SE445464B - PROCEDURE FOR THE PREPARATION OF A LUBRICAN OIL ADDITIVE CONTAINING A NITROGEN METAL SALT AND OIL CONCENTRATE OR OIL COMPOSITION CONTAINING THE ADDITIVE - Google Patents

Description

7910374-3 2 is formed in the initial stage leus carbon dioxide continuously in the reaction mixture until virtually all the oxide of the alkaline earth metal is converted to carbonate.

The net carbon carbonate is responsible for a reserve of the alkalinity in the sulfonate. As a final step in the process, water is added to the reaction mixture. The addition of water decomposes any remaining ammonium carbamate in the reaction mixture.

U.S. Patent Specification No. 4,034,037 teaches the preparation of metal carboxylates or N-organic substituted carbamates by reaction between a carboxylic acid or carbon dioxide with an amine in the presence of a soluble metal salt. These salts are shown to be of value as lubricating oil additives.

Katcnalski 331, J. Am. Chem soc. 1_5_, 1829-1831 (1951), describes the preparation of calcium methylenedicarbamate.

U.S. Patent Specification No. 2,957,826 and 5,056,820 disclose the use of carbamate salts as gelling agents in greases.

The practice of the invention provides a process for the preparation of lubricating oil additives, characterized by the step of bringing together in a solvent at a suitable reaction temperature the following substances: (a) at least one ash-free nitrogen-containing compound selected from the group consisting of ammonia, ammonium salts and organic compounds containing only carbon, hydrogen and nitrogen and having at least one NH group, (b) a metal compound having an alkaline reaction, (c) at least one suspending agent for component (b) and (d) a chalcogen compound selected from carbon dioxide, carbon disulfide, carbon monoxide sulfide and sulfur dioxide or mixtures thereof, in such a way that the ratios of the reactants (a), (b), (c) and (d) are such that approx. 1/5 - 3 / N of the alkalinity value of the additive composition derives from the ash-free part of said composition. 7910374-3 ßasxnïvzqxnc m? FURFARANDE; Component (a) - Ash-Free Nitrogen-Compound The nitrogen-containing portion of component (a) serves as a source of non-ash-forming basic material in the lubricating oil additive of this invention. "Ash-free" means a substance which, after vigorous heating, does not have a non-volatile residue. This ash-free nitrogenous substance may be ammonia, an ammonium salt (such as ammonium bicarbonate, ammonium acetate, ammonium carbonate and the like) or an organic compound containing only carbon, hydrogen and nitrogen atoms and having at least one NH group Mixtures of different nitrogen-containing compounds can also be used.The nitrogen compounds are generally selected from the readily available aliphatic amines, polyamines or ammonia.

The ash-free nitrogen-containing compounds preferred in this reaction are ammonia, ammonium bicarbonate, aliphatic monoamines having up to 50 carbon atoms in the aliphatic moiety, and aliphatic polyamines such as methylenediamine, polymethylene polyamines, ethyleneamines and propyleneamines.

Aliphatic monoamines include methylamine, ethylamine, propylamine, (di) octylamine, decylamine, coconut oil and tallow amines, eicosylamine and the like. The amine can be obtained from natural or synthetic sources through methodologies well known in the art.

The preferred monoamines are C1-20 alkylamines and especially C1-4 alkyl monoamines, especially methylamine.

Polymethylene polyamines are prepared from ammonia and formaldehyde and have a general repetitive structure H2N (CH2NH) x, H, where x 'is 1-20. Compounds with x 'in the range 1-6 are preferred.

Ethyleneamines are well known amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, triethylenepentamine, pentaethylenehexamine and the like, which are usually prepared by the reaction of enalkylenedichloroacionic ammonia or from ethyleneamine and ammonia. This reaction produces a complex mixture of alkyleneamines comprising certain cyclic condensation products. The reaction products are generally known in the industry as ethyleneamines as described above. k Propylenamines are a class of polyamines which are produced by reacting acrylonitrile with an ethyleneamine, e.g. those described above and which have the formula H2N (CH2Cn2Aß) x "ü_ with x" equal to 1-5, followed by hydrogenation of the resulting intermediate. For example, the products of ethylene diamine and acrylonitrile would be H21! (CI-Iz) 3NIHZ ) ZNH (CH 2) BNI-Iz.

The preferred amines in this invention are methylamine, ammonia and ethyleneamines. The most desirable amine from a cost point of view is ammonia. The most preferred amine based on action is ethylenediamine.

Component (b) - metal compound The alkaline reacting metal compound component (b) is such a metal compound which reacts as a base, i.e. with a pH greater than 7, and forms a salt with an organic acid. Typical such compounds are the oxide, hydroxide or methoxide of calcium or magnesium, barium oxide or hydroxide, aluminum, sodium or lithium hydroxide and some sodium alkoxide. Useful alkoxides are those of low formula weight such as methoxide, ethoxide, t-butoxide and the like. Preferred is an oxide or a hydroxide of the group 2 metals or an alkali metal hydroxide.

