US3130161A - Lubricating oil and anti-wear additives therefor - Google Patents
Lubricating oil and anti-wear additives therefor Download PDFInfo
- Publication number
- US3130161A US3130161A US850034A US85003459A US3130161A US 3130161 A US3130161 A US 3130161A US 850034 A US850034 A US 850034A US 85003459 A US85003459 A US 85003459A US 3130161 A US3130161 A US 3130161A
- Authority
- US
- United States
- Prior art keywords
- lubricating oil
- weight
- groups
- imine
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
-
- 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
- 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
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
- C10M2217/023—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group the amino group containing an ester bond
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/026—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrile group
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
-
- 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
- C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2221/02—Macromolecular compounds obtained by reactions of monomers involving only carbon-to-carbon unsaturated bonds
-
- 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
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
-
- 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
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
- C10N2040/253—Small diesel engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Definitions
- Combustion engines such as gasoline engines and diesel engines are more or less subject to Wear of cylinders, pistons and piston rings.
- automobile engines in particular, it is a known phenomenon that considerably increased wear occurs when the cylinder temperature remains relatively low, as is the case when driving short distances. According to the general view, this is due to moisture condensing on the cool cylinder Walls in the presence of acids such as sulfuric acid from sulfurous fuel, hydrohalic acids from lead scavengers, and organic acids from incompletely burnt gasoline.
- acids such as sulfuric acid from sulfurous fuel, hydrohalic acids from lead scavengers, and organic acids from incompletely burnt gasoline.
- the corrosion caused by these acids also termed cold corrosion, is responsible for much of the piston and cylinder wear in automobiles.
- metal salts are attended by drawbacks.
- One disadvantage for example, is the fact that the metal salts formed by neutralization of the acids resulting from the combustion are generally insoluble in oil. This may lead to disturbances, particularly as a result of the formation of deposits in the combustion space which may subsequently cause precombustion.
- R and R are hydrogen atoms or methyl groups
- R is an oleophilic group having 8 or more carbon atoms and it may be polar or non-polar, and R is a polar group.
- R may be an oleophilic group which is similar or dissimilar to R
- the oleophilic group R preferably contains 1220 carbon atoms.
- the olefin monomer (B) has the formula:
- R and R are hydrogen atoms or methyl groups
- R and R are hydrogen atoms, hydrocarbon radicals or polar substituents containing not more than 7 carbon atoms.
- the 1,2-alkylene radical of the 1,2-alkyleneimine are illustrated by ethylene, propylene, butylene groups or the like and the polar-containing groups contained in the telomeric compounds are illustrated by halogen, mercapto, nitro groups derived from aliphatic or aromatic halohydrocarbons, alkylmercaptans, nitro-alkanes and nitroaromatic compounds, the monoand dinitro benzenes or toluenes being preferred.
- the degree of polymerization of the alkylene imine and the monomer (A), respectively are such that each unit becomes at least equal to 5, preferably varying from 5 to 25 or higher such as 150.
- the molecular weight of the reaction product in telomeric form should not exceed 10,000 and preferably should be between 2000 and 5000, and when in non-telomeric form the molecular weight is at least 1000 and preferably from about 80,000 to about 500,000.
- the polymerized 1,2-alkylene imines which are used according to the invention and converted with the said telomers and/or polymers or copolymers are preferably polymerization products of ethylene imine and/ or propylene imine, although polymerization products derived from higher C-alkyl ethylene imines, such as 1,2-butylene imine, C-propyl ethylene imine, C-tetradecyl ethylene imine and others, are also suitable.
- polymerized alkylene imines may be prepared in a known manner, e.g., by treating the corresponding monomers with small quantities of acid catalysts such as hydrochloric acid as described in the German patent specification 665,791 or by condensation of alkylene dichlorides with a given ammonia as described in US. Patent 2,381,730 or by thermal decarboxylation of 2-oxazolidones.
