorporating in them the 3 soaps of lime, soda, potash, etc., as is customary in the preparation of lubricating greases. Oils treated by the hereindescribed process are particularly useful as gear oils, bearing oils, and cylinder oils in automotive engines. They may also be used as oils for hydraulic brakes, artillery recoil systems and similar equipment where rapid changes of viscosity with temperature are undesirable.
What I claim is:
1. An oil of improved viscosity-temperature coeflicient comprising a lubricating oil of relatively low viscosity index to which has been added a small quantity of an oil-soluble, viscous, heat polymerization product of an ester of alphamethacrylic acid and a monohydric saturated alcohol containing more than four carbon atoms.
2. An oil of improved viscosity-temperature coefficient and increased viscosity index comprising a lubricating oil of relatively low viscosity index to which has been added from 0.1 to 6% by weight of an oil-soluble, viscous, heat polymerization product which is a member of the group consisting of the amyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, myricyl, cetyl and octadecyl esters of alpha-methacrylic acid.
3. A lubricating oil of relatively high viscosity index consisting of an oil of relatively low viscosity index and a small amount of an oilsoluble joint polymer of at least two diflerent esters of alpha-methacrylic acid the alcohol radicals of which are saturated and contain more than 4 carbon atoms.
4. An oil of improved viscosity-temperature coefiicient comprising a lubricating oil of relatively low viscosity index to which has been added a small quantity of an oil-soluble, viscous, polymerization product 01 an ester of alpha-methacrylic acid and a monohydric saturated alcohol containing more than tour carbon atoms.
5. An oil, comprising a. lubricating oil to which has been added as a material for increasing the viscosity index, a small amount of a viscous, oilsoluble polymerization product of an ester having the formula wherein X" is an alkyl group and R is the radical of a monohydric saturated alcohol having more than 4 carbon atoms.
- 6. A lubricating 011, containing as a material for increasing its viscosity index, a small amount of an oil-soluble polymer of an ester of alphamethacrylic acid and a primary, aliphatic, monohydric alcohol containing from 8 to 18 carbon atoms inclusive.
'7. A lubricating oil containing as a material for increasing its viscosity index, a small amount of an oil-soluble joint polymer of at least two difierent esters having the formula x 4 ll CHI: -C-OR wherein X is an alkyl group and R. is the radical of an aliphatic monohydric saturated alcohol having more than 4 carbon atoms.
8. An oil having lubricating properties containing, as a material for increasing its viscosity index, a small amount of an oil-soluble, viscous polymerization product of an ester 0! alphamethacrylic acid and lauryl alcohol.
9. An oil having lubricating properties containing, as a material for increasing its viscosity index, a small amount or an oil-soluble, viscous polymerization product of an ester of alphamethacrylic acid and cetyl alcohol.
10. An oil having lubricating properties containing, as a material for increasing its viscosity index, a small amount of an oil-soluble, viscous polymerization product of an ester of alphamethacrylic acid and octadecyl alcohol.
HERMAN A. BRUSON.