The preferred additives to lubricating oil are prepared from magnesium, barium and calcium oxides or hydroxides, but sodium hydroxide is often desirable in certain applications. For use in lubricating oil additives, compositions prepared from a Lasian substance containing calcium, in particular calcium oxide and calcium hydroxide, are preferably used.

Component (C) - Suspending amino agent The suspending agent, component (c), which must be soluble in oil, is used to keep component (b) - the alkaline reacting metal component - ~ in solution so that it can form an effective proportion of the additive composition. ning. Many of the useful suspending agents also have a dispersing effect in the final composition of the lubricating oil additive. Typical suspending agents include alkali or alkaline earth metal hydrocarbyl sulfonates, hydrocarbyl succinimides, hydrocarbyl succinates or corresponding acid anhydrides, alkali or alkaline earth metal alkyl phenolates, Mannich alkyl phenolic alkaline base mannach alkaline earth metal alkalis.

Mixtures of suspending agents are also of value for carrying out the process of this invention.

Hydrocarbyl sulfonates of alkali and alkaline earth metals useful in the process of this invention are well known in the art. The hydrocarbon group must have a sufficient number of carbon atoms to make the sulfonate molecule oil-soluble. The hydrocarbon moiety usually has at least 20 carbon atoms and can be aromatic or aliphatic, but it is usually alkyl aromatic. Some sulfonates are typically prepared by sulfonating a petroleum fraction with aromatic groups, usually mono * or dialkylbenzene groups, after which the corresponding metal salt of the sulfonic acid is formed. Other starting materials for the preparation of the sulfonates include synthetically alkylated benzene compounds and aliphatic hydrocarbons prepared by polymerizing 4-mono- or diolefin, e.g. a polyisobutenyl group prepared from isobutylene by polymerization. The metal salts are formed directly or by metathesis, where the procedures are well known. Succinimide dispersants are also well known in the art, and a general method for treating them is set forth in U-5,327,892 and 3,272,746 Patent Specification Nos.3,219,666. , These compositions which are hereby referred to for details. 7910374-36 is prepared by reacting an oil-soluble alkyl or alkenyl succinic acid or anhydride with a nitrogen-containing substance.

The succinimide formed may be of the type commonly known as mono- or bissuccinimide. The nitrogen compounds preferred in this reaction are those known under the name ethyleneamines, with triethylenetetramine and tetraethylpentamine being particularly preferred. Preferably the alkyl or alkenyl groups should contain 50-300 carbon atoms and the most commonly used compositions are prepared from polyisobutylene. When this type of suspending agent is used, the amine moiety in the molecule contributes to the alkalinity value.

The oil-soluble alkyl or alkenyl succinic anhydrides used to synthesize the succinimides are themselves useful as suspending agents. However, they are more trusted as co-suspending agents; especially iko fi binatibn with a sulfonate-type suspending agent. The alkyl or alkenyl moiety is recommended to contain between 50 and 300 carbon atoms.

The succinic ester esters are prepared by reacting an alcohol with an alkenyl or alkyl succinic anhydride as above using a procedure of the type found in U.S. Pat. Patent Specifications Nos. 3,381, 022 and 3,522,127, to which reference is hereby made for details. Usually the alkyl or alkenyl group contains 50-300 carbon atoms.

'Alkali' or alkaline earth metal phenolates are well known in the industry and constitute alkali or alkaline earth metal salts of an oil-soluble alkyl-substituted phenol. It may be sulfurized. Typical phenolates are prepared by neutralizing C8-12 alkylphenol with calcium hydroxide or oxide.

Mannich bases are important suspending agents. They are prepared by reacting an oil-soluble phenol or alcohol (such as alkylphenol) with an aldehyde (such as formaldehyde or acetaldehyde) and a nitrogen-containing compound. Typical Mannich bases contain 8-128 (or more) carbon atoms in the alkyl group. If desired, the phenolic alkaline earth metal salt of a Mannich base can be used as a suspending agent. Preparation of the mixture The reaction for methodology number one of this invention is carried out by adding a reactant selected from carbon dioxide, carbon disulfide, carbon monoxide or sulfur dioxide or mixtures thereof to the reaction mixture of components (a), (b) and ( C). While said reactant is usually added in gaseous form, it can be added in liquid or solid form such as dry ice or liquid sulfur dioxide. Carbon dioxide is the preferred reactant.

The reaction takes place in a suitable solvent.

