PL89819B1 - - Google Patents

Description

The subject of the invention is a method for the preparation of an additive to lubricating oils, preventing the formation of deposits, especially used for synthetic lubricating oils, and constituting a nitrogen-containing product, which product dissolves in synthetic lubricants, such as polyglycols, esters of their mixtures, etc. The method according to the invention is particularly suitable for oils used in internal combustion engines. It is known that the phenomenon of water or sediment accumulation occurs most often when the engine is operated alternatively at high and low temperatures, especially in winter and with short and repetitive driving runs. One of the major problems with the use of conventional automotive engine lubricants is the presence of foreign particles inside (combustion residues, sediment, water, lead compounds, etc.). The presence of water and substances causing deposits depends largely on the operating temperature of the lubricant. The main object of the invention is to eliminate the above drawbacks by developing a method for producing a product that effectively disperses the deposits formed. at least one dicarboxylic acid is used in which one of the two acid groups is esterified with an epoxy polymer or epoxy copolymer, while the other is converted into an amide or amidine group by reaction with ammonia, aliphatic aromatic amines, heterocyclic or linear or cyclic amines Polamines • Dicarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, maleic and fumaric acids, malic acid, citraconic acid, mesaconic acid, itaconic acid , acid muconic, hydro-muconic acid, phthalic acid, terephthalic acid, etc, as amines are methylamine, N-methylethylamine, N-methyloctylamine, dibutylamine, 2 89819 cyclohexylamine, aniline, di-p-methylphenylamine, dodecylamine, octadecylamine, o-phenylenediamine, N, N-di-n-butyl-p-phenylenediamine. morpholine, indole, hexahydro-1,3,5-triazine, melamine, cyclohexamine, pyrrolidine, ethanolamine, diethanolamine, etc. Preferably polyamines are used as the source of nitrogen-containing groups, especially alkylene amines such as trimethyleneamines, tetromethyleneamines , heptamethyleneamines, etc., and cyclic amines, as well as higher homologues of the above-mentioned amines. Other sources of nitrogen-containing groups are ureas, thioureas, hydrazines, guanidines, amidines, amides, thioamides and cyanamides. The nitrogen group in the product produced according to the invention is characterized by in that the nitrogen atom is linked directly to the carboxyl group of the esterified dicarboxylic acid. Such a bond can be of the amide, amidine or salt type. The method of the invention gives in most cases a product which is a mixture of compounds with different types of bonds. The mutual ratios of these bonds are unknown, as they depend largely on the nature of the nitrogen-containing group and on the reaction conditions, e.g. temperature. lower than 70 ° C, the bond of the salt type of formula 1 will prevail. At a relatively higher temperature, e.g. higher than 80 ° C, the amide or amkJine type bonds of the formulas 2 or 3 will prevail. According to the invention, irrespective of the type and quantity ratio of the binding therein, it has an effective effect as an additive to synthetic oils and fulfills the objectives of the invention. anti-sludge in synthetic lubricating oils, therefore cannot be considered as limiting the scope of the inventory because they are illustrative only. Example 1 A polyethylene glycol monoester with an average molecular weight of 1000 is reacted with maleic anhydride in a molar ratio of 1: 1 to give a maleic acid semester with a hydroxyl number of 50 mg KOH / g. The reactions are carried out by stirring the reactants for 6 hours under nitrogen at a temperature of 90-100 ° C. One mole of semesteramine is added to one mole of triethylenetetramine and heated for 2 hours at 85-95 ° C and then for 4 hours at 170-180 ° C, while bubbling nitrogen through the mixture. After removing all the water, the product is drained off. Example II. A polypropylene glycol monoester with an average molecular weight of 2500 is reacted with succinic anhydride in a weight ratio of 1: 1 to give a succinic acid semester with a hydroxyl number of 22 mg KOH / g. The reactions are carried out by stirring the reactants under nitrogen for 8 hours at a temperature of 120 ° C. Then, to 1 mole of semester, 2 moles of tetraethylene pentamine are added and the mixture is heated for 1 hour at 100-110 ° C and for the next 6 hours at 170-180 ° C, while nitrogen bubbles are bubbled through the mixture. After all water has been removed, the product is drained. Example III. A polyglycol copolymer with a ratio of ethylene oxide to propylene oxide of 9: 4, non-etherified, with an average molecular weight of 1800, is reacted with an anhydride in a weight ratio of 1: 2 to obtain a phthalic acid semester with a hydroxyl value of 50 mg KOH / g. The reactions are carried out by stirring the reactants under nitrogen for 10 hours at a temperature of 90-100 ° C. Two moles of cyclohexylamine are added to one mole of semiester and the mixture is heated for 2 hours at 70-80 ° G and for a further 8 hours at 170-190 ° C, while nitrogen bubbles are bubbled through the mixture. After removing all the water, the product is drained off. Example IV. The product according to the invention is assessed as a dispersant and anti-deposit additive to synthetic lubricating oils in a Fiat 600 D engine start and stop test. diesel fuel moving on roads within cities. It is basically based on an assessment of the amount of sediment that is formed during the tests, which accumulates on the centrifugal filter of the engine. This test is based on the operation of the Fiat 600 D engine according to the cycle presented in Table I. 89819 Speed I rpm 1200 ± 100 800 ± 100 l 2500 ± 50 4000 ± 50 Water Inlet 3 & 80-85 Temperature ° C Outlet ± 5 ± 2 ± 2 90 ± 4 Oil Outlet ± 2 ± 2 ± 2 80 ± 4 Tablical Test cycle Fuel consumption kg / hr. 0.592 0.740 3.404 3.552, 032, 328 "Air ratio benzane * - 12/1 13/1 14/1 / 1 14/1 / 1 Pressure Kg / cm * 2-3 2-3 2-3.5 2-3, 5 Time in minutes 55 120 120; i The engine was stopped and the water and oil were cooled rapidly to 25 ° C. (Viscosity at 100 ° = 31.9 cSt Number of test cycles 9 18 27 \ 36 Polyglycol 12.0 24.0 36.5 56.6 Polyglycol + Anti-oxidant A 12.0, 1 26.0 34.5 Polyglycol + antioxidant A + 2% of the product produced in example 1.0 8.1 12.5 16.8 Polyglycol + antioxidant A + 2% of the product produced in example II 2.5, 4 9.2 11 , 9 Polyglycol [+ antioxidant A + 1.5% of the product - f prepared in example III 8.2 14.0 18.5 26.0 1 Table III Tests with ester (Viscosity at 100 ° C = 29, 08 cSt) number of test cycles 9 18 27 36 Ester 62.5 Sediment accumulated in ph centrifugal filter (g) Ester + antioxidant B 45 89 Ester + antioxidant B + 2% of the product prepared in example I 9.7 16.0 23.5 27.3 Ester + antioxidant of the product prepared in example II.0 14.2 , 1 26.5 Ester + antioxidant B + 1.5% of the product prepared in example III 26.1 49.2 PL EN

