US3903003A - Lubricating compositions containing an amido-amine reaction product of a terminally carboxylated isoprene polymer - Google Patents
Lubricating compositions containing an amido-amine reaction product of a terminally carboxylated isoprene polymer Download PDFInfo
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- US3903003A US3903003A US448603A US44860374A US3903003A US 3903003 A US3903003 A US 3903003A US 448603 A US448603 A US 448603A US 44860374 A US44860374 A US 44860374A US 3903003 A US3903003 A US 3903003A
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- Prior art keywords
- reaction product
- amido
- hydrogenated
- polyisoprene
- carboxylated
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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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
- C10M133/56—Amides; Imides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
- C08C19/36—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with carboxy radicals
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
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- 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
- C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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- 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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- 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
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
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- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
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- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
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- C10M2229/043—Siloxanes with specific structure containing carbon-to-carbon double bonds
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- C10M2229/04—Siloxanes with specific structure
- C10M2229/044—Siloxanes with specific structure containing silicon-to-hydrogen bonds
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Definitions
- lubricants which meet a F viscosity specification and a 2l0F viscosity specification. such as is shown for motor oils by the following table derived from SAE. 1300a taken from the SAE Handbook for I969:
- an SAE l0W/50 oil must have a viscosity at 0F between 12 and 24 poises and a viscosity at 2 l0F of between 85 and l SUS.
- VI viscosity index
- pour point depressants A common limitation of essentially all of these is shear sensitivity. This is not unexpected. since most of these polymers are relatively high molecular weight materials. and consequently are readily subject to shear degradation. On the other hand. relatively low molecular weight polymeric materials, at least up to the present time. have proven to be relatively ineffective as thickeners or VI improvers in automotive engine lubricants, even though they may have reasonably good shear stability.
- a number of polymeric additives having a certain polarity have been suggested as lubricating oil additives. These include. for example, polymers shown as sludge dispersants in-U.S. Pat. No. 2.838.456. In this patent. reference is made to graft copolymers wherein a polar monomer is grafted onto a polymer of an isoolefin or a diene. Not only is the polymer left in a nonhydrogenated state (and therefore susceptible to oxidation) but also the proportion of the polar monomer em ployed was so high as to seriously reduce oil solubility of the graft copolymer.
- lubrieating compositions comprising a major proportion of a lubricating oil and 0.1-109? by weight of the halogen-free nitrogen-containing amido amine reaction product of a terminally carhoxylated substantially completely hydrogenated polyisoprenc having an average molecular weight between about 20,000 and 250,000 and a nitrogen compound ofthe group consisting of polyalkylene amines (sometimes referred to as polyalkylene imines) and hydroxyl polyalkylene amines.
- amido amine reaction products to be described more fully hereinafter, not only increase the viscosity of hydrocarbon oils but also increase the viscosity index thereof and provide detergency and dispersancy properties. Furthermore, these reaction products are stable with respect to oxidation and shear.
- the percursors of the polymeric additives are preferably formed by polymerization of isoprene using a lithium-base initiator, preferably a lithium alkyl in an inert solvent medium predominating in hydrocarbons under conditions known in the art to produce a polyisoprene referred to as a living polymer wherein the growing end of the polymer chain is associated with a lithium radical.
- This living polymer is then subjected to carboxylation such as by reaction with carbon dioxide to form a polyisoprene bearing a terminal carboxyl group.
- the carboxylated polymer is then subjected to hydrogenation under conditions leading to substantially complete reduction of all aliphatic unsaturation.
- substantially complete means hydrogenation to an extent sufficient to reduce at least about 9871 of the olefinic unsaturation and preferably higher than about 99% thereof.
- Hydrogenation is preferably effected by the use of catalysts which are the reaction products of a nickel or cobalt carboxylate and a halogen-free organo alkenc compound. preferably an aluminum trialkyl.
- the temperature of hydrogenation may vary from about room temperature to about 175C for times from about 1 minutes to 4 hours. Hydrogenation is normally conducted in a saturated hydrocarbon medium and may be carried out in a batch operation in an autoclave or in a continuous process utilizing trickle phase techniques. for example.
- the average molecular weight of the polyisoprene component may vary over a wide range. It is preferred that it lie between about 21,500 and 250.000, still more preferably between about 23,000 and 80.000.
- the nitrogen compounds utilized for the formation of the amido amines of this invention may be polyalkylene amines, and hydroxy alkyl polyalkylene amines as well as mixtures thereof.
- polyalkylene amine is meant to include those polyamines having the formula:
- R is a hydrogen or a lower alkyl hydrocarbon substituent and alkylene" is a lower alkylene, i.e. divalent open chain hydrocarbon group having from 1 to 8 carbon atoms.