Preferably, this is a lubricating oil so that it is not necessary to remove the solvent before incorporating the additive with the lubricating oil. Other useful solvents are otherwise low-boiling hydrocarbons such as hexanes or petroleum ether. Mixtures between oil and any of these are also possible. After the reaction is complete, the low boiling hydrocarbons are easily removed by heating if desired.

Promoter In a preferred embodiment of the invention, a promoter is added. This probably acts as a solubility enhancer for the basic reacting compound and retains water formed in solution during the reaction. The promoter is preferably an alkanol having 1-6 carbon atoms or an alkanediol having 2-6 carbon atoms such as netanol, ethanol, isopropanol, butanol, ethylene glycol, 1,4-butanediol and the like. Ethanol is preferred.

Since the usability of the product is adversely affected by water, the process is preferably carried out under anhydrous conditions. If the basic reacting metal compound is such that water is formed in the reaction of this invention, a sufficient amount of promoter must be used to keep this water in solution. Water that comes out of solution leads to gel formation and the irreversible formation of metal carbonate, which prevents effective filtration. The process of this invention can be carried out at any temperature from the freezing point of the mixture to its boiling point. The reaction is usually carried out in a temperature range of -75 ° C, more preferably 20-75 ° C and most preferably 25-50 ° C. However, when component (a) is ammonia, initial temperatures as low as cza -10 ° C are used. While the reaction proceeds satisfactorily at atmospheric pressure, higher or lower pressures may be applied if desired.

The mutual proportions of suspending agent, carbon dioxide and the nitrogen-containing material are adjusted so that from 1/3 to 3/4 of the alkalinity value compared to the final composition is obtained from the ash-free nitrogen-containing products. It is desirable to have about one equivalent of nitrogen-containing compound per equivalent of the alkali-reacting metal compound. Under typical conditions and based on one equivalent of basic metal compound, the reaction mixture would contain 0.3-2.0 (preferably 0.5-1.5) equivalents of nitrogen compound, 1-3 (preferably 1.5-2.5) equivalents of nitrogen compound. chalkogenic compound and 2-20 (preferably 4-10) parts by weight of suspending agent per part of basic metal compound. The solvent in the form of a hydrocarbon would be present in sufficient quantity to allow good mixing of the reactants and this usually means 5-50 (preferably 10-25) ml per gram of basic metal compound. In addition, the promoter uses 0-5 (preferably 1-2) ml per basic metal compound.

In the method preferably used to carry out the reaction, a sodium, calcium or magnesium alkylbenzenesulfonate is used as the suspending agent. Usually, an alkenyl succinimide or an alkenyl succinic anhydride is used as an auxiliary substance to increase the solubility. if this combination of solubility promoters is used, an increased alkalinity value of the product is obtained if the mixture is pretreated before the addition of component (a) - the nitrogen compound - and the basic reacting component (b) (preferably an oxide or hydroxide of an alkaline earth metal). 7910574-3 component (b) and the solvent with a small amount of component (d), for example with 1-10% (preferably about 5%) of the total amount of component (d).

The carbamates preferred by formulas I, II and III are those where M = Ba, Mg or Ca. The latter two are particularly represented. * According to formulas I, II and III, R is an aliphatic hydrocarbon group having 1-50 carbon atoms. For those groups where the carbon chain has at least 3 carbon atoms, it may be straight or branched and may contain one or more sites with unsaturated olefin or acetylene type bonds. Most commonly represented are straight or branched chain alkyl radicals having 1 to 20 carbon atoms such as methyl, ethyl, propyl, decyl and octyl or those which can be derived from tallow or carbon atoms. The most common are alkyl radicals having 1 to 4 carbon atoms. R 'represents hydrogen or an aliphatic hydrocarbon group as defined for R. However, R' and R 'need not be identical hydrocarbon groups. Preferably, carbamates are used where R 'is a hydrogen atom. As far as compositions III are concerned, dc preferably consists of derivatives from ethylene amines and propylene amines, i.e. those for which x is 2 or 3 and z is 0-4. The amines for the production of desacarbamates are well known.

Typical dispersants that may come in handy to keep the carbamate in solution. includes hydrocarbyl physulfonates of alkali or alkaline earth metals, hydrocarbyl succinic anhydrides, alkylphenolates of said metals, alkylphenol-type Mannich bases and alkaline earth metal salts of such Mannich bases. Mixtures of suspending agents are also of value in the art of the process of this invention.

If the carbamate is to be prepared in §¿Ep_pix a mixture of ammonia or the amine in question, a dispersant as described above, an oxide or the like. hydroxide of an alkali or alkaline earth metal and a C1_6 promoter. Carbon dioxide or carbon disulfide is added to form carbamate and thiocarbamate, respectively. This process should be performed in an anhydrous environment. The carbamate which is aliphatic amine based, when prepared as above, can be dispersed into a liquid non-gelled lubricating oil, and since water has an adverse effect, the process is carried out under anhydrous conditions. If it is the alkaline reacting metal compound that generates water as a result of the reaction of the invention, a sufficient amount of promoter should be used to keep the water in solution. Water without solution leads to gel formation and the irreversible formation of meta-carbonate which prevents effective filtration.