- acid catalysts such as hydrochloric acid as described in the German patent specification 665,791 or by condensation of alkylene dichlorides with a given ammonia as described in US. Patent 2,381,730 or by thermal decarboxylation of 2-oxazolidones.
- the telomers and/ or copolymers with which the alkylene imine polymerization products are to be converted them selves have acid properties, direct use may also be made of these telomers and/ or copolymers in polymerizing by means of acids.
- the resultant products generally consist of mixtures of polymerization products of varying degrees of polymerization and may contain either branched-chain or straight chain molecules.
- polymerized 1,2-alkylene imines of any degree of polymerization may be used, products having an average degree of polymerization greater than 5, particularly greater than 25, are preferred. It is unnecessary for the polyalkylene imines employed to be soluble in oil.
- a suitable product for example, is Polymin P which is a 40-70% water solution of polyethylene irnine commercially available from Badishe Aniline and Soda Fabrik, A6.
- telomers and/or copolymers suitable for the conversion with polymerized 1,2-alkylene imines are oil-soluble compounds containing at least one polar group.
- the polar groups may be solely present at ends of the chains or at any desired points in the molecule including the chain ends.
- the telomer compound may be imagined as formed by polymerizing or copolymen'zing one or more olefinic unsaturated monomers (A), or such monomers (A) together with one or more olefinic unsaturated monomers (B), in the presence of a telomen'zation agent containing at least one polar group.
- the copolymer may be correspondingly derived by copolymerizing a monomer (A) with one or more monomers (B), at least one of the monomers (B) containing one or more polar groups.
- telomers and/ or copolymers are usually obtained in the above-described manner, other methods of preparation are not excluded. It is possible, for example, to start from a polymer, copolymer or telomer in which no polar groups need be present, and to introduce the desired polar groups in a known manner, for instance by substitution. It is also possible to change polar groups already present by chemical reactions, for instance by hydrolysis, exchange, etc.
- oleophilic groups present in monomer (A) and represented by symbol R are here meant substituents whose presence solubilizes the telomer or copolymer molecules in hydrocarbon media.
- the said oleophilic groups contain or entirely consist of cyclic and/ or acyclic hydrocarbon radicals having at least 8 carbon atoms.
- polar groups and/ or heteroatoms may also occur in the oleophilic groups, provided their presence does not result in the telomer or copolymer becoming insoluble in oil.
- oleophilic groups include cyclic hydrocarbon radicals among which may be mentioned, for example, alkaryl groups, particularly alkylphenyl groups such as the p-octylphenyl group.
- Acyclic hydrocarbon radicals are also important, preferably branched or unbranched aliphatic hydrocarbon chains such as di-isobutyl, dodecyl, tetradecyl and hexadecyl groups.
- the oleophilic groups may also contain polar groups, e.g.,
- oleophilic groups represented by such groups as ?OR5, fiNH-R5, ( ⁇ 1R5 in which R represents a substituted or non-substituted hydrocarbon radical.
- the R group is generally a cyclic or acyclic hydrmarbon radical which may or may not be substituted by polar groups and/ or heteroatoms, although a branched or unbranched alkyl group, such as the lauryl, tri-isobutyl, hexadecyl and stearyl group, is preferred.
- Suitable (A) monomers include olefins, particularly such alpha-olefins as decene and cetene styrene derivatives, such as aralkyl styrenes, e.g., para-octyl styrene and ardodecyl alpha-methyl styrene; ethers such as propenyl 2-ethylhexyl ether and vinyl octadecyl ether; esters of alkenols and carboxylic acids, preferably aliphatic carboxylic acids, e.g., vinyl stearate, allyl palmitate and methallyl oleate; esters of unsaturated acids and alcohols derived from such acids as acrylic acid, methacrylic acid, maleic acid, fumeric acid, the crotonic acids, citraconic acid and cinnamic acid, e.g., lauryl and stearyl (meth)-
- the monomer (A) is an alkyl ester of acrylic acid or methacrylic acid.