- alkyl polyalkylene amines are those in which the terminal hydrogen atom in the above structural formula is replaced by a hydroxy alkyl radical or a polyalkylene oxide, hydroxy terminated radical in which the alkyl group has from 1 to 8 carbon atoms.
- Typical species of reactants falling within the above-described group of compounds are the following:
- the amido amine reaction products are directly prepared by reaction of the earboxylated hydrogenated polyisoprene and one or more of the above-described nitrogen-containing compounds. While little or no reaction occurs at relatively lower temperatures such as 145C. it has been found that satisfactory rates of reaction are experienced at temperatures in the order of lC or higher, preferably 185-250 in the presence of a lubricating oil if desired or in bulk form. By this means when using a lubricating oil medium for the reaction. a concentrate of the amido amine can be conveniently prepared.
- Heating is continued for periods of time which will vary with the reactants and temperature but it normally will be between about 15 minutes and 8 hours. If the product is prepared in the absence of a lubricating oil it may be recovered for example by dissolving in toluene, washing with a lower alcohol such a methanol and precipitating the product between addition of still further alcohol.
- the reaction products prepared as described above comprise a hydrogenated polyisoprene segment connected by a single amido linkage with the polyamine. It is preferred as referred to hereinabove that the hydrogenated polyioprene segment have an average molecular weight between about 23,000 and 80,000 and in conjunction therewith that the nitrogen compound utilized to form the amido amine have an average molecular weight between about 150 and 1800 although polyalkylene amines having average molecular weights up to about 2,500 may in fact be used.
- the oil component of the lubricating compositions according to the present invention is especially designed for the preparation of multi-grade lubricants although single grade lubricants may be compounded as well. Still more specifically, the present combination of block copolymer and pour point depressant is especially beneficial in wax-containing lubricating oil cuts such as found in Mid Continent oils, West Texas Ellenburger crudes, East Texas crudes, Oklahoma crudes, Pennsylvania crudes and California crudes and similar waxy crudes which may be referred to as paraffin base crudes, naphthenic crudes or mixed based crudes as distinguished from asphalt base crudes. While lubricating oils of any viscosity may be used as the base for the present compositions.
- High Viscosity lndex Neutrals such as HVl 100 Neutral, HVI 250 Neutral and HVI Bright Stock as well as combinations of the same.
- the numerals before Neutral are approximate viscosities at 100F in Saybolt Universal Seconds.
- very high viscosity index (VHVI) oils such as those prepared via hydrocracking of poor quality oils, such as low viscosity index (LVI) oils
- LVI low viscosity index
- More volatile oils may be employed for special purposes such as (HVI) N.
- These neutral oils are produced by well-known refining meth ods, such as distillation. dewaxing, deasphalting, dearomatizing as by solvent extraction, etc, as may be needed. dependent largely on the crude oil used. Typical properties of these HVI oils are the following;
- EXAMPLE I EXAMPLE III Polyisoprene was prepared in isopentane solution using secondary butyllithium as the initiator to produce a polymer having an average molecular weight of about 30.000.
- the living polymer was carboxylated at about 40C by the use of carbon dioxide. This was subjected to hydrogenation in the presence of a catalyst comprising the reaction product of nickel octoate and aluminum triethyl to form the hydrogenated carboxylated polymer.
- the product was dissolved in xylene and reaction at 145C was attempted with pentaethylene hexamine (PEHA). Little or no reaction occurred at this temperature. However. when the temperature was increased to 200C reaction occurred to form a homogenous mixture after several hours.
- the cooled polymer was dissolved in an excess of toluene and washed with methanol which caused the product to precipitate free of unreaetcd polyamine.
- the polymer was dissolved in toluene dried with sodium sulfate and the solvent stripped off.
- the product characterized by the infra red spectra and physical properties was shown to be the same as the amido amines obtained by way of the intermediate acid chloride reactant referred to hercinabove.
- EXAMPLE II In order to determine the dispersant properties of the two amido amines prepared as described in Example I. the additives were dispersed in a base blend and subjected to Micro Air Oxidation Tests (MAOT). The
- This lubricating oil had an SAE grade of iOW/40.
- the Dispersant VI lmprover of this Invention present in an amount of 2.0 wt.% was the amido amine of hydrogenated carboxylatcd polyisoprene and polyethylene iminc. the respective average molecular weights of each were 48.000 and 600. The following ratings were obtained and are compared with specification limits.
- a lubricating composition comprising a major proportion of a lubricating oil and 0. l-l by weight. sufficient to raise the viscosity index and impart deter- ,gcncy to the oil of a halogen-free nitrogen-containing amido amine reaction product of a terminally carboxylated substantially completely hydrogenated polyisoprenc containing less than 27: of the original olefinic unsaturation and having an average molecular weight between about 20.000 and 250000 and a nitrogen compound of the group consisting of polyalkylene amines and hydroxy alkyl polyalkylene amines, said reaction product resulting from heating the hydrogenated carboxylated polyisoprenc and nitrogen compound for l480 minutes at l75250C.