The compositions of the components of the present invention act to provide a high alkalinity at a lower ash content than that found in most conventional dispersants and / or acid neutralizers used as lubricating oil additives.

The alkalinity value is a method of specifying the degree of excess base in the lubricating oil composition. It is also a measure of the acid neutralizing properties of this. The method of predetermining the alkalinity value commonly used for such a compilation is set forth in ASTM Method D-2896. Briefly, the alkalinity value is the total base number given in mg of potassium hydroxide per gram of sample. This is the quantity of potassium hydroxide required to neutralize. the same amount of perchloric acid that I acid neutralize. For example, the composition is given the alkalinity value 10 if it has the same acid neutralizing ability per gram as lexmgfkaliium hydroxide. A lower limit on the alkalinity value of Q applies to a neutral composition. Values of 200 or more are particularly desirable for use in lubricants that are exposed to decomposition products from sulfur-containing diesel fuels. Typical alkalinity values for additive compositions of this invention range from up to 300 to 400 or more.

Lubricating oil compositions containing additives of this invention are prepared by mixing the appropriate amount of additives of this invention with a lubricating oil by conventional mixing techniques. The selection of a particular base oil depends on the intended area of use and on the presence of other additives. In general, the amount of additives varies according to this invention between 0.1 and 40% by weight based on the lubricating oil and should preferably be in the range of 2-35% by weight. The resulting lubricating oil mixture will then exhibit an alkalinity value in the range 1-120, usually 2.5-100.

The oils that can be used in this invention include a wide variety of hydrocarbon-based oils such as naphthenic bases, paraffin bases, and blend bases. The lubricating oils can be used individually or in combination and generally have a viscosity ranging from 50 to 5000 SUS (Saybolt Universal Seconds) and usually from 50 to 1500 SUS at 38 ° C.

In many cases it may be advantageous to form concentrates of additives according to this invention in a carrier liquid. These concentrates provide a convenient method of handling and transporting these additives prior to their subsequent dilution and use. The concentration of the additives in this invention may in the concentrates vary from 40-90% by weight but a concentration of 50-70 is preferred. The method recommended for obtaining the concentrates is to carry out the preparation of additive in a limited amount of the lubricating oil to be used in the final dilute oil composition. Alternatively, the additive can be prepared in a low boiling hydrocarbon which is removed by distillation after a limited addition of lubricating oil.

Other additives may be added at will to the lubricating oil compositions of this invention. These additives include antioxidants or oxidation inhibitors, dispersants, rust inhibitors, anti-corrosive agents, etc. Other types of additives to the oil which may be considered are antifoams, stabilizers, anti-staining agents, tackifiers, anti-knock agents, droplet improvers, anti-pressure agents, anti-crackers, odor control agents, etc. 791Û574'3 12 ISXLIÉPIJL The following examples serve to illustrate this invention and may in no way be construed as limiting the scope of the invention. Example 1 A 5-liter 3-necked flask was charged with 700 g of 67% concentrate of a calcium alkyl alkyl aryl sulfonate in petroleum ether, 350 g of a polyisobutenyl succinimide prepared from a polyisobutenyl succinic anhydride having an average molecular weight of the 57 lubricating oil and which contained 2.13% nitrogen, 200ml petroleum ether and 140ml 95% ethanol. The mixture was stirred at room temperature for 10 minutes after which 29-carbon dioxide was added over a 35-minute period at a temperature of 25-28 ° C. Then, methylethylenediamine and 180.5 g of calcium hydroxide were added to the mixture. An additional 206 g of carbon dioxide was added over a period of 2 hours 17 minutes at a temperature of zs-32 ° C. The silica gel is added to the mixture which is then filtered through a pad of diatomaceous earth. The filtrate was evaporated heated (pulled off) at 25 inches Hg vacuum. Then 250 g of lubricating oil were added and this product was evaporated heated: 111.1 ° C via 40 mm ng pressure. The sianemingem gave 1441 g 'of proauke msà an alkali value of 329.4 containing 6.21% calcium and 4.47% nitrogen. Example 2 To an S-liter 3-necked flask was added 440 g of the calcium sulfonate described in Example 1, 2000 ml of petroleum ether and 92 ml of methanol. This mixture was stirred and 73.2 g of ethylenediamine and 68.4 g of calcium oxide were added. To this mixture was added 101 g of carbon dioxide for a period of 1 hour 4 minutes at a temperature of 35-50 ° C. The product was evaporated to 115 ° C at atmospheric pressure, and 250 ml of petroleum ether and 40 g of kieselguhr were added. The mixture was filtered through auxiliary filters and the filtrate was evaporated after adding 500 g of neutral lubricating oil to 10 ° C at 20 mm high pressure to give a yield of 865 g of product as 52% concentrate in oil with an alkalinity value of 184 , 6 and which contained 3.55% calcium and 2.43% nitrogen.