- Lauryl methacrylate and stearyl methacrylate have been found particularly suitable, although in a very advantageous embodiment of the invention use is made of mixtures of lauryl methacrylate and stearyl methacrylate for example, since the lubricating oil additives produced there With act as pour point depressants with regard to the unmixed components.
- the hydrocarbon radicals may be cyclic and/ or acyclic, e.g., tolyl, cyclohexyl, benzyl as well as branched or unbranched alkyl and alkenyl groups such as methyl.
- polar substituents which may be present in monomer (B) and represented by symbols R and R include nonmetallic atoms of groups V to VII of the periodic table, e.g., nitrogen, phosphorus, oxygen, sulfur and chlorine, in particular nitrogen and oxygen, or groups containing such atoms; the said atoms and groups may or may not form part of or be bound to hydrocarbon radicals.
- groups V to VII of the periodic table e.g., nitrogen, phosphorus, oxygen, sulfur and chlorine, in particular nitrogen and oxygen, or groups containing such atoms; the said atoms and groups may or may not form part of or be bound to hydrocarbon radicals.
- the said groups are XR, -CXXR, -NO CN, SCN, NR
- polar substituents examples include hydroxyl, carboxyl, cyano and amino groups.
- Another important type contains a tertiary amino group in the form of a heterocyclic nitrogen-containing group such as a pyridine group or a pyrrolidone group.
- polar substituents are here also included such substituents as w, fi l0: %
- Suitable substituents of this type are represented by the group in which the hydrocarbon radical R is preferably substituted by one or more hydroxyl and/ or amino groups, particularly the -(IZIlOCHZ-CH OH OH and (EOCHZ-OHZN(CQH5)Q groups.
- Suitable (B) monomers include olefins, e.g., propylene, 1- or Z-butylene, di-isobutylene and others, and aromatic hydrocarbons such as styrene, although use is preferably made of acids, e.g., maleic acid or the anhydride thereof, particularly methacrylic acid; of alcohols such as vinyl alcohol and allyl alcohol; of pyridine derivatives such as Z-methyl-S-vinyl pyridine, and of pyrrolidone derivatives such as N-vinyl-alpha-pyrrolidone.
- olefins e.g., propylene, 1- or Z-butylene, di-isobutylene and others
- aromatic hydrocarbons such as styrene
- acids e.g., maleic acid or the anhydride thereof, particularly methacrylic acid
- alcohols such as vinyl alcohol and allyl alcohol
- pyridine derivatives such as Z-methyl-S-viny
- Esters and amides of acrylic acid and methacrylic acid, ethers and esters of enols such as vinyl alcohol and allyl alcohol, and others, are also suitable. Esters having such groups as in which the R substituent contains one or more hydroxyl and/ or amino groups, have also been found particularly valuable. Use is preferably made of beta-hydroxy ethyl methacrylate and beta-diethyl amino ethyl methacrylate.
- Very suitable telomers and/or copolymers for the conversion with polymerized 1,2-alkylene imines according to the invention are derived from lauryl methacrylate and/ or stearyl methacrylate on the other hand, and methacrylic acid and/or beta-hydroxy ethyl methacrylate on the other.
- telomerization agents are the substances usual for this purpose such as mercaptans, chloroalkanes, e.g., carbon tetrahalides, organic nitro compounds and others.
- mercaptans e.g., chloroalkanes
- chloroalkanes e.g., carbon tetrahalides
- organic nitro compounds e.g., organic nitro compounds and others.
- aromatic nitro compounds such as nitro benzene which, if desired, may also contain other polar groups, such as p-nitrothiophenol.
- the telomer group according to the invention is produced by polymerizing or copolymerizing together with one or more (B) monomers one or more (A) monomers in the presence of a telomer such as an aromatic nitro compound.
- a telomer such as an aromatic nitro compound.
