Classifications

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  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
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  • 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
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  • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
  • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
  • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
  • C08G14/12—Chemically modified polycondensates
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  • C10M2207/28—Esters
  • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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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
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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
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/062—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups bound to the aromatic ring
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  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/223—Five-membered rings containing nitrogen and carbon only
  • C10M2215/224—Imidazoles
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  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
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  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
  • C10M2215/226—Morpholines
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  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/26—Amines
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  • C10M2215/30—Heterocyclic compounds
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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
  • C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
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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
  • C10M2217/043—Mannich bases
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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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  • 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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  • 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
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
  • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
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  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
  • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives

Definitions

• the products of the herein-described invention are oil-soluble, and are highly effective additives for imparting dispersant-detergent properties to lubricant oil compositions.
• Lubricants containing these products provide a high degree of protection against the deposition of sludge and varnish, and corrosion when used as crankcase lubricant additives.
• This invention relates to improved lubricating oils and particularly concerns automobile and diesel crankcase lubricating oil formulations containing a minor amount of a new class of oil-soluble addition agents which improve the performance of the oil, particularly its dispersant-detergent function thus enabling lubricating oils to provide a high degree of protection of the lubricated parts of internal combustion engines.
• crankcase lubricating oils present-day automobile and diesel engines have been designed for higher power output, lower combustion products emission and longer in-service periods of use of crankcase lubricating oils. These design changes have resulted in such severe operating conditions as to necessitate devising higher efliciency lubricating oils that will, under the increased severity of in-service use, afford proper protection against corrosion and the accumulation or deposition of sludge, varnish and resinous materials on the surface of engine parts which rapidly accelerate decrease in both operating efficiency and life of the engine.
• the principal ingredient of crankcase lubricants is a base lubricating oil, a mixture of hydrocarbons derived from petroleum.
• a lubricant base oil Even when highly refined by removal of deleterious components, such as polymerizable components, acid formers, waxes, etc., a lubricant base oil still requires the addition of a number of oil-soluble chemical additives to enable the oil to resist oxidation, deposition of sludge and varnish on, and corrosion of, the lubricated metal parts, and to provide added lubricity and regulated viscosity change from low to high temperature.
• crankcase oil formulations not only to reduce thermal decomposition of the oil and addition agents (antioxidants) but also to keep in suspension (as a dispersant) and to resuspend (as a detergent) insoluble combustion and degradation products as well as to neutralize acidic products (anti-corrosion agents).
• a separate additive is usually added for each improvement to be effected.
• additives suggested by the prior art are amine salts, amides, imides, and amidines of polybutenyl-substituted polycarboxylic acids and polymeric compounds having pendant or grafted-on polar groups.
• Mannich condensation products derived from alkylsubstituted hydroxyaromatic compounds having a relatively low molecular weight alkyl substituent, i.e., 2 to 20 carbon atoms in the alkyl substituent and chlorinated 'wax (straight chain) type alkyl-substituents are described in US. Pat, Nos. 2,403,453; 2,353,491; 2,363,134; 2,459,112; 2,984,550 and 3,036,003.
• none of such prior Mannich condensation products are suitable for use as dispersant-detergent addition agents for present-day long drain oil interval in-service use.
• the prior C C alkyl-substituted Mannich condensation products commonly are prepared by the conventional technique of adding the aliphatic aldehyde to a heated mixture of the alkylhydroxyaromatic and amine reagents, in the presence or absence of a solvent, and then heating the resultant mixture to a temperature between -350 F. until dehydration is complete.
• a solvent such as benzene, toluene, xylene, methanol and others easily separated from the reaction mixture and light mineral oils, such as those used in blending stocks to prepare lubricating oil formulations in which the product is formed as a mineral oil concentrate are usually used.
• the water by-product is removed by heating the reaction mixture to a temperature sufficiently high, at
• the neutralized or overbased alkaline earth metal salts (alkaline earth metal phenates) of those prior low molecular weight Mannich condensation products have been suggested for use in providing lubricating oils with a combination of detergent-inhibitor properties in one addition agent.
• the neutralized alkaline earth metal salts have one equivalent of alkaline earth metal for each bydroxy group present.
• the overbased salts have, for each hydroxy group present, more than one equivalent of alkaline earth metal in the form of a hydroxy metaloxy, alkoxy metaloxy and even alkaline earth metal carbonate complex with hydroxy metaloxy on each benzene group as a replacement for the phenol hydroxy group.
