-
Oil soluble compounds suitable as lubricant additives and of formula R1-X-A-Bn where R1 is an alkyl or alkenyl group having at least 12 carbon atoms, X is an ester, amide or imide grouping, A is an organic radical containing at least one basic nitrogen atom, n is 1 to 6 and B is -(CRR)mSO3H and is attached through the carbon atom to a nitrogen atom of A, where each R is hydrogen, alkyl, substituted alkyl, phenyl, substituted phenyl or any two substituents R on adjoining carbon atoms are taken together to form a cyclic system and m is 3 or 4, or a salt thereof, may be prepared by reacting the corresponding alkyl or alkenyl ester, amide or imide with an amine and a sultone or with a prereaction product of the amine and sultone. R1 is preferably derived from a polyolefin, e.g. polyisobutylene of molecular weight 700-3000, hydrogenated if desired. Preferred compounds may be prepared by reacting polyisobutenyl succinic anhydrides with polyamines, optionally modifying the intermediate with a carboxylic acid, aldehyde or ketone, and further reacting the intermediate or modified intermediate with a sultone. Many suitable starting materials are described, and in examples propane sultone is reacted with intermediates prepared from polyisobutenyl succinic anhydride and (I and XXX) tetraethylene pentamine, (IV) reaction product of pentaethylene hexamine and dicyandiamide, (V and XXXII) commercial isomeric pentaethylene hexamines and hexamines containing piperazine rings, (VI and XXXI) pentaethylene hexamine, (VII, XXVIII and XXXVII) triethylene tetramine, (VIII) diethylene triamine, (IX) ethylene diamine, (X and XI) polyethylene imines, (XII) mixed polyethylene polyamines, (XIII and XXXIII) N - b - aminoethyl piperazine, (XIV); dimethylaminopropylenediamine, (XV) N-2-aminoethyl morpholine, (XVI) p - phenylene diamine, (XVII) N-2-aminoethyl ethanolamine, (XVIII) hydroxytetraethylene tetramine, (XIX) reaction product of g -butyrolactone and tetraethylene pentamine, (XX) guanidine carbonate, and tetrathylene pentamine together with (XXI) acetic acid, (XXII) lauric acid, (XXIII) oleic acid, (XXIV) adipic acid, (XXV) salicylaldehyde, (XXVI) benzaldehyde and (XXVII) formic acid; polyisobutenyl succinic anhydride is reacted with (XXXIV) tetraethylene pentamine and 1,1,3 - trimethylp opane sultone, (XXXV) tetraethylene pentamino sulphonic acid and (XXXVI) a mixed polyaminosulphonic acids; and a polyisobutenyl monocarboxylic acid is reacted with a polyalkylene polyamine and propane sultone. The product of (I) is further reacted with (II and III) barium hydroxide and (XXXIX) calcium oxide and carbon dioxide.ALSO:Lubricating compositions comprise a major proportion of a lubricating oil and a minor proportion of a detergent and dispersant additive of formula R1-X-A-Bn, where R1 is an alkyl or alkenyl group having at least 12 carbon atoms, X is an ester, amide or imide grouping, A is an organic radical containing at least one basic nitrogen atom, n is 1 to 6 and B is -(CRR)mSO3H and is attached through the carbon atom to a nitrogen atom of A, where each R is hydrogen, alkyl, substituted alkyl, phenyl, substituted phenyl or any two substituents R on adjacent carbon atoms are taken together to form a cyclic system and m is 3 or 4, or a salt thereof. Preferred additives are formed by reacting polyisobutenyl succinic anhydrides with polyamines, optionally with an acid, aldehyde or ketone, and finally with a sultone; or by reacting the polyisobutenyl succinic anhydrides with polyamine/sultone reaction products. The compositions may also comprise conventional copper deactivators, pour-point depressants, antioxidants and viscosity index improvers. Examples describe compositions comprising mineral lubricating oil and additives of the invention prepared by reacting propane sultone with intermediates from polyisobutenyl succinic anhydride and tetraethylene pentamine alone and with acetic, lauric, oleic, adipic or formic acid, salicylaldehyde or benzaldehyde, reaction product of pentaethylene hexamine and dicyandiamide, isomeric commercial pentaethylene hexamines and hexamines containing piperazine rings, pentaethylene hexamine, triethylene tetramine, diethylene triamine, ethylene diamine, polyethylene polyimines, mixed polyethylene polyamines, N-b -aminoethyl piperazine, dimethylaminoethyl propylenediamine, N - 2 - aminoethyl morpholine, p - phenylene-diamine, N - 2 - aminoethyl ethanolamine, hydroxytetraethylene tetramine, reaction product of g -butyrolactone and tetraethylene pentamine and guanidine carbonate; by reacting polyisobutenyl succinic anhydrides with tetraethylene pentamine and 1,1,3 - trimethylpropane sulphone, tetraethylene