- suitable combinations of the (A) and (B) monomers are mixtures of lauryl methacrylate and/ or stearyl methacrylate on the one hand and methacrylic acid and/or beta-hydroxy ethyl methacrylate on the other.
- the polymerization products of 1,2-alkylene imines may be converted with the said oilsoluble telomers and/or copolymers by contacting the components, preferably in the liquid phase in a homogeneous medium.
- the polymerized 1,2-alkylene imine is generally employed as a solution in an organic solvent which, if desired, may also contain water.
- Suitable solvents are in particular alcohols having from 1 to 4 carbon atoms, e.g., methanol, ethanol, isopropanol and the butanols as well as mixtures thereof with water and/ or hydrocarbons.
- the hydrocarbons are, for example, gasoline fractions or benzenoid hydrocarbons.
- telomers and/ or copolymers are preferably also used as a solution in an organic solvent.
- Suitable solvents for this purpose are hydrocarbons, e.g., gasoline fractions or aromatic hydro pizirbons such as benzene, toluene, the xylenes, and the
- the polymeric alkylene imines are reacted in situ even during the copolymrization or telomerization with the resultant copolymers.
- a solution of a polymerized 1,2-alkylene irnine in a water/isopropanol mixture is contacted with a solution of one or more telomers and/ or copolymers in toluene, after which the solvents are removed by distillation, if desired, under reduced pressure.
- the reaction is generally carried out at temperatures in the range of from 20 C. to 130 (3., although higher or lower temperatures are also possible.
- lubricants in which are incorporated the products obtained according to the invention have excellent weaninhibiting properties. This applies in particular to the inhibition of the wear of pistons, piston rings and cylinders, which occurs in engine cylinders, e.g., in combustion engines such as automobile engines, diesel engines and aero piston engines. Since the starting telomers and copolymers incorporated in lubricants generally have a fairly high detergency with respect to the cylinder fouling in engines in such cases the conversion with the polymerized 1,2-alkylene imines results in products having in addition to detergent properties also wear inhibiting properties.
- the said products are suitable as additives to lubricants of various types.
- mineral lubricating oils of diverse viscosity, although the products are also suitably incorporated into synthetic lubricating oil as well as into lubricating oils containing fatty oils.
- the products may also be worked up in lubricating greases.
- the products may be added as such to the lubricant.
- the product is only partly freed from the solvent and/ or telomerization agent, e.g., by steam distillation; a small quantity of a lubricating oil is then added and the remnants of the solvents and/or telomerization agents are finally distilled off by steam, preferably under reduced pressure.
- the resultant concentrate may now be diluted with a lubricating oil and/ or worked up into a lubricating grease.
- the quantity of the products of the invention incorporated into lubricants may vary within wide limits. In general the desired improvement is already obtained when the quantity incorporated lies between 0.5 and 5%, particularly between 1 and 3% based on the weight of the finished lubricant. In special cases, however, quantities even greater than the said quantities may be incorporated, e.g., in the case of diesel engines in which use is made of fuel having a high sulfur content.
- the starting material was a copolymer of stearyl meth- 0 acrylate and methacrylic acid in which the monomers were present in a molar ratio of 7: 1.
- the starting material was a copolymer of stearyl methacrylate, beta-hydroxy ethyl methacrylate and methacrylic acid in which the monomers were present in a molar ratio of 10:2:1.
- the resultant concentrate was diluted with the said lubricating oil to 3860 parts by weight.
- the lubricating oil thus prepared which contained 1.55% by weight of the additive, was used in the engine tests given below.
- EXAMPLE III The starting material was a telomer prepared by copolymerizing stearyl methacrylate and beta-hydroxy ethyl methacrylate in the presence of nitrobenzene, and in which the two monomers were present in a molar ratio of 5:1.
- a solution of 73 parts by weight of the said telomer in 870 parts by weight of toluene was heated to approximately 70 C.