• said addition agents form objectionable metal ash deposits and have other performance deficiencies.
• This invention pertains to a new class of compounds useful as multifunctional addition agents for lubricating oils, particularly such oils used in internal combustion engines in which they function as highly efiicient dispersant-detergent and oxidation inhibitor agents.
• the new class of compounds which comprise our invention are oil-soluble high molecular aliphatic acid modified high molecular weight Mannich condensation products, which are further treated with an aliphatic aldehyde. They can be made by condensing in the usual manner under Mannich reaction conditions at a temperature in the range of ISO-325 F.
• alkyl-substituted hydroxyaromatic compound in which the alkyl-substituent has an average molecular weight of about 600-100,000, preferably a polyalkylphe- 1101 whose polyalkyl substituent is derived from l-monoolefin polymers having an average molecular weight of about 850-2500;
• An amine containing at least one NH group preferably an alkylene polyamine of the formula NHz(A-N)H wherein A is a divalent alkylene radical having 2 to 6 carbon atoms, and x is an integer from 1 to 10;
• the above resultant modified Mannich condensation product is then treated with (5) an aliphatic aldehyde in an amount of from about 2 to about 6 moles of the aldehyde per mole of the alkyl-substituted hydroxy compound used in the preparation of said modified Mannich product.
• the foregoing high molecular weight products of this invention are preferably prepared according to the conventional methods employed for the preparation of Mannich condensation products, using the first four above mentioned reactants in the respective molar ratios of about l.0:0.1-l0:1.0l0:0.0l41.0.
• Suitable condensation procedure involves adding at a temperature of from room temperature to about 200 F. the aldehyde reagent (3) to a mixture of reagents (1), (2), and (4), above, or such reagents in an easily removed organic solvent, such as benzene, Xylene, or toluene, or in a solvent refined mineral oil; completing the reaction at 300 F.; then slowly adding the additional aldehyde, reactant (5) at 180-300" F.
• the reaction mass is then heated at an elevated temperature of about 275-375 F., preferably with blowing with an inert stripping gas, such as nitrogen, carbon dioxide, etc. until dehydration is complete.
• the preferred additives are high molecular weight bis-Mannich condensation products formed by reacting 1) 3. 850-2500 molecular weight polybutylphenol; (2) an ethylene polyamine; (3) formaldehyde; and (4) an aliphatic acid in the respective molar ratio of 1.0:0.7-1.0:1.52.1:0.0l40.62, and treating the resultant modified Mannich condensation product with 2-4 moles of paraformaldehyde per mole of the polybutylphenol.
• the preferred aliphatic acid reactant is an acid having 10-20 carbon atoms per carboxylic acid group.
• the high molecular weight products of this invention are effective additives for lubricating oil lubricants, imparting thereto dispersant-detergent properties and high temperature oxidation stability, at relatively low concentrations, e.g., 0.05% to about 10% in formulated crankcase lubricating oil compositions. Higher concentrations, e.g., 10% to about 70%, are useful concentrates for the preparation of such lubricating oil compositions.
• High molecular weight alkyl-substituted Hydroxyaromatics are polypropylphenol, polybutylphenol and other polyalkylphenols. These polyalkylphenols may be obtained by the alkylation, in the presence of an alkylating catalyst, such as BF of phenol with high molecular weight polypropylene, polybutaylene and other polyalkylene compounds to give alkyl substituents on the benzene ring of phenol having an average 600-100,000 fin.
• an alkylating catalyst such as BF of phenol with high molecular weight polypropylene, polybutaylene and other polyalkylene compounds to give alkyl substituents on the benzene ring of phenol having an average 600-100,000 fin.
• the 600 Mn and higher Mn alkyl-substituents on the hydroxyaromatic compounds may be derived from high molecular weight polypropylenes, polybutenes and other polymers of mono-olefins, principally l-mono-olefins. Also useful are copolymers of mono-olefins with monomers copolymerizable therewith wherein the copolymer molecule contains at least 90%, by weight, of mono-olefin units.
• copolymers of butenes (butene-1, butene-2 and isobutylene) with monomers copolymerizable therewith wherein the copolymer molecule contains at least 90%, by weight, of propylene and butene units, respectively.
• Said monomers copolymerizable with propylene or said butenes include monomers containing a small proportion of unreactive polar groups such as chloro, bromo, keto, ether, aldehyde, which do appreciably lower the oil-solubility of the polymer.