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US729699A US2091627A (en) | 1934-06-08 | 1934-06-08 | Composition of matter and process |
Applications Claiming Priority (1)
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US729699A US2091627A (en) | 1934-06-08 | 1934-06-08 | Composition of matter and process |
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US2091627A true US2091627A (en) | 1937-08-31 |
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US729699A Expired - Lifetime US2091627A (en) | 1934-06-08 | 1934-06-08 | Composition of matter and process |
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Cited By (69)
Publication number | Priority date | Publication date | Assignee | Title |
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US2426852A (en) * | 1943-09-15 | 1947-09-02 | Jasco Inc | High temperature lubricant |
US2435777A (en) * | 1945-01-31 | 1948-02-10 | Rohm & Haas | Preparation of quaternary ammonium polyacrylates |
US2435950A (en) * | 1945-02-03 | 1948-02-10 | Rohm & Haas | Hydraulic fluids |
US2438446A (en) * | 1945-05-25 | 1948-03-23 | Standard Oil Dev Co | Lubricant and hydraulic fluid composition |
US2441023A (en) * | 1945-01-26 | 1948-05-04 | Shell Dev | Lubricating oil compositions containing polymerized allyl esters of carboxylic acids |
US2442741A (en) * | 1945-09-06 | 1948-06-01 | Cities Service Oil Co | High viscosity damping fluid |
US2449335A (en) * | 1942-10-28 | 1948-09-14 | Frank J Sowa | Hydraulic pressure device and actuating fluid therefor |
US2455961A (en) * | 1944-06-10 | 1948-12-14 | Du Pont | Hydraulic fluid |
US2467147A (en) * | 1945-03-22 | 1949-04-12 | Standard Oil Dev Co | Low-temperature lubricant |
US2475246A (en) * | 1944-12-30 | 1949-07-05 | Standard Oil Dev Co | Lubricants |
US2499723A (en) * | 1947-07-28 | 1950-03-07 | Du Pont | Lubricants containing copolymers of ethylene and vinyl acetate |
US2512255A (en) * | 1947-12-31 | 1950-06-20 | Gulf Research Development Co | Hydraulic fluids |
US2512771A (en) * | 1947-09-17 | 1950-06-27 | Rohm & Haas | Operating fluids based on acetals |
US2528347A (en) * | 1948-07-13 | 1950-10-31 | California Research Corp | Nonflammable hydraulic fluid |
US2528348A (en) * | 1948-07-13 | 1950-10-31 | California Research Corp | Nonflammable hydraulic fluid |
US2541590A (en) * | 1948-02-13 | 1951-02-13 | Shell Dev | Lubricating compositions |
US2544376A (en) * | 1948-08-21 | 1951-03-06 | Monsanto Chemicals | Lubricating oil containing a polymer of oleyl methacrylate |
US2544375A (en) * | 1948-08-21 | 1951-03-06 | Monsanto Chemicals | Lubricating oil containing a polymer of tetradecyl vinyl ether |
US2549270A (en) * | 1948-07-19 | 1951-04-17 | Shell Dev | Lubricant and hydraulic fluid composition |
US2583588A (en) * | 1949-06-08 | 1952-01-29 | Mosteller James Calvin | Less inflammable hydraulic fluid |
US2602048A (en) * | 1949-01-24 | 1952-07-01 | Standard Oil Dev Co | Lubricating oil additives |
US2602780A (en) * | 1945-08-17 | 1952-07-08 | William A Zisman | Hydraulic fluid |
US2612475A (en) * | 1949-10-28 | 1952-09-30 | Standard Oil Dev Co | Lubricating oil additive |
US2615799A (en) * | 1948-04-03 | 1952-10-28 | Sinclair Refining Co | Diesel fuel |
US2616854A (en) * | 1943-11-13 | 1952-11-04 | Fenske Merrell Robert | Hydraulic fluid |
US2616852A (en) * | 1947-06-21 | 1952-11-04 | Mineral oil composition | |