- 19.5 parts by weight of Polymin P an approximately 70% by weight aqueous solution of polyethylene imines
- the resultant clear solution was then heated over a steam bath for approximately 15 minutes using a reflux condenser.
- 2000 parts by weight of a Venezuelan mineral lubricating oil (viscosity: 114 cs. at 100 F.) were then added and the solvents distilled off in vacuo (0.3 mm. Hg) at 75 C.
- the resultant concentrate was diluted with the said lubricating oil to 5200 parts by weight.
- the lubricating oil thus prepared which contained 1.66% by Weight of the additive, was used in the engine tests given below.
- the two solutions (1) and (2) were mixed by stirring, in a clear and homogeneous mixture being obtained. This mixture was then heated, using a reflux condenser, and passing through nitrogen, while stirring, and 0.5 part by weight of azodiisobutyric acid nitrile was added, followed by an equal quantity of azodi-isobutyric acid nitrile after 1 /2 hours, the mixture being boiled for a total of 18 hours.
- the fuel used was a motor gasoline which had a sulfur content of 0.06% and contained 0.7 ml. TEL per US. gallon.
- the temperature of the cooling water was 40 C.
- the figures in the following table show the ring wear in mg. of iron in experiments of 45 hours. The ring wear relates to all four piston rings.
- the present products may also be combined with other additives such as anti-oxidants, detergent dopes, viscosity-index improvers, corrosion inhibitors, anti-foaming agents, pour point depressants, extreme pressure and oiliness agents and other materials generally added to lubricants.
- additives such as anti-oxidants, detergent dopes, viscosity-index improvers, corrosion inhibitors, anti-foaming agents, pour point depressants, extreme pressure and oiliness agents and other materials generally added to lubricants.
- An, improved mineral lubricating oil composition comprising a major amount of mineral lubricating oil and, from about 0.5% to about 5% by weight of an oilsoluble reaction product of a polymerized 1,2-alkylene imine having from 5 to 150 imine units with a polymer of a mono-olefinic monomer containing an acidic polar group selected from carboxyl and hydroxy groups and an oleophilic hydrocarbyl group of from 8 to 18 carbon atoms, said reaction product having a molecular Weight of from 1000 to 500,000.
- An improved mineral lubricating oil composition comprising a major amount of mineral lubricating oil and from about 0.5% to about 5% by Weight of an oilsoluble reaction product of polymerized 1,2-alkylene imine having from 5 to imine units and a copolymer of free methacrylic acid and a C alkyl acrylate ester, the acid portion of the ester being selected from the group consisting of acrylic acid and methacrylic acid, the molecular weight of the total product being from 80,000 to 500,000.
- An improved mineral lubricating oil composition comprising a major amount of mineral lubricating oil and from about 0.5% to about 5% by Weight of an oilsoluble reaction product of polymerized 1,2-alkylene imine having from 5 to 150 imine units and a copolymer of a hydroxy alkyl acrylate and a C alkyl acrylate ester, the acid portion of said C ester being selected from the group consisting of acrylic acid and methacrylic acid, the total molecular weight of the product being from 80,000 to 500,000.
- An improved mineral lubricating oil composition comprising a major amount of mineral lubricating oil and from about 0.5% to about 5% by Weight of an oilsoluble reaction product of polymerized 1,2-alkylene imine having from 5 to 150 imine units and a copolymer of free acrylic acid and a C alkyl acrylate ester, the acid portion of the ester being selected from the group consisting of acrylic and methacrylic acid, the total molecular weight of the product being from 80,000 to 500,000.
- a telomerizing agent selected from the group consisting of haloalkane, alkyl mercaptan, nitro alkane, and nitrobenzene
- An improved mineral lubricating oil composition comprising a major amount of mineral lubricating oil and about 0.5% to about 5% by weight of an oil-soluble reaction product of polyethylene imine having from 5 to 25 imine units and a copolymer of stearyl methacrylate and methacrylic acid in the mol ratio of 7:1, respectively, said product having a molecular Weight of from 80,000 to 500,000.