Example 3 To a 1 liter 3-necked flask was added 110 g of calcium sulfonate (as in Example 1), 200 ml of petroleum ether and 25 ml of methanol. With stirring, 18.3 g of ethylenediamine and 1.7 g of calcium oxide were added. This mixture was heated to 50 ° C after which 26 g of carbon dioxide were introduced for 1 hour. The mixture was evaporated to 75 ° C at atmospheric pressure and then 5 ml of water were added. The product formed a particle. After the addition of 15 ml of water, the gel decomposed. The mixture was heated to 75 ° C and 10 g of diatomaceous earth was added, after which it was filtered through diatomaceous earth and then evaporated to 90 ° C at 20 mm Hg pressure. The yield was 63 products with an alkalinity value of 404.3 and containing 4.76% nitrogen and 28.54, 28.75% sulphate ash.

Example 4 To a 2 liter 3-necked flask were added 184 g of calcium sulfonate (see Example 1), 420 g of petroleum ether and 23 ml of methanol. The mixture was stirred and to it were added 9.3 g of ethylenediamine and 33.9 g of calcium hydroxide. The mixture was heated to 45 ° C after which 29 g of carbon dioxide were introduced at a temperature of 45-48 ° C. The product evaporation heat temperature 132; 132 ° C under atmospheric pressure. The product was then filtered through kieselguhr and evaporated to 160 ° C at atmospheric pressure and then to 204 ° C at 20 mm Hg pressure; which gave a yield of 133 g of product. Its alkalinity value was 275.1 and contained 29.52. suifa bag and 1.72 nitrogen.

Example 5 A 5-liter 3-necked flask was charged with 700 g of calcium sulfonate (see Example 1), 350 g of succinimide (see Example 1), 2100 ml of petroleum ether and 140 ml of 95% ethanol. The reaction mixture was stirred at room temperature for 10 minutes after which 6 g of carbon dioxide were introduced at 25 ° C over a period of 28 minutes. The mixture was added with 140 g of ethylenediamine and 180.5 g of calcium hydroxide. To this mixture was added 203 g of carbon dioxide over a period of 2 hours 20 minutes at a temperature of 32 ° C. The product was evaporated to 10 ° C and 50 g of kieselguhr were added. The product was filtered through kieselguhr and then 250 g of 100 neutral lubricating oil were added. The mixture was evaporated to 110 DEG C. at a pressure of 20 mm Hg to give a yield of 1316 g of preauk: with a power line ratio of 299.5 units with nitrogen and calcium contents of 3.7%, respectively. 6.54%. The alkalinity value measured according to ASTM Method D-664 was 327.

Example gel 6 To a 5-liter 3-necked flask was added 440 g of calcium sulfonate (see Example 1), 2000 ml of petroleum ether and 150 ml of isopropyl alcohol. The mixture was stirred and to it were added 73.2 g of ethylenediamine and 68.4 g of calcium oxide. Then, 99 g of kelaiexia was introduced at as -47 ° c for 1 μm 1 min. The product was evaporated to 115 ° C (bottoms) and 60 g of kieselguhr were added. The mixture was allowed to cool with stirring and then filtered through diatomaceous earth. The filtrate was treated with 40 g diatomaceous earth and filtered again through diatomaceous earth. To this filtrate was added 400 g of 100 neutral lubricating oil and the mixture was evaporated to 95 ° C at 20 mm Hg pressure.

The synthesis gave 819 g of product as a 49% concentrate in oil and with an alkalinity value of 207. It contained 3.66% calcium and 2.89% nitrogen.

Example 7 An S-liter 3-necked flask was charged with 560 g of calcium sulfonate (see Example 1), 280 g of polyisobutenyl succinic anhydride where the polyisenebuenyl group had an average molecular weight of 1050 (cf. Example 1), 140 g of ethylenediamine and 2100 ml of petroleum ether. The mixture was stirred for 15 minutes at room temperature after which 140 ml of ethanol and 169 g of calcium hydroxide were added. 188 g of carbon dioxide were introduced into this mixture for 2 hours 12 minutes at 25-38 ° C. The mixture was evaporated to 150 ° C and added with 50 g of kieselguhr. The mixture was cooled to 40 ° C with stirring and then filtered through kieselguhr. The product was evaporated heated to 110 ° C at 40 mm Hg pressure to give 938 g of product whose alkalinity value was 374.3 and containing 4.20% nitrogen and 27.34% sulphate ash. The alkalinity value according to ASTM Method D-664 was 407. Example 1 To a 1 liter 3-necked flask was added 150 g of calcium sulfonate (see Example 1), 30 g of succinimide (see Example 1), 350 ml of petroleum ether, ml 95% ethanol and 22.6 g calcium hydroxide.