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Abstract
Lubricating oil compositions for internal combustion engines comprise a lubricant modified with an amido amine reaction product formed between certain carboxylated hydrogenated polyisoprenes and certain polyamines, imines (or ''''poly'''') and hydroxyl alkyl polyamines.
Description
United States Patent Murphy et al. 1 Sept. 2, 1975 [54] LUBRICATING COMPOSITIONS 3.641633 2/ 1972 Eckert et a1. 252/515 A X CONTAINING AN AMIDO AMlNE 3,761,458 9/1973 Holler ct a1 252/515 A X 3,772,196 11/1973 St. Clair ct a1 252/515 A X REACTION PRODUCT OF A TERMINALLY 3,816,314 6/1974 Pappas ct a1 252/515 A CARBOXYLATED ISOPRENE POLYMER [75] Inventors: Zatis L. Murphy, St. Louis, Mo.;
Roland Schobohm, Bethalto m. Prmzar IL.\'ummerDeIbert E. Gantz Assistant Examiner--Andrew H. Metz [73] Assignee: Shell Oil Company, Houston, Tex.
[22] Filed: Mar. 6, 1974 211 Appl. No.: 448,603 [571 ABSTRACT Lubricating oil compositions for internal combustion [52] U5. C1, 252/515 A; 260/935 A engines comprise a lubricant difi d with an amidc, 1 f amine reaction product formed between certain car- [58] Field of Search 252/5115 A; 260/935 A boxylated hydrogenated polyisoprenes and certain poiyamines. imines (or po1y") and hydroxyl alkyl [56] References Cited polyamines UNITED STATES PATENTS 2.9%,455 8/1961 Brown ct al. 252/5175 A X 5 Claims, No Drawings LUBRICATING COMPOSITIONS CONTAINING AN AMIDO-AMINE REACTION PRODUCT OF A TERMINALLY CARBOXYLATED ISOPRENE POLYMER BACKGROUND OF THE INVENTION This invention relates to novel lubricating compositions containing a critically defined block copolymer imparting to the compositions increased viscosity. viscosity index and detergency. The lubricants are especially useful in internal combustion engines but may be employed for other related purposes such as in transmission fluids, gear lubricants and the like.
DESCRIPTION OF THE PRIOR ART The art of lubricating oil formulation has become increasingly complex with the ever more stringent demands made by the developing automotive technology. One of the primary requirements is to provide an economical lubricant which may be utilized over a wide range of operating conditions. especially insofar as temperature variations are concerned. At the same time. the formulated lubricant should also possess an ability to withstand oxidative influences and. if possible. impart detergency and dispersancy during its use as well as during storage. Multi-grade lubricants are becoming virtually a necessity in this field.
By multi-grade lubricants is meant lubricants which meet a F viscosity specification and a 2l0F viscosity specification. such as is shown for motor oils by the following table derived from SAE. 1300a taken from the SAE Handbook for I969:
According to the table, for example, an SAE l0W/50 oil must have a viscosity at 0F between 12 and 24 poises and a viscosity at 2 l0F of between 85 and l SUS.
The art has evolved a number of multi-grade oils such as SAE l0W/3O and SAE W/40 oils but with few exceptions has not been able to formulate wider multigrade oils such as SAE l0W/50 having low oil consumption and high shear stability. Commercially, such formulations should be economically feasible. capable of large scale production, versatile in regard to the base stock and preferably resistant to degradation under conditions of high shear.
A large variety of polymeric additives have been em ployed primarily as thickening agents. viscosity index (VI) improvers and pour point depressants. A common limitation of essentially all of these is shear sensitivity. This is not unexpected. since most of these polymers are relatively high molecular weight materials. and consequently are readily subject to shear degradation. On the other hand. relatively low molecular weight polymeric materials, at least up to the present time. have proven to be relatively ineffective as thickeners or VI improvers in automotive engine lubricants, even though they may have reasonably good shear stability.
A number of polymeric additives having a certain polarity have been suggested as lubricating oil additives. These include. for example, polymers shown as sludge dispersants in-U.S. Pat. No. 2.838.456. In this patent. reference is made to graft copolymers wherein a polar monomer is grafted onto a polymer of an isoolefin or a diene. Not only is the polymer left in a nonhydrogenated state (and therefore susceptible to oxidation) but also the proportion of the polar monomer em ployed was so high as to seriously reduce oil solubility of the graft copolymer.
Two other patents of related subject matter are US. Pat. Nos. 2,965,571 and 3,378,492. Each of these teaches the use of certain graft copolymers but in neither case is reference made to hydrogenated polymers or to polymers having only a low proportion of the polar graft material such as acrylates or acrylonitrile.