US2616851A (en) * | 1947-04-29 | 1952-11-04 | Socony Vacuum Oil Co Inc | Mineral oil composition containing esters of product obtained by reaction between maleic anhydride and vinyl acetate |
US2637698A (en) * | 1948-12-30 | 1953-05-05 | Standard Oil Dev Co | Mineral oil lubricating composition containing a copolymer of an alkyl ester of itaconic acid and an alkyl acrylate or methacrylate |
US2653133A (en) * | 1950-12-07 | 1953-09-22 | Du Pont | Copolymers and lubricants containing the same |
US2655479A (en) * | 1949-01-03 | 1953-10-13 | Standard Oil Dev Co | Polyester pour depressants |
US2666033A (en) * | 1951-04-11 | 1954-01-12 | Texas Co | Lithium soap grease containing methacrylate ester polymer for bearing noise suppression |
US2671760A (en) * | 1951-05-18 | 1954-03-09 | William S Port | Lubricating oil compositions |
US2672446A (en) * | 1949-11-30 | 1954-03-16 | Standard Oil Co | Lubricants |
US2710842A (en) * | 1950-05-19 | 1955-06-14 | Texas Co | Hydraulic transmission fluid |
US2737496A (en) * | 1952-02-16 | 1956-03-06 | Du Pont | Lubricating oil compositions containing polymeric additives |
US2751039A (en) * | 1952-12-23 | 1956-06-19 | California Research Corp | Filters coated with thickened oils |
US2834733A (en) * | 1949-04-01 | 1958-05-13 | Douglas Aircraft Co Inc | Hydraulic fluid and lubricant composition |
US2841558A (en) * | 1955-06-06 | 1958-07-01 | Monsanto Chemicals | Hydrocarbon oil compositions |
US2851421A (en) * | 1951-08-07 | 1958-09-09 | Pure Oil Co | Power transmission fluids |
US2880175A (en) * | 1952-05-01 | 1959-03-31 | Exxon Research Engineering Co | Lubricating oil additive compatibility improver |
US2894911A (en) * | 1957-12-16 | 1959-07-14 | Douglas Aircraft Co Inc | Fire-resistant hydraulic fluid |
DE1075776B (en) * | 1960-02-18 | Berlin-Weißensee Wilhelm E. Müller | Process for the production of lubricating greases based on mineral oil | |
US2982715A (en) * | 1958-02-11 | 1961-05-02 | Shell Oil Co | Separation of normal paraffin wax from lubricating oil utilizing molecular sieve |
US2992987A (en) * | 1958-06-26 | 1961-07-18 | Monsanto Chemicals | Lubricating oil additive concentrate |
US3194777A (en) * | 1956-05-14 | 1965-07-13 | Pittsburgh Plate Glass Co | Coating compositions |
US3226326A (en) * | 1962-07-30 | 1965-12-28 | Shell Oil Co | Lubricating composition |
US3227696A (en) * | 1960-02-26 | 1966-01-04 | Shell Oil Co | Phosphorous and chlorine-containing copolymers as lubricant additives |
US3268494A (en) * | 1962-12-28 | 1966-08-23 | Shell Oil Co | Lubricating compositions |
US3278500A (en) * | 1960-12-07 | 1966-10-11 | Union Carbide Corp | Sulfur-containing polymers |
US3496103A (en) * | 1967-05-25 | 1970-02-17 | Us Army | Friction reduction by poly(n-alkyl methacrylates) in solution and dry films |
US3510425A (en) * | 1967-06-23 | 1970-05-05 | Timothy C Wilson | Oil mist lubrication process and novel lubricating oil composition for use therein |
US3542680A (en) * | 1963-04-23 | 1970-11-24 | Lubrizol Corp | Oil-soluble carboxylic acid phenol esters and lubricants and fuels containing the same |
US3853497A (en) * | 1972-11-08 | 1974-12-10 | Texaco Inc | Low pour vacuum gas oil compositions |
US4088589A (en) * | 1976-05-20 | 1978-05-09 | Exxon Research & Engineering Co. | Dual pour depressant combination for viscosity index improved waxy multigrade lubricants |
US4146492A (en) * | 1976-04-02 | 1979-03-27 | Texaco Inc. | Lubricant compositions which exhibit low degree of haze and methods of preparing same |