• the co-monomers polymerized with propylene or said butenes may be aliphatic and can also contain non-aliphatic groups, e.g., styrene, methylstyrene, p-dimethylstyrene, divinyl benzene and the like. From the foregoing limitation placed on the monomer copolymerized with propylene or said butenes, it is abundantly clear that said polymers and copolymers of propylene and said butenes are substantially aliphatic hydrocarbon polymers. Thus the resulting alkylated phenols contain substantially alkyl hydrocarbon substituents having fin upward from 600.
• others which may be used include those which have been used to prepare prior low molecular weight Mannich condensation products, e.g., high molecular weight alkyl-substituted derivatives of resorcinol, hydroquinone, cresol, catechol, xylenol, hydroxy diphenyl, benzylphenol, phenethylphenol, naphthol, tolylnaphthol, among others.
• Mannich condensation products e.g., high molecular weight alkyl-substituted derivatives of resorcinol, hydroquinone, cresol, catechol, xylenol, hydroxy diphenyl, benzylphenol, phenethylphenol, naphthol, tolylnaphthol, among others.
• Preferred for the preparation of the aforementioned preferred bis Mannich condensation products are the polyalkylphenol reactants, e.g., polypropylphenol and polybutylphenol whose alkyl group has an average number molecular weight of 6003000, the most preferred being polybutylphenol Whose alkyl group has an average number molecular weight of 850-2500.
• polyalkylphenol reactants e.g., polypropylphenol and polybutylphenol whose alkyl group has an average number molecular weight of 6003000, the most preferred being polybutylphenol Whose alkyl group has an average number molecular weight of 850-2500.
• HN group containing reactants Representative of this class of reactants are alkylene polyamines, principally polyethylene polyamines.
• Other representative organic compounds containing at least one HN group suitable for use in the preparation of Mannich condensation products are well known and include the monoand di-amino alkanes and their substituted analogs, e.g., ethylamine and diethanol amine; aromatic diamines, e.g., phenylene diamine, diamino naphthalenes; heterocyclic amines, e.g., morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and their substituted analogs.
• Suitable alkylene polyamine reactants include ethylenediamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene hepta-amine, heptaethylene octamine, octaethylene nonamine, nonaethylene decamine and decaethylene undecamine and mixture of such amines having nitrogen contents corresponding to the alkylene polyamines, in the formula H N(A-NH) H, mentioned before, A is divalent ethylene and x is 1 to 10 of the foregoing formula.
• propylene polyamines such as propylene diamine and di-, tri-, tetra-, penta-propylene tri-, tetra-, pentaand hexaamines are also suitable reactants.
• the alkylene polyamines are usually obtained by the reaction of ammonia and dihalo alkanes, such as dichloro alkanes.
• the alkylene polyamines obtained from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of dichloro alkanes having 2 to 6 carbon atoms and the chlorines on different carbons are suitable alkylene polyamine reactants.
• ALDEHYDE REACTANTS Representative of this aldehyde class of reactants for use in the preparation of the high molecular products of this invention include the aliphatic aldehydes such as formaldehyde (also as paraformaldehyde and formalin), acetaldehyde and aldol (b-hydroxybutyraldehyde). We prefer to use formaldehyde, para-formaldehyde or a formaldehyde yielding reactant.
• formaldehyde also as paraformaldehyde and formalin
• acetaldehyde acetaldehyde
• aldol b-hydroxybutyraldehyde
• the aliphatic acid reactant of this invention has a carbon atom content of a total (including the carbon of the carboxylic acid group) of from about six to about 30 and consists of the alkanoic (saturated) and alkenoic (mono-unsaturated) acids.
• the upper limit of the carbon content is restricted only by the largest carbon atom content of such acids available or capable of feasible preparation.
• Such aliphatic acids can be natural and synthetic mono-, diand tri-carboxylic acids.
• Suitable natural aliphatic acids are the natural fatty acids obtainable by known hydrolysis (acid and alkaline) of vegetable and animal oils and fats and wax esters.
• Suitable synthetic acids can be derived from oxidation of the alcohol moiety of the Wax ester where such alcohol moiety has at least six carbon atoms; from the polymerization of unsaturated natural acids having two or three carbon to carbon double bonds (dimer and trimer acids) and the hydrogenation of residual carbon to carbon double bonds in such polymer acids.
• the polymer acids obtained from oleic acid, uric acid, linoleic acid and linolenic acid and other unsaturated acids; and from oxidation or other reactions of polypropenes and polybutenes (e.g. polyisobutenes) which introduce one or more carboxylic acid group on the polymer chain.