The reaction mixture was cooled to 5 ° C and 20 g of monomethylamine was added. A dry ice cooler was placed on the reaction flask to avoid loss of methylamine during the addition, the reaction system was flooded with nitrogen prior to carbonation and then 26 g of carbon dioxide was added at 17-2s ° C for 5 minutes. The product was centrifuged (11,000 r.p.m.). The solids which separated were rinsed with mixed nexanes, centrifuged and dried in a vacuum oven. The alkalinity value of the solids was 1008.4.

Example 9 To a 1 liter 3-necked flask was added 90 g of sodium sulfonate prepared by sulfonating a 60% (w / w) petroleum fraction and 40% (w / w) synthetic alkylbenzene 300 ml of petroleum ether, 15 ml of 100% ethanol, 9.2 g 98% ethylenediamine and 12.0 g of sodium hydroxide. The reaction mixture was fed with 139 carbon dioxide at 25-30 ° C for 1 hour 6 minutes. The mixture was evaporated to 115 ° C (bottoms), cooled to room temperature and then 15 g of kieselguhr were added. The mixture was filtered through kieselguhr, and the filtrate was evaporated to a heat of evaporation: iii 110 ° C at 15 mm ng pressure. yields were 82 g of product with an alkalinity value of 30.6, a hatr¿umha1¿ of 2.87¿ and a nitrogen content of 0.28% 7910374-3 16 egg rape 1 lo To a 5-liter 3-necked flask was added 880 g of calcium sulphonate (see Example 1), 2000 ml of petroleum ether, 140 ml of 95% ethanol, 140 g of 98% ethylenediamine and 118.5 g of aluminum hydroxide. To this mixture was added 101 g of carbon dioxide at the temperature of 25-35 ° C for 1 hour 15 minutes, after which 84 g of calcium hydroxide were added. The mixture was evaporated to 115 ° C and the product was centrifuged (11,000 r.p m.) For 30 minutes. The mixture was filtered through kieselguhr and the filtrate was heated to 115 ° C at 20 mm Hg pressure to give 579 g of product having an alkalinity value of 61.7% and containing 0.0002% aluminum, 0.1361% calcium and 1.88% nitrogen. EXAMPLE 11 A 1 liter 3-necked flask was charged with 1918 g of sodium bicarbonate, 1 ml of water, 20 ml of methanol, 10.3 g of magnesium oxide, 1709 sulfonate (see Example 1) and 400 ml of petrol eumeter. This mixture was stirred and 15.3 g of ethylenediamine was added. To this mixture was added at the temperature of about 3 ° C 23 g of carbon dioxide for a period of possibly 3 hours. ßieooningeo was evaporated to 115 ° C (bottoms). Diatomaceous earth was added, filtered, centrifuged (30 minutes at 11,000 rpm) and filtered again through diatomaceous earth. The filtrate was evaporated heated to 115-120 ° C at 4 mm Hg pressure to give a yield of 159 g of product with an alkalinity value of 208.

Example 12 120 g of calcium sulfonate (see Example 1), 600 ml of petroleum meter, S0ml of ethanol, 80 g of succinimide (see Example 1) and 22.6 g of calcium hydroxide were combined in a 2-liter 3-necked flask. The reaction mixture was cooled to 55 ° C. Ammonia gas was let in at a flow rate of 50 ml / min for 43 minutes. During the last 28 minutes of this time, 28 g of carbon dioxide were introduced at the same time. As the gases were supplied, the temperature I rose from -s ° c eiii zs ° c. The reaction mixture was then evaporated and heated to 115 ° C (bottoms) at atmospheric pressure, cooled to 25 ° C and then 25 g of kieselguhr were added. The product was filtered through kieselguhr, and the filtrate was evaporated to 110 ° C at 20 mm Hg pressure. The yield was 166 g of product with an alkalinity value of 144.8 and containing 4.82% calcium and 1.00% nitrogen.