pentamino sulphonic acid and mixed polyaminosulphonic acids; and by reacting a polyisobutenyl monocarboxylic acid with a polyalkylene polyamine and propane sultone; the first above additive being optionally reacted with barium hydroxide or calcium oxide and carbon dioxide. Other ingredients of the compositions are a methacrylate polymer V.I. improver, a barium salt of phosphosulphurized polyisobutylene neutralized in the presence of an alkylphenol and treated with carbon dioxide, zinc dialkyl dithiophosphates derived from isopropanol and methyl isobutyl carbinol or from isopropanol and 1-methylheptyl alcohol, and a hindered phenol antioxidant.ALSO:Amino alkane sulphonic acids are prepared by reacting amines with sultones. In examples (XXXV) tetraethylene pentamino propane sulphonic acid is prepared by reacting tetraethylene pentamine with propane sultone and (XXXVI) a polyamine trimethylpropane sulphonic acid is prepared by reacting a commercial mixture said to comprise isomeric pentaethylene hexamines and related hexamines containing piperazine rings with 1,1,3-trimethylpropane sultone.
Lubricating compositions comprise a lubricating oil and a minor proportion, sufficient to provide the desired degree of cold sludge dispercency or detergency, of an additive which is the reaction product of (a) a monoalkenyl substituted succinic anhydride wherein the alkenyl group has a molecular weight of at least 700; and (b) a reaction product of dicyandiamide with a primary alkylene polyamine having at least two primary amino groups and containing the group where A is 2 to 4. Preferred additives are obtained by reacting polyisobutylene/maleic anhydride adducts with reaction products of dicyandiamide with polyethylene polyamines, imino bis propylamine and polyethylene imines. The oil may be a mineral oil, solvent refined mineral oil or mixture thereof, or a spindle oil, and the compositions may also comprise copper deactivators, pour point depressants, antioxidants, viscosity index improvers and other conventional additives, particularly zinc dialkyl dithiophosphates, alkaline earth metal petroleum sulphonates, phenates or phenol sulphides, alkaline earth metal salts of phosphosulphurized hydrocarbons, and copolymers of long chain alkyl methacrylates with vinyl pyridine or N-vinyl pyrrolidone. Many examples are given of lubricating compositions comprising mineral oils, reaction products of polyisobutylene succinic anhydride with reaction products of dicyandiamide and triethylene tetramine, diethylene triamine, tetraethylene pentamine, pentaethylene hexamine and imino bis propylamine, together with other additives such as zinc dialkyl dithiophosphates derived from isopropanol and methyl butyl carbinol or from isopropanol and 1-methylheptyl alcohol, barium salts of phosphosulphurized polyisobutylene and alkyl methacrylate copolymers. Example 41 describes a composition of di(2-ethylhexyl) sebacate, an additive of the invention wherein the alkenyl group is polyisobutylene and the amine is tetraethylenepentamine, phenyl-a -naphthylamine, 3,7-dioctyl phenothiazine and benzotriazole.ALSO:An additive for a lubricating oil is a reaction product of (a) a mono alkenyl substituted succinic anhydride wherein the alkenyl group has a molecular weight of at least 700 and (b) a reaction product of dicyandiamide with a primary alkylene polyamine having at least two primary amino groups and containing the group where A is 2 to 4. The monoalkenyl substituted succinic anhydride may be obtained by reaction between a normally liquid oil soluble polyolefine having a molecular weight of 700 to 3000 and maleic anhydride. Reaction product (b) is preferably prepared at a temperature from 240 DEG to 280 DEG C. and the molar ratio of (a) to (b) may be from 1:1 to 5:1. The alkylene polyamine preferably has the formula H2N-(RNH)n-RNH2 where R is an alkylene radical, preferably -CH2CH2- and n is an integer from 1 to 5 or more. Other alkylene polyamines may also be used e.g. imino bis propylamine; polymerization products of ethylene imine and a mixture of isomeric polyethylene hexamines and related hexamines containing piperazine rings and 12 C atoms. In the examples polyisobutenyl succinic anhydride is prepared either (i) by refluxing polyisobutylene with maleic anhydride and di-t-butyl peroxide in toluene, distilling off toluene, treating with hexane and then distilling off the hexane or (ii) refluxing polyisobutylene with maleic anhydride and then treating with hexane. The products are reacted with reaction products of dicyandiamide and triethylene tetramine, diethylene triamine, tetraethylene pentamine, pentaethylene hexamine and imino bis propylamine.