OBJECTS or THE INVENTION It is an object of the present invention to provide improved lubricating compositions. It is another object of the invention to provide improved multi-grade lubricants. It is a particular object of the invention to provide high viscosity index lubricating compositions exhibiting detergency and dispersancy characteristics. Other objects will become apparent during the following detailed description of the invention.
STATEMENT OF THE INVENTION Now, in accordance with the present invention, lubrieating compositions are provided comprising a major proportion of a lubricating oil and 0.1-109? by weight of the halogen-free nitrogen-containing amido amine reaction product of a terminally carhoxylated substantially completely hydrogenated polyisoprenc having an average molecular weight between about 20,000 and 250,000 and a nitrogen compound ofthe group consisting of polyalkylene amines (sometimes referred to as polyalkylene imines) and hydroxyl polyalkylene amines.
DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with. this invention. it has been found that the amido amine reaction products to be described more fully hereinafter, not only increase the viscosity of hydrocarbon oils but also increase the viscosity index thereof and provide detergency and dispersancy properties. Furthermore, these reaction products are stable with respect to oxidation and shear.
The percursors of the polymeric additives are preferably formed by polymerization of isoprene using a lithium-base initiator, preferably a lithium alkyl in an inert solvent medium predominating in hydrocarbons under conditions known in the art to produce a polyisoprene referred to as a living polymer wherein the growing end of the polymer chain is associated with a lithium radical. This living polymer is then subjected to carboxylation such as by reaction with carbon dioxide to form a polyisoprene bearing a terminal carboxyl group.
The carboxylated polymer is then subjected to hydrogenation under conditions leading to substantially complete reduction of all aliphatic unsaturation. Substantially complete means hydrogenation to an extent sufficient to reduce at least about 9871 of the olefinic unsaturation and preferably higher than about 99% thereof. Hydrogenation is preferably effected by the use of catalysts which are the reaction products of a nickel or cobalt carboxylate and a halogen-free organo alkenc compound. preferably an aluminum trialkyl. The temperature of hydrogenation may vary from about room temperature to about 175C for times from about 1 minutes to 4 hours. Hydrogenation is normally conducted in a saturated hydrocarbon medium and may be carried out in a batch operation in an autoclave or in a continuous process utilizing trickle phase techniques. for example.
While the average molecular weight of the polyisoprene component may vary over a wide range. it is preferred that it lie between about 21,500 and 250.000, still more preferably between about 23,000 and 80.000.
The nitrogen compounds utilized for the formation of the amido amines of this invention may be polyalkylene amines, and hydroxy alkyl polyalkylene amines as well as mixtures thereof. The term polyalkylene amine" is meant to include those polyamines having the formula:
H:N alky lene-N H wherein is an integer from 2 to about 10. R is a hydrogen or a lower alkyl hydrocarbon substituent and alkylene" is a lower alkylene, i.e. divalent open chain hydrocarbon group having from 1 to 8 carbon atoms. The hydroxy alkyl polyalkylene amines are those in which the terminal hydrogen atom in the above structural formula is replaced by a hydroxy alkyl radical or a polyalkylene oxide, hydroxy terminated radical in which the alkyl group has from 1 to 8 carbon atoms. Typical species of reactants falling within the above-described group of compounds are the following:
ethylene diamine diethylene triamine tricthylene tetramine tetraethylene pentamine pentaethylenc hexamine polyethylene imine hydroxyethyl diethylene triamine poly(hydroxyalkyl) derivatives of ethylene diamine homologs poly propoxylatcd pentaethylene hexamine While it is possible to form these reaction products by converting the carboxylated hydrogenated polyisoprene to its acryl chloride by reaction with thionyl chloride and then by reaction with the polyamine, this not only entails an extra process step. but also inherently causes emulsifieation difficulties due probably to the detergency properties of the resulting products. This becomes especially evident during water washing of the reaction product for the removal of hydrogen chloride or any amine hydrochlorides. Thus. in accordance with the preferred aspect of this invention the amido amine reaction products are directly prepared by reaction of the earboxylated hydrogenated polyisoprene and one or more of the above-described nitrogen-containing compounds. While little or no reaction occurs at relatively lower temperatures such as 145C. it has been found that satisfactory rates of reaction are experienced at temperatures in the order of lC or higher, preferably 185-250 in the presence of a lubricating oil if desired or in bulk form. By this means when using a lubricating oil medium for the reaction. a concentrate of the amido amine can be conveniently prepared. Heating is continued for periods of time which will vary with the reactants and temperature but it normally will be between about 15 minutes and 8 hours. If the product is prepared in the absence of a lubricating oil it may be recovered for example by dissolving in toluene, washing with a lower alcohol such a methanol and precipitating the product between addition of still further alcohol.