• Suitable alkanoic acids having 6 or more total carbon atoms are those obtainable from the glycerides: vegetable oils and animal fats and the wax esters by the known hydrolysis or saponification-acidification or acid treatment processing of said oil and fat glycerides and the wax esters (i.e. natural waxes), the oxidation of the monoalcohol obtainable from the simple ester of the wax esters and known acid synthesis.
• suitable alkanoic acids i.e.
• R groups of 6 to 30 carbon atoms include caproic acid, caprylic acid, capric acid, hendecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, medullic acid, behenic acid, lignoceric acid, pentacosoic acid, cerotic acid, heptacosoic acid, monocosoic acid, montanic acid, and melissic acid.
• alkanoic acids are obtained first in mixtures of two, three or more alkanoic acids of different carbon contents from said glycerides and wax esters; said mixtures can be used in this invention in place of a single alkanoic acid reactant.
• said mixtures of alkanoic acids also contain unsaturated acids it is preferred that such mixture of acids be reduced to a product which is substantially free of unsaturation.
• Suitable alkenoic acids having a total of at least six carbon atoms include those from hexenoic, heptenoic, octenoic, etc. acids up to oleic (Cm) and erucic (C acids. Also suitable are the dimer acid of linoleic and its saturated dimer analog; dimer and trimer acids of linolenic acid and the saturated dimer and trimer analogs. Other polymeric acids, e.g. co-dimers of oleic and linoleic or linolenic acids and the saturated analogs of those dimer acids are also suitable.
• EXAMPLE I 2085 grams (0.61 mole) of a 1600 average molecular weight polybutyl-substituted phenol (47% polybutylphenol, 53% polybutene and diluent oil), 765 grams of a solvent-extracted W mineral oil, 109 grams (0.56 mole) tetraethylene pentamine, and 109 grams (0.38 mole) of a modified saturated G -C fatty acid, identified as Emery 896 Fatty Acid by Emery Industries Inc., were admixed and heated to 150 F. 84 ccs. (1.12 moles) of formalin were then rapidly added to the mixture. Thereafter, there were slowly added 168 ccs.
• reaction mass was filtered.
• the recovered filtrate was clear, had a nitrogen content of 1.30%, and a SSU viscosity at 210 F. of 954.
• Part B To 3200 grams of an oleic acid-modified Mannich condensation product prepared as in part A, above,
• the composite product was crystal clear and had a SSU viscosity at 210 F. of 1028.
• the thermal oxidation stability of the aldehyde treated acid-modified high molecular weight Mannich condensation product is demonstrated by the so-called Hot Tube Test.
• This test measures the oxidation and thermal stability of dispersant additives for lubricating oils, particularly automotive crankcase lubricants.
• the subject dispersant is incorporated in a typical crankcase lubricating oil composition formulation, and the composition subjected to the following test:
• the oil composition being tested is passed, at the rate of 0.1 cc. per minute downward through a 20 inch, 8 mm. vertical glass tube 6 inches of which are surrounded by a furnace and heated at 495 F. for 100 minutes, while air at the rate of 20 cos. per minute is passed downwardly through the tube.
• a prefect tube is rated 10A, where the numerical value refers to the varnish in the heated portion of the tube, and the letter rating refers to the varnish formed in the cool zone of the tube below the furnace. The lower the numerical rating and the higher the letter rating, the poorer is the oxidation and thermal stability of the dispersant.
• This Mannich condensation product was prepared by mixing together 260 grams (0.073 mole) of a 1600 average molecular weight polybutyl-substituted phenol (42% polybuty1- phenol, 58% polybutene and oil), 39 grams of a solventextracted 5W mineral oil, 13 grams (0.067 mole) tetraethylene pentamine, and the mixture heated to B2, 10 cos. (0.134 mole) formalin were then added, and the mixture reacted at 300-320 F. for 3 hours while blowing with nitrogen at the rate of 1 c.f.h. At the end of the reaction period the product wfarizgtered. The filtrate had a SSU viscosity at 210 F. o
• oils can be any normally liquid oleaginous lubricants, such as hydrocarbon oils, both natural, i.e., petroleum oils, and synthetic lubricating oils, for example, those obtained by the polymerization of olefins, as well as synthetic lubricating oils of the alkylene oxide type, and the polycarboxylic acid ester type, such as the oil-soluble esters of adipic acid, sebacic acid, azelaic acid, etc.