- An improved mineral lubricating oil composition comprising a major amount of mineral lubricating oil and from about 0.5% to about 5% by Weight of an oilsoluble reaction product of polyethylene imine having from 5 to 25 imine units and a copolymer of stearyl methacrylate, beta-hydroxy ethyl methacrylate and methacrylic acid in the mol ratio of 10:2:1, respectively said product having a molecular Weight of from 80,000 to 500,000.
- An improved mineral lubricating oil composition comprising a major amount of mineral lubricating oil and from about 0.5% to about 5% by weight of an oil-soluble reaction product of polyethylene imine having from 5 to 25 imine units and a nitrobenzene telomer of a copolymer of stearyl methacrylate and beta-hydroxyethyl methacrylate in the mol ratio of 5:1, respectively, said product having a molecular weight of 1000 to 10,000.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL233326 | 1958-11-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3130161A true US3130161A (en) | 1964-04-21 |
Family
ID=19751433
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US850034A Expired - Lifetime US3130161A (en) | 1958-11-18 | 1959-11-02 | Lubricating oil and anti-wear additives therefor |
Country Status (6)
Country | Link |
---|---|
US (1) | US3130161A (pt) |
BE (1) | BE584708A (pt) |
DE (1) | DE1211739B (pt) |
FR (1) | FR1241970A (pt) |
GB (1) | GB898056A (pt) |
NL (1) | NL101069C (pt) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3326804A (en) * | 1965-10-01 | 1967-06-20 | Exxon Research Engineering Co | Oleaginous compositions containing sludge dispersants |
WO2013093104A1 (en) * | 2011-12-22 | 2013-06-27 | Shell Internationale Research Maatschappij B.V. | Grease composition |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB466270A (en) * | 1935-08-22 | 1937-05-24 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of nitrogenous products |
US2296225A (en) * | 1935-08-07 | 1942-09-15 | Gen Aniline & Film Corp | Nitrogenous condensation products and a process of producing same |
US2440800A (en) * | 1942-04-10 | 1948-05-04 | Du Pont | Halogenated hydrocarbons and method for their preparation |
US2628941A (en) * | 1950-02-04 | 1953-02-17 | Shell Dev | Extreme pressure lubricant |
GB760554A (en) * | 1953-05-18 | 1956-10-31 | Bataafsche Petroleum | Lubricating compositions and additives therefor |
US2839512A (en) * | 1955-12-30 | 1958-06-17 | Shell Dev | Vinylpyridine long chain acrylic ester copolymers and their preparation |
US2870129A (en) * | 1953-11-30 | 1959-01-20 | United Shoe Machinery Corp | Water vapor permeable resins |
US2889282A (en) * | 1956-09-17 | 1959-06-02 | Shell Dev | Lubricating oil compositions |
US2892788A (en) * | 1956-07-30 | 1959-06-30 | California Research Corp | Lubricant composition |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1009807B (de) * | 1954-08-31 | 1957-06-06 | Basf Ag | Verfahren zur Herstellung von Umsetzungsprodukten aus N-Vinyllactampolymerisaten |
-
0
- BE BE584708D patent/BE584708A/xx unknown
- NL NL101069D patent/NL101069C/xx active
-
1959
- 1959-11-02 US US850034A patent/US3130161A/en not_active Expired - Lifetime
- 1959-11-16 FR FR810242A patent/FR1241970A/fr not_active Expired
- 1959-11-16 DE DES65853A patent/DE1211739B/de active Pending
- 1959-11-16 GB GB38735/59A patent/GB898056A/en not_active Expired
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2296225A (en) * | 1935-08-07 | 1942-09-15 | Gen Aniline & Film Corp | Nitrogenous condensation products and a process of producing same |
GB466270A (en) * | 1935-08-22 | 1937-05-24 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of nitrogenous products |