The reaction products prepared as described above comprise a hydrogenated polyisoprene segment connected by a single amido linkage with the polyamine. It is preferred as referred to hereinabove that the hydrogenated polyioprene segment have an average molecular weight between about 23,000 and 80,000 and in conjunction therewith that the nitrogen compound utilized to form the amido amine have an average molecular weight between about 150 and 1800 although polyalkylene amines having average molecular weights up to about 2,500 may in fact be used.
The oil component of the lubricating compositions according to the present invention is especially designed for the preparation of multi-grade lubricants although single grade lubricants may be compounded as well. Still more specifically, the present combination of block copolymer and pour point depressant is especially beneficial in wax-containing lubricating oil cuts such as found in Mid Continent oils, West Texas Ellenburger crudes, East Texas crudes, Oklahoma crudes, Pennsylvania crudes and California crudes and similar waxy crudes which may be referred to as paraffin base crudes, naphthenic crudes or mixed based crudes as distinguished from asphalt base crudes. While lubricating oils of any viscosity may be used as the base for the present compositions. the preferred oils are referred to as High Viscosity lndex Neutrals, such as HVl 100 Neutral, HVI 250 Neutral and HVI Bright Stock as well as combinations of the same. The numerals before Neutral are approximate viscosities at 100F in Saybolt Universal Seconds. Also included in this general term HVI for the purpose of this description, are very high viscosity index (VHVI) oils such as those prepared via hydrocracking of poor quality oils, such as low viscosity index (LVI) oils More volatile oils may be employed for special purposes such as (HVI) N. These neutral oils are produced by well-known refining meth ods, such as distillation. dewaxing, deasphalting, dearomatizing as by solvent extraction, etc, as may be needed. dependent largely on the crude oil used. Typical properties of these HVI oils are the following;
Properties of Base ()ils H\'l HVI H\'l HVI \'H\-l Designation 80 N N 250 B5 100 N V15 1 llll' (Sl'S) 38.0 39.8 50.0 I57 3811 Us 100F (SL'S) s2 107 205 2775 82.7 VI [03 )3 )3 5 12b (inn-it (lbs/gal) 7.0K 7.20 7.33 7.44 7.2l Pour Point (l-) 5 1o 20 1S 0 Flash Point 1F) 300 405 430 575 400 Continued Properties of Base ()ils EXAMPLE I EXAMPLE III Polyisoprene was prepared in isopentane solution using secondary butyllithium as the initiator to produce a polymer having an average molecular weight of about 30.000. The living polymer was carboxylated at about 40C by the use of carbon dioxide. This was subjected to hydrogenation in the presence of a catalyst comprising the reaction product of nickel octoate and aluminum triethyl to form the hydrogenated carboxylated polymer.
The product was dissolved in xylene and reaction at 145C was attempted with pentaethylene hexamine (PEHA). Little or no reaction occurred at this temperature. However. when the temperature was increased to 200C reaction occurred to form a homogenous mixture after several hours. The cooled polymer was dissolved in an excess of toluene and washed with methanol which caused the product to precipitate free of unreaetcd polyamine. The polymer was dissolved in toluene dried with sodium sulfate and the solvent stripped off. The product characterized by the infra red spectra and physical properties was shown to be the same as the amido amines obtained by way of the intermediate acid chloride reactant referred to hercinabove.
EXAMPLE II In order to determine the dispersant properties of the two amido amines prepared as described in Example I. the additives were dispersed in a base blend and subjected to Micro Air Oxidation Tests (MAOT). The
base blend was as follows:
HVl HIU Neutral lube oil Methylene bistZ (1-di-tert hutyl phenol) Alkyl yinc dithiophosphate Highly overbased calcium petroleum sulfonate TABLE I Additive '4 w Hours to Fail None EP-PEHA* 4Q ;;-3 4x EP-HEDTA** 45 3 "amido amine of hydrogenated carhinylated polyisoprene and pentactliylene hL\illIli"L' "amido amine ol' hydrogenated carhoxylnted polyisoprene and hydrovwthyl tiicti'| \|\.t\e trlamlnc It will be noted that the addition of the two amido amines substantially improved the Micro Air Oxidation Test results over that obtained with the base blend.
Two of theamido amines of this invention were dispersed in 100 HVl Neutral to determine their viscosity index effect. For comparison, the hydrogenated carboxylated polyisoprene precursor was likewise tested as was the unmodified lubricating oil. The following table shows that the unmodified oil had a viscosity index of 93. In order to increase the original 2 1 ()F viscosity of the oil to 77 SUS, it was necessary to add 4.7% of the free carboxyl precursor. In this concentration. the resulting oil had a viscosity index of 152. Both of the amido amines of this invention required substantially less polymer to raise the 2l0F viscosity to 77 but in spite of this the resulting oils had substantially higher viscosity indicics than that obtained with the oil contaning the precursor.