Example 13 A 2-liter a-liter flask is charged with 250 g of calcium sulfonate (see Example 1) and 600 ml of petroleum ether. With stirring, 50 ml of liquid ammonia and 38 g of carbon dioxide were introduced into this mixture at room temperature. The reaction mixture was kept at 25 ° C throughout the reaction. To this mixture was added 40 ml of methanol and 25.2 g of calcium oxide, and stirring was first carried out at room temperature, after which the mixture was heated to 45 ° C and 100 ml of methanol was added. The product was evaporated to 130 ° C (bottoms), centrifuged for 30 minutes at 11,000 r.p.m. and evaporated again at 95 ° C at 20 mm Hg pressure to give 147 g of product. Its alkalinity value was 53.3 with levels of 9.74% sulphate ash and 0.43% nitrogen.

Example 14 To a 2-liter 3-necked flask was added 160 g of calcium sulfonate (see Example 1) and 420 ml of petroleum ether. This mixture was stirred while 17 ml of liquid ammonia and 28 g of carbon dioxide were introduced at room temperature. The temperature of the mixture was maintained throughout at 25 ° C during the reaction.

Then 40 ml of methanol and 25.29 g of calcium oxide were added. This mixture was stirred at room temperature, then warmed to 45 ° C with the addition of 100 ml of methanol. The product was evaporated to 130 ° C (bottoms), centrifuged for 30 minutes (11,000 r.p.m.) and then evaporated to 95 ° C at 20 mm Hg pressure. 147 g of product were formed with an alkalinity value of 185.3 and which contained 6.9% calcium and 0.73% nitrogen. To a 1 liter 3-necked flask were added 120 g of calcium sulfonate (see Example 1), 200 ml of hexane and 25 ml of methanol. The mixture was stirred, after which 18.3 g of ethylenediamine and 12.3 g of magnesium oxide were added. The mixture was refluxed for 1 hour at 56-58 ° C. Carbon dioxide was added at a flow of 100 ml / min at 5300 for 1 hour. The mixture was heated under reflux for 30 minutes and evaporated to 75 ° C at atmospheric pressure. While cooling to 40 ° C, 5 g of diatomaceous earth were added and the mixture was filtered through diatomaceous earth and evaporated to 80 DEG C. at 20 mm Hg pressure to give 37 g of product.

This had an alkalinity value of 101.6 and showed levels of 0.0629% magnesium, 0.4050% calcium and 3.14% nitrogen.

Example Gel 16 A 1 liter 3-necked flask was charged with 90 g of sodium sulfonate (see Example 9), 300 ml of petroleum ether, 15 ml of 100% ethanol, 9.2 g of ethylenediamine and 16.2 g of sodium methoxide.

Then 8 g of carbon dioxide were added for 1 hour 8 minutes at 30 ° C. The mixture was evaporated to 150 ° C (bottoms).

It was cooled to 40 ° C and 10 g of kieselguhr was added. After centrifugation at 11,000 r.p.m. for half an hour the mixture was filtered through kieselguhr. The filtrate was evaporated to 15 ° C at 20 mm Hg pressure. 73 g of product were obtained which had an alkalinity value of 153.3 and which contained 6.6% sodium and 1.05% nitrogen.

Example 17 To a 1 liter 3-necked flask was added 90 g of sodium sulfonate (see Example 9), 300 ml of petroleum ether, 15 ml of 100% ethanol, 9.2 g of ethylenediamine and 12.0 g of sodium hydroxide. For a period of 1 hour 44 minutes and a temperature range of 25-30 ° C, 13 g of carbon dioxide were added. The mixture was evaporated to 115 ° C (bottoms), cooled to room temperature, and then 15 g of kieselguhr was added. The mixture was filtered through kieselguhr, and the filtrate was heated to 110 ° C at 15 mm Hg pressure to give 82 g of product having an alkalinity of 30.6 and containing 0.28% nitrogen.

Example gel 18 A 5-liter 3-necked flask was charged with 880 g of calcium sulfonate (see Example 1), 280 g of succinimide (see Example 1), 2100 ml of petroleum ether and 140 ml of ethanol. 6 g of sulfur dioxide was added to this mixture at room temperature for 45 minutes. 140 g of ethylenediamine and 180.5 g of calcium hydroxide were added, after which 194 g of carbon dioxide and 21 g of sulfur dioxide were added for 2 hours and 20 minutes.

The reaction mixture was evaporated to 10 ° C (bottoms), centrifuged (30 minutes at 11000 rpm) and then filtered through kieselguhr and evaporated to 110 ° C at 20 mm Hg pressure. Then 150 g of 100 neutral lubricating oil were added to give 1035 g of product having an alkalinity value of 234.3 and having the following contents: 1.26% sulfur, 2.78, 2.75% nitrogen and 5.17% calcium.