US2440800A (en) * | 1942-04-10 | 1948-05-04 | Du Pont | Halogenated hydrocarbons and method for their preparation |
US2628941A (en) * | 1950-02-04 | 1953-02-17 | Shell Dev | Extreme pressure lubricant |
GB760554A (en) * | 1953-05-18 | 1956-10-31 | Bataafsche Petroleum | Lubricating compositions and additives therefor |
US2870129A (en) * | 1953-11-30 | 1959-01-20 | United Shoe Machinery Corp | Water vapor permeable resins |
US2839512A (en) * | 1955-12-30 | 1958-06-17 | Shell Dev | Vinylpyridine long chain acrylic ester copolymers and their preparation |
US2892788A (en) * | 1956-07-30 | 1959-06-30 | California Research Corp | Lubricant composition |
US2889282A (en) * | 1956-09-17 | 1959-06-02 | Shell Dev | Lubricating oil compositions |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3326804A (en) * | 1965-10-01 | 1967-06-20 | Exxon Research Engineering Co | Oleaginous compositions containing sludge dispersants |
WO2013093104A1 (en) * | 2011-12-22 | 2013-06-27 | Shell Internationale Research Maatschappij B.V. | Grease composition |
RU2628512C2 (ru) * | 2011-12-22 | 2017-08-17 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Композиция консистентной смазки |
Also Published As
Publication number | Publication date |
---|---|
DE1211739B (de) | 1966-03-03 |
FR1241970A (fr) | 1960-09-23 |
GB898056A (en) | 1962-06-06 |
BE584708A (pt) | |
NL101069C (pt) |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3361673A (en) | Lubricating oil compositions containing alkenyl succinimides of tetraethylene pentamine | |
US3024195A (en) | Lubricating oil compositions of alkylpiperazine alkenyl succinimides | |
US3288714A (en) | Lubricating oil compositions containing alkenyl succinic anhydrides | |
US3154560A (en) | Nu, nu'-azaalkylene-bis | |
US3131150A (en) | Lubricating oil compositions containing n-substituted alkenyl succinimides in combination with polyamines | |
US3428615A (en) | Detergent copolymer acyl amido alkyl ethers of polyalkylene glycol | |
US3235503A (en) | Lubricant containing alkylene polyamine reaction product | |
US3438899A (en) | Alkenyl succinimide of tris (aminoalkyl) amine | |
US3525693A (en) | Alkenyl succinic polyglycol ether | |
US3684713A (en) | Compositions containing oil-soluble azo compounds | |
US3844958A (en) | Hydrocarbyl amines for lubricating oil detergents | |
US3342735A (en) | Alkenyl succinic anhydride-amine-ps reaction product | |
US3311559A (en) | Oil additive | |
US3210283A (en) | Lubricant containing alkenyl succinimide and hydroxypolyamine | |
US3220949A (en) | Lubricating oil compositions containing iodine and ashless nitrogen-containing oil-soluble derivatives of alkenyl succinic anhydride | |
US2637698A (en) | Mineral oil lubricating composition containing a copolymer of an alkyl ester of itaconic acid and an alkyl acrylate or methacrylate | |
US3664955A (en) | Lubricating oil compositions of improved thermal stability | |
US3130161A (en) | Lubricating oil and anti-wear additives therefor | |
US3200075A (en) | Lactone amides in lubricating oils | |
US3397146A (en) | Lubricating compositions | |
US3912641A (en) | Sulfur and nitrogen-containing organic compositions processes for making them and fuels and additives containing them | |
US3844956A (en) | Lubricants containing amino and hydroxy-substituted polyphenylthioethers | |
US3192165A (en) | Mineral oil composition | |
US3647731A (en) | Condensation product of oil-soluble polymers with polyamine | |
US4005021A (en) | Oil-soluble reaction products of (a) a high molecular weight olefin polymer, acrylonitrile, chlorine, an amine and maleic anhydride, with (g) an aliphatic amines; and lubricant compositions containing the same |