TABLE II Viscometric Properties of H\'l lUt) Neutral (WR) Containing Block Polymers See footnote in 'lahle l "Aniido amine of hydrogenated c:tr| 0\ \la\ctl polyisoprene and polyethylene lmine lNlltl mol at EXAMPLE 1V Sequence VC Engine Tests were performed on the following lubricating oil composition:
This lubricating oil had an SAE grade of iOW/40. The Dispersant VI lmprover of this Invention". present in an amount of 2.0 wt.% was the amido amine of hydrogenated carboxylatcd polyisoprene and polyethylene iminc. the respective average molecular weights of each were 48.000 and 600. The following ratings were obtained and are compared with specification limits.
TABLE III Sequence Results Specification Limits Average Sludge Deposits 9.2 8.5 min. Piston Skirt Varnish Deposits 8.4 7.) min. Average Varnish Deposits 8.0 81) min.
"Rating lU clean We claim as our invention:
1. A lubricating composition comprising a major proportion of a lubricating oil and 0. l-l by weight. sufficient to raise the viscosity index and impart deter- ,gcncy to the oil of a halogen-free nitrogen-containing amido amine reaction product of a terminally carboxylated substantially completely hydrogenated polyisoprenc containing less than 27: of the original olefinic unsaturation and having an average molecular weight between about 20.000 and 250000 and a nitrogen compound of the group consisting of polyalkylene amines and hydroxy alkyl polyalkylene amines, said reaction product resulting from heating the hydrogenated carboxylated polyisoprenc and nitrogen compound for l480 minutes at l75250C.
2. A composition according to claim 1 wherein the methacrylate.
Claims (5)
1. A LUBRICATING COMPOSITION COMPRISING A MAJOR PROPORTION OF A LUBRICATING OIL AND 0.1-10% BY WEIGHT, SUFFICIENT TO RAISE THE VISCOSITY INDEX AND IMPART DETERGENCY TO THE OIL OF A HALOGEN-FREE NITROGEN-CONTAINING AMIDO AMINE REACTION PRODUCT OF A TERMINALLY CARBOXYLATED SUBSTANTIALLY COMPLETELY HYDROGENATED POLYISOPRENE CONTAINING LESS THAN 2% OF THE ORIGINAL OLEFINIC UNSATURATION AND HAVING AN AVERAGE MOLECULAR WEIGHT BETWEEN ABOUT 20,000 AND 250,000 AND A NITROGEN COMPOUND OF THE GROUP CONSISTING OF POLYALKYLENE AMINES AND HYDROXY ALKYL POLYALKYLENE AMINES, SAID REACTION PRODUCT RESULTING FROM HEATING THE HYDROGENATED CARBOXYLATED POLYISOPRENE AND NITROGEN COMPOUND FOR 15-480 MINUTES AT 175*-250*C.
2. A composition according to claim 1 wherein the reaction product is formed between monocarboxylated hydrogenated polyisoprene and a pentaethylene hexamine.
3. A composition according to claim 1 wherein the reaction product is formed between monocarboxylated hydrogenated polyisoprene and a hydroxy ethyldiethylene triamine.
4. A composition according to claim 1 wherein the carboxylated hydrogenated polyisoprene has an average molecular weight between about 23,000 and 80,000 and the nitrogen compound has an average molecular weight between about 150 and 1800.
5. A composition according to claim 1 containing in addition a power point depressing amount of a polymethacrylate.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US448603A US3903003A (en) | 1974-03-06 | 1974-03-06 | Lubricating compositions containing an amido-amine reaction product of a terminally carboxylated isoprene polymer |
GB8896/75A GB1505143A (en) | 1974-03-06 | 1975-03-04 | Amido amine reaction products and lubricating oil compositions containing them |
FR7506719A FR2263253B1 (en) | 1974-03-06 | 1975-03-04 | |
NL7502510A NL7502510A (en) | 1974-03-06 | 1975-03-04 | PROCESS FOR PREPARING AMIDO-AMINE REACTION PRODUCTS AND LUBRICATING OIL COMPOSITIONS CONTAINING THESE PRODUCTS. |
JP50025723A JPS50122505A (en) | 1974-03-06 | 1975-03-04 | |
DE19752509374 DE2509374A1 (en) | 1974-03-06 | 1975-03-04 | AMIDO-AMINE REACTION PRODUCTS CONTAINING NITROGEN AND THEIR USE IN LUBRICATING OIL MIXTURES |
AU78774/75A AU483961B2 (en) | 1974-03-06 | 1975-03-04 | Amido amine reaction products and lubricating oil compositions containing them |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US448603A US3903003A (en) | 1974-03-06 | 1974-03-06 | Lubricating compositions containing an amido-amine reaction product of a terminally carboxylated isoprene polymer |
Publications (1)
Publication Number | Publication Date |
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US3903003A true US3903003A (en) | 1975-09-02 |