• hydrocarbon oils both natural, i.e., petroleum oils
• synthetic lubricating oils for example, those obtained by the polymerization of olefins, as well as synthetic lubricating oils of the alkylene oxide type, and the polycarboxylic acid ester type, such as the oil-soluble esters of adipic acid, sebacic acid, azelaic acid, etc.
• Lubricating oil compositions containing the aldehyde treated acid-modified Mannich condensation products of the present invention may also contain other additives such as for example, VI improvers, rust inhibitors, oiliness agents, pour point depressors, etc.
• An oil-soluble aliphatic acid-modified high moleclar weight Mannich condensation product prepared by the process comprising (A) reacting at a temperature of from about 150 F. to 325 F.:
• An oil-soluble aliphatic acid modified high molecular weight Mannich condensation product prepared by the process comprising, (A) reacting at a temperature of from 150 to 325 F.:
• alkyl-substituted phenol (a) is selected from the group consisting of polypropylphenol and a polybutylphenol in which the polypropyl and the polybutyl substituents have average molecular weight of from about 600 to about 3,000
• the amine reactant (b) has the formula wherein at is an integer from 1 to 10, aldehyde (0) is formalin, the aliphatic acid (d) is a fatty acid having from about 10 to about 20 total carbon atoms per carboxylic acid group, and the additional aldehyde (e) is paraformaldehyde.
• alkyl-substituted phenol is a polybutylphenol (a) in which the polybutyl substituent has an average molecular weight of about 1,500
• the alkylene polyamine (b) is tetraethylene 'pentarnine
• aldehyde (c) in formalin
• the aliphatic acid (d) is oleic acid
• the additional aldehyde (e) is paraformaldehyde.
• a method of preparing the oil-soluble acid-modified high molecular weight Mannich product of claim 1 as solute in the presence of hydrocarbon diluent consisting essentially of aliphatic hydrocarbon of 600-100,000 average molecular Weight and mineral lubricating oil which comprises reacting at a temperature in the range of 325 F. and in the presence of said diluent said reactants (a), (b), (c) and (d) in the respective molar ratio of 1.0:0.11.0:1.010:0.0l41.0 and then further reacting (e) 26 moles additional formaldehyde per mole of reactant (a) at a temperature in the range of 27 5-37 5 F. while blowing with inert stripping gas until the resultant product is dehydrated, wherein the amount of said diluent used provides 10-70 weight percent of said Mannich product as solute.
• hydrocarbon diluent consisting essentially of aliphatic hydrocarbon of 600-100,000 average molecular Weight and mineral lubricating oil
• hydrocarbon diluent is butene polymer derived hydrocarbon of about 1500 number average molecular weight and SAE-SW oil
• reactant (a) is about 1500 number average molecular weight polybutyl-substituted phenol
• (b) is tetraethylene pentamine
• (c) is formaldehyde
• (d) is oleic acid
• (e) is paraformaldehyde and wherein the amount of said diluent provides 40 weight percent of said Mannich product as solute.

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

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• 1970
  • 1970-08-31 US US00068469A patent/US3787458A/en not_active Expired - Lifetime
• 1971
  • 1971-07-30 NL NLAANVRAGE7110554,A patent/NL169494C/xx not_active IP Right Cessation
  • 1971-08-09 CA CA120092A patent/CA927842A/en not_active Expired
  • 1971-08-23 BE BE771672A patent/BE771672A/xx not_active IP Right Cessation
  • 1971-08-24 LU LU63769D patent/LU63769A1/xx unknown
  • 1971-08-25 GB GB3989771A patent/GB1362013A/en not_active Expired
  • 1971-08-25 DE DE2142592A patent/DE2142592C3/de not_active Expired
  • 1971-08-25 SU SU1696403A patent/SU526293A3/ru active
  • 1971-08-26 FR FR7131063A patent/FR2103629B1/fr not_active Expired
  • 1971-08-28 PL PL1971150245A patent/PL82213B1/pl unknown
  • 1971-08-30 YU YU2216/71A patent/YU39599B/xx unknown
  • 1971-08-31 JP JP6694571A patent/JPS5725593B1/ja active Pending
  • 1971-08-31 RO RO7168080A patent/RO70125A/ro unknown
  • 1971-08-31 CS CS7600000751A patent/CS183645B2/cs unknown
  • 1971-08-31 CS CS7100006223A patent/CS183629B2/cs unknown
  • 1971-08-31 HU HU71SA2230A patent/HU165124B/hu unknown
• 1976
  • 1976-05-31 SU SU762364204A patent/SU617018A3/ru active

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