本发明描述了可用作分散剂的多接枝低分子量聚合物的组合物和制备。所描述的分散剂适用于控制油泥和漆膜以及烟炱。产品可用作润滑剂添加剂和燃料添加剂。
Lubricating oil, gasoline and fuel oil additives are products obtained by reacting 1 equivalent of a hydrocarbon-substituted succinic acid producing compound having at least 50 aliphatic carbon atoms in the substituent with at least 0.5 equivalent of an alkylene amine of the formula where n is an integer preferably less than 10, A is H or a substantially hydrocarbon radical preferably having up to 30 C atoms, and the alkylene radical is preferably a lower alkylene radical of less than 8 C atoms, cyclic derivatives thereof such as piperazines, pyrimidine, and imidazolines, or alkylene amines having one or more hydroxyalkyl substituents on the nitrogen atoms, and at least 0.1 equivalent of an alkenyl or aryl-substituted alkenyl cyanide. Cyanides specified are acrylonitrile and methacrylonitrile; 1-butyl-, 1-hexyl-, 1-cyclohexyl-, 1-t-butyl-and 1-isopropyl-vinyl cyanide; crotonitrile; 2 - dodecyl -, 2,21 - didodecyl -, 2-cyclopentyl -, 2 - octyl - 2 - methyl -, 2 - decyl-2 - hexyl -, and 2 - t - pentyl - vinyl cyanide; 3 - hexenyl - and 2 - octenyl - cyanide; and 1-phenyl-, 2-phenyl-, 1-tolyl-, and 2-phenethylvinyl cyanide. Higher homologues of the alkylene amines or hydroxyalkyl substituted alkylene amines obtained by condensation through amino or hydroxy radicals may be employed. The hydrocarbon radical may be derived from a polyolefin, such as a polymer of e.g. ethylene, 1-butene, isobutene, 2-butene, 1-octene, 4-octene, 2-methyl-1-heptene, 3-cyclohexyl - 1 - butene, 3 - pentene, or a copolymer e.g. of isobutene/styrene, isobutene/butadiene, propene/isoprene, ethylene/piperylene, isobutene/chloroprene, 1 - hexene/1,3 - hexadiene, or isobutene/styrene/piperylene, or may be derived from high molecular weight white oils or synthetic alkanes obtained by hydrogenating high molecular weight polyolefines or olefinic substances. More than one succinic group can be attached to a single substantially hydrocarbon radical. In Example 1, polyisobutene-substituted succinic anhydride, tetraethylene pentamine, crotonitrile, and mineral oil are mixed and heated at 100-200 DEG C. for 7 hours. Example 2 reacts a mixture of diethylene triamine and triethylene tetramine, and acrylonitrile first, and then reacts with the substituted succinic anhydride. Example 9 reacts the substituted succinic anhydride with an ethylene amine mixture having an average composition corresponding to tetraethylene pentamine and then reacts the product in oil with acrylonitrile. Example 13 reacts ethylene diamine, 2,2-dimethylvinyl cyanide, and polypropene-substituted succinic anhydride in oil. Example 14 uses polyethylene-substituted succinic anhydride. Example 17 first reacts 1-methyl-2-dodecylvinyl cyanide and octamethylene diamine, and then reacts with an isobutene/ piperylene copolymer substituted succinic anhydride in oil. The products may be added in amounts from 0.1-10% by weight to gasolines, to hydraulic fluids, and to burner fuel, cutting and lubricating oils, including synthetic oils such as didodecyl adipate and di-2-octyl sebacate. The products impart oxidation- and corrosion-inhibiting and detergent properties to oils. A test lubricant contains mineral oil, polyacrylic acid ester V.I. improver, polyacrylic acid ester pour-point depressant, zinc dialkylphosphorodithioate, and the product of the invention. Ash-containing detergents such as the Na, K, Li, Ca, Mg, Sr and Ba salts of sulphonic, carboxylic and organic phosphorus acids containing at least one direct C-to-P linkage, e.g. a phosphorized polyolefine, may be present and may have been prepared using a promoter (many specified). Polyamines acylated with high molecular weight hydrocarbon-substituted succinic acid or