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Family Applications (1)
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US448603A Expired - Lifetime US3903003A (en) | 1974-03-06 | 1974-03-06 | Lubricating compositions containing an amido-amine reaction product of a terminally carboxylated isoprene polymer |
Country Status (6)
Country | Link |
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US (1) | US3903003A (en) |
JP (1) | JPS50122505A (en) |
DE (1) | DE2509374A1 (en) |
FR (1) | FR2263253B1 (en) |
GB (1) | GB1505143A (en) |
NL (1) | NL7502510A (en) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2820211A1 (en) * | 1977-05-11 | 1978-11-16 | Shell Int Research | OIL SOLUBLE PRODUCT AND ITS USES |
US4141847A (en) * | 1977-05-11 | 1979-02-27 | Shell Oil Company | Star-shaped polymer reacted with dicarboxylic acid and amine as dispersant viscosity index improver |
US4735736A (en) * | 1985-07-08 | 1988-04-05 | Exxon Chemical Patents Inc. | Viscosity index improver-dispersant additive |
US4857217A (en) * | 1987-11-30 | 1989-08-15 | Exxon Chemical Patents Inc. | Dispersant additives derived from amido-amines |
US4929374A (en) * | 1987-09-22 | 1990-05-29 | Shell Oil Company | Lubricating oil composition |
US4956107A (en) * | 1987-11-30 | 1990-09-11 | Exxon Chemical Patents Inc. | Amide dispersant additives derived from amino-amines |
US5034018A (en) * | 1987-11-30 | 1991-07-23 | Exxon Chemical Patents Inc. | Fuel additives derived from amido-amines (PT-731) |
US5043084A (en) * | 1987-07-24 | 1991-08-27 | Exxon Chemical Patents, Inc. | Novel polymer substituted amino phenol mannich base amido-amine dispersant additives (PT-742) |
US5053151A (en) * | 1989-05-30 | 1991-10-01 | Exxon Chemical Patents Inc. | Multifunctional viscosity index improver derived from amido-amine exhibiting improved low temperature viscometric properties |
US5152908A (en) * | 1987-05-07 | 1992-10-06 | Tipton Craig D | Gear lubricant package containing a synergistic combination of components |
US5213698A (en) * | 1990-07-03 | 1993-05-25 | Exxon Chemical Patents Inc. | Amido-amine ashless dispersants |
US5229020A (en) * | 1989-05-30 | 1993-07-20 | Exxon Chemical Patents Inc. | Branched amido-amine dispersant additives |
US5230834A (en) * | 1989-05-30 | 1993-07-27 | Exxon Chemical Patents Inc. | Viscosity stable multifunctional viscosity index modifier additives derived from amido amines |
US5252238A (en) * | 1989-05-30 | 1993-10-12 | Exxon Chemical Patents Inc. | Multifunctional viscosity index improver derived from amido-amine exhibiting improved low temperature viscometric properties |
US5603822A (en) * | 1995-11-03 | 1997-02-18 | Mobil Oil Corporation | Catalytic dewaxing of lube basestock raffinates in contact with pour point depressants |
US5629434A (en) * | 1992-12-17 | 1997-05-13 | Exxon Chemical Patents Inc | Functionalization of polymers based on Koch chemistry and derivatives thereof |
US5643859A (en) * | 1992-12-17 | 1997-07-01 | Exxon Chemical Patents Inc. | Derivatives of polyamines with one primary amine and secondary of tertiary amines |
US5646332A (en) * | 1992-12-17 | 1997-07-08 | Exxon Chemical Patents Inc. | Batch Koch carbonylation process |
US5650536A (en) * | 1992-12-17 | 1997-07-22 | Exxon Chemical Patents Inc. | Continuous process for production of functionalized olefins |
US5681797A (en) * | 1996-02-29 | 1997-10-28 | The Lubrizol Corporation | Stable biodegradable lubricant compositions |
US5767046A (en) * | 1994-06-17 | 1998-06-16 | Exxon Chemical Company | Functionalized additives useful in two-cycle engines |
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US4088708A (en) * | 1975-06-13 | 1978-05-09 | The B. F. Goodrich Company | Thermoplastic, thermosetting elastomeric compositions and methods for making the same |
US4233168A (en) * | 1978-06-19 | 1980-11-11 | Chevron Research Company | Lubricant compositions containing dispersant additives |
CA1138889A (en) * | 1978-10-17 | 1983-01-04 | Changkiu K. Riew | Hydroxyl-terminated liquid polymers and process for preparation thereof |
US4843127A (en) * | 1985-04-19 | 1989-06-27 | Allied-Signal Inc. | Reactive elastomeric block co-oligomer and lactam-block copolymers derived therefrom |
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- 1975-03-04 JP JP50025723A patent/JPS50122505A/ja active Pending