US4149984A (en) * | 1977-09-08 | 1979-04-17 | Rohm Gmbh | Lubricating oil additives |
JPS5911638B1 (en) * | 1971-05-05 | 1984-03-16 | Shell Int Research | |
JPS60110790A (en) * | 1983-10-28 | 1985-06-17 | レーム・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | N-paraffin-containing lubricating oil additive |
US4734446A (en) * | 1985-03-25 | 1988-03-29 | The Lubrizol Corporation | Polymeric compositions comprising an oil-soluble polymer and an oil-soluble acrylate polymerization of product |
US4822508A (en) * | 1985-12-13 | 1989-04-18 | Rohm Gmbh | Shear stable multirange oils having an improved viscosity index |
US4844829A (en) * | 1987-08-19 | 1989-07-04 | Pennzoil Products Company | Methacrylate pour point depressants and compositions |
US4867894A (en) * | 1986-03-07 | 1989-09-19 | Rohm Gmbh | Pour point improving additives for mineral oils |
US4956111A (en) * | 1987-08-19 | 1990-09-11 | Pennzoil Products Company | Methacrylate pour point depressants and compositions |
US5043087A (en) * | 1986-04-25 | 1991-08-27 | Rohn Gmbh | Addives for paraffinic lubricants |
WO1993012212A1 (en) * | 1991-12-09 | 1993-06-24 | Exxon Research And Engineering Company | Wax isomerate having a reduced pour point |
US5520832A (en) * | 1994-10-28 | 1996-05-28 | Exxon Research And Engineering Company | Tractor hydraulic fluid with wide temperature range (Law180) |
US20080108533A1 (en) * | 2006-11-07 | 2008-05-08 | Peer William J | Methacrylate copolymer pour point depressants |
US20090151235A1 (en) * | 2007-12-18 | 2009-06-18 | Eugene Scanlon | Biodiesel cold flow improver |
WO2013076424A1 (en) | 2011-11-22 | 2013-05-30 | Universite Du Sud Toulon-Var | Poly(n-alkyl acrylate) polymers and use thereof as oil pour point depressants |
-
1934
- 1934-06-08 US US729699A patent/US2091627A/en not_active Expired - Lifetime
Cited By (74)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1075776B (en) * | 1960-02-18 | Berlin-Weißensee Wilhelm E. Müller | Process for the production of lubricating greases based on mineral oil | |
US2449335A (en) * | 1942-10-28 | 1948-09-14 | Frank J Sowa | Hydraulic pressure device and actuating fluid therefor |
US2426852A (en) * | 1943-09-15 | 1947-09-02 | Jasco Inc | High temperature lubricant |
US2616854A (en) * | 1943-11-13 | 1952-11-04 | Fenske Merrell Robert | Hydraulic fluid |
US2455961A (en) * | 1944-06-10 | 1948-12-14 | Du Pont | Hydraulic fluid |
US2475246A (en) * | 1944-12-30 | 1949-07-05 | Standard Oil Dev Co | Lubricants |
US2441023A (en) * | 1945-01-26 | 1948-05-04 | Shell Dev | Lubricating oil compositions containing polymerized allyl esters of carboxylic acids |
US2435777A (en) * | 1945-01-31 | 1948-02-10 | Rohm & Haas | Preparation of quaternary ammonium polyacrylates |
US2435950A (en) * | 1945-02-03 | 1948-02-10 | Rohm & Haas | Hydraulic fluids |
US2467147A (en) * | 1945-03-22 | 1949-04-12 | Standard Oil Dev Co | Low-temperature lubricant |
US2438446A (en) * | 1945-05-25 | 1948-03-23 | Standard Oil Dev Co | Lubricant and hydraulic fluid composition |
US2602780A (en) * | 1945-08-17 | 1952-07-08 | William A Zisman | Hydraulic fluid |
US2442741A (en) * | 1945-09-06 | 1948-06-01 | Cities Service Oil Co | High viscosity damping fluid |
US2616851A (en) * | 1947-04-29 | 1952-11-04 | Socony Vacuum Oil Co Inc | Mineral oil composition containing esters of product obtained by reaction between maleic anhydride and vinyl acetate |