anhydride may also be present. Other additives are chlorinated wax, organic sulphides and polysulphides (many specified), phosphosulphurized hydrocarbons, phosphorus esters such as phosphites (many specified), zinc dioctyl and barium heptylphenyl dithiocarbamates; and Group II metal phosphorodithioates (many specified). In examples: (I) S.A.E. 20 oil contains 0.5% of the product of Example 1; (II) S.A.E. 30 oil contains 0.75% of the product of Example 2 and the Ba salt of di-n-nonylphosphorodithioic acid; (III) S.A.E. 30 oil, a product according to the invention, the zinc salt of a mixture of diisopropylphosphorodithioic and di - n - decylphosphorodithioic acids, and the product obtained by carbonating at 150 DEG C. mineral oil, barium didodecylbenzenesulphonate and barium hydroxide in the presence of water and octylphenol; (IV) S.A.E. 10W-30 oil, a product according to the invention, zinc di-n-octylphosphorodithioate, and the steam-hydrolyzed reaction product of polyisobutene with P2S5; and (V) S.A.E. 20 oil, the product of Example 1, the reaction product of polyisobutene-substituted succinic anhydride and an ethylene amine mixture having an average composition corresponding to tetraethylene pentamine, and zinc dioctylphosphorodithioate.ALSO:A nitrogen-containing composition is obtained by reacting 1 equivalent of a hydrocarbon-substituted succinic acid-producing compound having at least 50 aliphatic carbon atoms in the hydrocarbon substituent with at least 0.5 equivalents of an alkylene amine or a hydroxyalkyl substituted alkylene amine and at least 0.1 equivalents of an alkenyl or aryl-substituted alkenyl cyanide. The alkylene amines have the general formula where n is an integer preferably less than 10, A is hydrogen or a substantially hydrocarbon radical preferably having up to 30 carbon atoms, and the alkylene radical is preferably a lower alkylene radical having less than 8 carbon atoms. Cyclic and higher homologues of such amines such as piperazines may also be used. The substantially hydrocarbon-substituted succinic acid producing compounds include succinic acids, anhydrides, halides and esters and they may be derived from homo- or co-polymers of olefines having 2 to 30 C atoms (e.g. ethylene, 1-butene, isobutene, 2-butene, 1-octene, 4-octene, 3 - cyclohexyl - 1 - butene, propene/isoprene, ethylene/piperylene, isobutene/chloroprene, 1 - hexene/1,3 - hexadiene, and isobutene/styrene/piperylene) by heating the polymer or copolymer with maleic anhydride at 100 DEG -200 DEG C. More than one succinic group can be attached to a single substantially hydrocarbon radical, and the hydrocarbon radical may also be derived from high molecular weight white oils or synthetic alkanes obtained by hydrogenating high molecular weight polyolefines or olefinic substances. The alkenyl cyanides are preferably vinyl cyanides having the general formula where R1 and R2 are H or hydrocarbon radicals. Alternatively, the cyanide group may be separated from the olefinic group by one or more methylene radicals. Preferably the alkylene amine is reacted with the alkenyl cyanide and the product then reacted with the succinic reactant. Numerous examples are given, and the products are used as lubricating oil additives.
-
Mannich condensation products prepared by the condensationof a compound having the formula: Image (A)wherein R is hydrogen, lower alkyl having 1 through 6carbon atoms, hydroxy or lower alkoxy having 1 through6 atoms; R1 is polyalkyl having an average molecularweight of about from 400 to 5000 and n is 0 or a wholeinteger of from 1 through 10with ammonia, alkylamine, polyamine and an aldehyde. The condensation products and their fuel-soluble salts areuseful as fuel additives for the prevention and control ofengine deposits.