Claims (5)

1. Claims 1. A method for the preparation of a nitrogen-containing product for lubricating oils, characterized in that in at least one dicarboxylic acid, one of the two acid groups is esterified with an epoxy polymer or an epoxy copolymer, and then the other is converted into the group of amide or amidine by reaction with ammonia, aliphatic-aromatic amines, heterocyclic amines, or linear or cyclic polyamines. 2. The method according to p. The process of claim 1, wherein the epoxy compounds are ethylene oxide, propylene oxide or butylene oxide. 3. The method according to p. 4. A process according to claim 1, characterized in that the dicarboxylic acid is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, maleic acid, fumaric acid, malic acid, citraconic acid, mesaconic acid. , itaconic acid, muconic acid, hydromuconic acid, phthalic acid, or terephthalic acid. 4. The method according to p. A method according to claim 1, characterized in that the amine is methylamine, N-methylethylamine, N-methyloctylamine, dibutylamine, cyclohexylamine aniline, di-p-methylphenylamine dodecylamine, octadecylamine, o-phenylenediamine, N, N-di-n- butyl-p-phenylenediamine, morpholine, indole, hexahydro-1,3,5-triazine, melamine cyclohexamine, pyrrolidine or ethanolamine. 5. The method according to p. The method of claim 1, characterized in that the amines are trimethyleneamines, tetramethyleneamines, hexamethyleneamines, sevenethyleneamines, cyclic and liberal homologues of these amines, ureas, thioureas, hydrazines, guanidines, amidines, amides, thioamides or cyanamides. o II (-) tt (^ C-0) HN (- Pattern 1 0 II (-CN () Pattern N- II (-C -N () Pattern 3 Printing works UP PRL circulation 120 + 18 Price PLN 10 PL PL