US2616852A (en) * | 1947-06-21 | 1952-11-04 | Mineral oil composition | |
US2499723A (en) * | 1947-07-28 | 1950-03-07 | Du Pont | Lubricants containing copolymers of ethylene and vinyl acetate |
US2512771A (en) * | 1947-09-17 | 1950-06-27 | Rohm & Haas | Operating fluids based on acetals |
US2512255A (en) * | 1947-12-31 | 1950-06-20 | Gulf Research Development Co | Hydraulic fluids |
US2541590A (en) * | 1948-02-13 | 1951-02-13 | Shell Dev | Lubricating compositions |
US2615799A (en) * | 1948-04-03 | 1952-10-28 | Sinclair Refining Co | Diesel fuel |
US2528348A (en) * | 1948-07-13 | 1950-10-31 | California Research Corp | Nonflammable hydraulic fluid |
US2528347A (en) * | 1948-07-13 | 1950-10-31 | California Research Corp | Nonflammable hydraulic fluid |
US2549270A (en) * | 1948-07-19 | 1951-04-17 | Shell Dev | Lubricant and hydraulic fluid composition |
US2544375A (en) * | 1948-08-21 | 1951-03-06 | Monsanto Chemicals | Lubricating oil containing a polymer of tetradecyl vinyl ether |
US2544376A (en) * | 1948-08-21 | 1951-03-06 | Monsanto Chemicals | Lubricating oil containing a polymer of oleyl methacrylate |
US2637698A (en) * | 1948-12-30 | 1953-05-05 | Standard Oil Dev Co | Mineral oil lubricating composition containing a copolymer of an alkyl ester of itaconic acid and an alkyl acrylate or methacrylate |
US2655479A (en) * | 1949-01-03 | 1953-10-13 | Standard Oil Dev Co | Polyester pour depressants |
US2602048A (en) * | 1949-01-24 | 1952-07-01 | Standard Oil Dev Co | Lubricating oil additives |
US2834733A (en) * | 1949-04-01 | 1958-05-13 | Douglas Aircraft Co Inc | Hydraulic fluid and lubricant composition |
US2583588A (en) * | 1949-06-08 | 1952-01-29 | Mosteller James Calvin | Less inflammable hydraulic fluid |
US2612475A (en) * | 1949-10-28 | 1952-09-30 | Standard Oil Dev Co | Lubricating oil additive |
US2672446A (en) * | 1949-11-30 | 1954-03-16 | Standard Oil Co | Lubricants |
US2710842A (en) * | 1950-05-19 | 1955-06-14 | Texas Co | Hydraulic transmission fluid |
US2653133A (en) * | 1950-12-07 | 1953-09-22 | Du Pont | Copolymers and lubricants containing the same |
US2666033A (en) * | 1951-04-11 | 1954-01-12 | Texas Co | Lithium soap grease containing methacrylate ester polymer for bearing noise suppression |
US2671760A (en) * | 1951-05-18 | 1954-03-09 | William S Port | Lubricating oil compositions |
US2851421A (en) * | 1951-08-07 | 1958-09-09 | Pure Oil Co | Power transmission fluids |
US2737496A (en) * | 1952-02-16 | 1956-03-06 | Du Pont | Lubricating oil compositions containing polymeric additives |
US2880175A (en) * | 1952-05-01 | 1959-03-31 | Exxon Research Engineering Co | Lubricating oil additive compatibility improver |
US2751039A (en) * | 1952-12-23 | 1956-06-19 | California Research Corp | Filters coated with thickened oils |
US2841558A (en) * | 1955-06-06 | 1958-07-01 | Monsanto Chemicals | Hydrocarbon oil compositions |
US3194777A (en) * | 1956-05-14 | 1965-07-13 | Pittsburgh Plate Glass Co | Coating compositions |
US2894911A (en) * | 1957-12-16 | 1959-07-14 | Douglas Aircraft Co Inc | Fire-resistant hydraulic fluid |
US2982715A (en) * | 1958-02-11 | 1961-05-02 | Shell Oil Co | Separation of normal paraffin wax from lubricating oil utilizing molecular sieve |
US2992987A (en) * | 1958-06-26 | 1961-07-18 | Monsanto Chemicals | Lubricating oil additive concentrate |
US3227696A (en) * | 1960-02-26 | 1966-01-04 | Shell Oil Co | Phosphorous and chlorine-containing copolymers as lubricant additives |