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Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4141847A (en) * | 1977-05-11 | 1979-02-27 | Shell Oil Company | Star-shaped polymer reacted with dicarboxylic acid and amine as dispersant viscosity index improver |
DE2820211A1 (en) * | 1977-05-11 | 1978-11-16 | Shell Int Research | OIL SOLUBLE PRODUCT AND ITS USES |
US4735736A (en) * | 1985-07-08 | 1988-04-05 | Exxon Chemical Patents Inc. | Viscosity index improver-dispersant additive |
US5152908A (en) * | 1987-05-07 | 1992-10-06 | Tipton Craig D | Gear lubricant package containing a synergistic combination of components |
US5043084A (en) * | 1987-07-24 | 1991-08-27 | Exxon Chemical Patents, Inc. | Novel polymer substituted amino phenol mannich base amido-amine dispersant additives (PT-742) |
US4929374A (en) * | 1987-09-22 | 1990-05-29 | Shell Oil Company | Lubricating oil composition |
US4857217A (en) * | 1987-11-30 | 1989-08-15 | Exxon Chemical Patents Inc. | Dispersant additives derived from amido-amines |
US4956107A (en) * | 1987-11-30 | 1990-09-11 | Exxon Chemical Patents Inc. | Amide dispersant additives derived from amino-amines |
US5034018A (en) * | 1987-11-30 | 1991-07-23 | Exxon Chemical Patents Inc. | Fuel additives derived from amido-amines (PT-731) |
US5230834A (en) * | 1989-05-30 | 1993-07-27 | Exxon Chemical Patents Inc. | Viscosity stable multifunctional viscosity index modifier additives derived from amido amines |
US5229020A (en) * | 1989-05-30 | 1993-07-20 | Exxon Chemical Patents Inc. | Branched amido-amine dispersant additives |
US5053151A (en) * | 1989-05-30 | 1991-10-01 | Exxon Chemical Patents Inc. | Multifunctional viscosity index improver derived from amido-amine exhibiting improved low temperature viscometric properties |
US5252238A (en) * | 1989-05-30 | 1993-10-12 | Exxon Chemical Patents Inc. | Multifunctional viscosity index improver derived from amido-amine exhibiting improved low temperature viscometric properties |
US5308364A (en) * | 1989-05-30 | 1994-05-03 | Exxon Chemical Patents Inc. | Fuel compositions containing improved branched amido-amine dispersant additives |
US5385684A (en) * | 1989-05-30 | 1995-01-31 | Exxon Chemical Patents, Inc. | Branched amido-amine dispersant additives |
US5213698A (en) * | 1990-07-03 | 1993-05-25 | Exxon Chemical Patents Inc. | Amido-amine ashless dispersants |
US5643859A (en) * | 1992-12-17 | 1997-07-01 | Exxon Chemical Patents Inc. | Derivatives of polyamines with one primary amine and secondary of tertiary amines |
US5629434A (en) * | 1992-12-17 | 1997-05-13 | Exxon Chemical Patents Inc | Functionalization of polymers based on Koch chemistry and derivatives thereof |
US5646332A (en) * | 1992-12-17 | 1997-07-08 | Exxon Chemical Patents Inc. | Batch Koch carbonylation process |
US5650536A (en) * | 1992-12-17 | 1997-07-22 | Exxon Chemical Patents Inc. | Continuous process for production of functionalized olefins |
US5696064A (en) * | 1992-12-17 | 1997-12-09 | Exxon Chemical Patents Inc. | Functionalization of polymers based on Koch chemistry and derivatives thereof |
US5698722A (en) * | 1992-12-17 | 1997-12-16 | Exxon Chemical Patents Inc. | Functionalization of polymers based on Koch chemistry and derivatives thereof |
US5703256A (en) * | 1992-12-17 | 1997-12-30 | Exxon Chemical Patents Inc. | Functionalization of polymers based on Koch chemistry and derivatives thereof |
US5717039A (en) * | 1992-12-17 | 1998-02-10 | Exxon Chemical Patents Inc. | Functionalization of polymers based on Koch chemistry and derivatives thereof |
US5767046A (en) * | 1994-06-17 | 1998-06-16 | Exxon Chemical Company | Functionalized additives useful in two-cycle engines |
US5603822A (en) * | 1995-11-03 | 1997-02-18 | Mobil Oil Corporation | Catalytic dewaxing of lube basestock raffinates in contact with pour point depressants |
US5681797A (en) * | 1996-02-29 | 1997-10-28 | The Lubrizol Corporation | Stable biodegradable lubricant compositions |
Also Published As
Publication number | Publication date |
---|---|
FR2263253A1 (en) | 1975-10-03 |
JPS50122505A (en) | 1975-09-26 |
GB1505143A (en) | 1978-03-30 |
NL7502510A (en) | 1975-09-09 |
AU7877475A (en) | 1976-09-09 |
DE2509374A1 (en) | 1975-09-11 |
FR2263253B1 (en) | 1977-04-15 |
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