US3278500A (en) * | 1960-12-07 | 1966-10-11 | Union Carbide Corp | Sulfur-containing polymers |
US3226326A (en) * | 1962-07-30 | 1965-12-28 | Shell Oil Co | Lubricating composition |
US3268494A (en) * | 1962-12-28 | 1966-08-23 | Shell Oil Co | Lubricating compositions |
US3542680A (en) * | 1963-04-23 | 1970-11-24 | Lubrizol Corp | Oil-soluble carboxylic acid phenol esters and lubricants and fuels containing the same |
US3496103A (en) * | 1967-05-25 | 1970-02-17 | Us Army | Friction reduction by poly(n-alkyl methacrylates) in solution and dry films |
US3510425A (en) * | 1967-06-23 | 1970-05-05 | Timothy C Wilson | Oil mist lubrication process and novel lubricating oil composition for use therein |
JPS5911638B1 (en) * | 1971-05-05 | 1984-03-16 | Shell Int Research | |
US3853497A (en) * | 1972-11-08 | 1974-12-10 | Texaco Inc | Low pour vacuum gas oil compositions |
US4146492A (en) * | 1976-04-02 | 1979-03-27 | Texaco Inc. | Lubricant compositions which exhibit low degree of haze and methods of preparing same |
US4088589A (en) * | 1976-05-20 | 1978-05-09 | Exxon Research & Engineering Co. | Dual pour depressant combination for viscosity index improved waxy multigrade lubricants |
US4149984A (en) * | 1977-09-08 | 1979-04-17 | Rohm Gmbh | Lubricating oil additives |
US4968444A (en) * | 1983-10-28 | 1990-11-06 | Rohm Gmbh | Lubricating oil additives |
JPS60110790A (en) * | 1983-10-28 | 1985-06-17 | レーム・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | N-paraffin-containing lubricating oil additive |
US4734446A (en) * | 1985-03-25 | 1988-03-29 | The Lubrizol Corporation | Polymeric compositions comprising an oil-soluble polymer and an oil-soluble acrylate polymerization of product |
US4822508A (en) * | 1985-12-13 | 1989-04-18 | Rohm Gmbh | Shear stable multirange oils having an improved viscosity index |
US4867894A (en) * | 1986-03-07 | 1989-09-19 | Rohm Gmbh | Pour point improving additives for mineral oils |
US5043087A (en) * | 1986-04-25 | 1991-08-27 | Rohn Gmbh | Addives for paraffinic lubricants |
US4844829A (en) * | 1987-08-19 | 1989-07-04 | Pennzoil Products Company | Methacrylate pour point depressants and compositions |
US4956111A (en) * | 1987-08-19 | 1990-09-11 | Pennzoil Products Company | Methacrylate pour point depressants and compositions |
US5229021A (en) * | 1991-12-09 | 1993-07-20 | Exxon Research & Engineering Company | Wax isomerate having a reduced pour point |
WO1993012212A1 (en) * | 1991-12-09 | 1993-06-24 | Exxon Research And Engineering Company | Wax isomerate having a reduced pour point |
US5520832A (en) * | 1994-10-28 | 1996-05-28 | Exxon Research And Engineering Company | Tractor hydraulic fluid with wide temperature range (Law180) |
US20080108533A1 (en) * | 2006-11-07 | 2008-05-08 | Peer William J | Methacrylate copolymer pour point depressants |
US8143202B2 (en) | 2006-11-07 | 2012-03-27 | Ciba Corp. | Methacrylate copolymer pour point depressants |
US20090151235A1 (en) * | 2007-12-18 | 2009-06-18 | Eugene Scanlon | Biodiesel cold flow improver |
US8900333B2 (en) | 2007-12-18 | 2014-12-02 | Basf Se | Biodiesel cold flow improver |
KR101574815B1 (en) | 2007-12-18 | 2015-12-04 | 바스프 에스이 | Biodiesel Cold Flow Improver |
WO2013076424A1 (en) | 2011-11-22 | 2013-05-30 | Universite Du Sud Toulon-Var | Poly(n-alkyl acrylate) polymers and use thereof as oil pour point depressants |
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