Example 19 To an S-liter 3-necked flask was added 880 g of calcium sulfonate (see Example 1), 280 g of succinimide (see Example 1), 2100 ml of petroleum ether and 140 ml of 95% ethanol. For 35 minutes, 3 g of sulfur dioxide and 4 g of carbon dioxide were introduced. After 140 g of ethylenediamine and 180.5 g of calcium hydroxide were added, an additional 186 g of carbon dioxide and 35 g of sulfur dioxide were introduced over 2 hours 50 minutes at 30-42 ° C. The reaction mixture was evaporated heated to 115 ° C (bottoms), centrifuged for 30 mm at 11000 r.p.m. and was then filtered through kieselguhr. The filtrate was heated to evaporation: at 11 ° C at 0 mm 3: jerks and 1 g of neutral lubricating oil were added. The final product weighed 128.8 g, had an alkalinity value of 318.3 and contained 2.10% sulfur, 6.81% calcium and 3.75% nitrogen. The alkalinity value based on titration according to ASTM D-664 was 342. Example 10 560 g of calcium sulfonate (see ex. 1) / k80 g of succinic anhydride (see ex. 7), 140 g of ethylenediamine and 2100 ml of petroleum ether were mixed in an S-liter_3-necked piston. The mixture was allowed to stand for 15 minutes at room temperature after which 140 ml of 95% ethanol and 169 g of calcium hydroxide were added. Then 183 g of carbon dioxide and 10 ml of carbon disulfide were introduced for 2 hours 25 minutes at 30-35 ° C. The sample was evaporated, heated to 11 ° C, filtered through kieselguhr and the filtrate was evaporated heated to 10 ° C at 40 mm Hg pressure. but the product formed had an alkalinity value of 352.6 and contained 4.41% nitrogen, 7.72% calcium and 1.53% sulfur. Example 21 To a 5-liter 3-necked flask was added 6000 g of succinimide (see ex. 1), 2500 ml of petroleum ether and 150 mL-95% ethanol. The mixture was added and 110 g of ethylenediamine and 158 g of calcium hydroxide were added. 175 g of carbon disulfide were added over 2 hours 9 minutes at 30-38 ° C. The mixture was evaporated to 100 ° C (bottoms), centrifuged (30 minutes, 1000 rpm) and filtered through kieselguhr. The filtrate was treated with 50 g of kieselguhr and evaporated to 105 ° C at 20 mm Hg pressure. 647 g of product were formed with an alkalinity value of 385.3 and which had contents of 5.58% nitrogen and 23.19% sulphate ash.

Example gel 22 A 2-liter 3-necked flask was charged with 200 g of succinic anhydride (see Example 7) dissolved in 1000 ml of petroleum ether and 43.6 g of ethylenediamine. The mixture was heated to 100 ° C, allowed to cool to room temperature after which 48.5 g of calcium hydroxide and 50 ml of 95% ethanol were added. Then 40 g of carbon dioxide were introduced for 41 minutes at 30-45 ° C. The mixture was evaporated to 115 ° C (bottoms) and filtered through kieselguhr. The filtrate was evaporated to 105 ° C at 20 mm Hg to give 214 g of product. The alkalinity value was 344.1 and the nitrogen content was 4.85% and the calcium content 6.76%. u 791Û374 “3 Exemoel 23 To a 2-liter 3-necked flask were added 36 g of succinic anhydride (see ex. 7), 18.4 g of ethylenediamine and 500 ml of petroleum ether. This mixture was heated to 50 ° C for half an hour. It was then cooled to room temperature and 110 g of calcium sulfonate (see Example 1) were added along with 25 ml of ethanol and 22.2 g of calcium hydroxide. The mixture was stirred and 45 g of sulfur dioxide were added. An additional 200 ml of petroleum ether was added after which the product was evaporated heated to 120 ° C (bottoms).

After centrifugation, a portion of the precipitate was taken, which was treated with hexanes and allowed to stand. This portion was centrifuged at 18,000 r.p.m. for 30 min. The product was dried in a vacuum desiccator to give the following analytical values: 8.48% nitrogen and 37.0% sulphate ash.

Example 24 A 2-liter 3-necked flask was charged with 250 ml of succinimide (see Example 1) and 1000 ml of petroleum ether. The mixture was stirred and 50 ml of ethanol, 45.2 g of calcium hydroxide and 37 g of ethylenediamine were added. This mixture was stirred at room temperature and 50 g of carbon dioxide were introduced for 1.2 hours. An additional 6 g of calcium hydroxide and 3 g of carbon dioxide were added.

The temperature of the reaction mixture rose to 42 ° C during the addition of the carbon dioxide. The mixture was evaporated to 115 ° C (bottoms). The product was centrifuged at 11,000 r.p.m. for half an hour, then filtered twice through kieselguhr and evaporated to 105 ° C (bottoms) at 20 mm Hg pressure. The yield was 299 g of product which had the alkalinity value 297.1 and contained 5.22% calcium and 4.69, 4.73% nitrogen.

Exemgel 25 The compositions in the examples in Table I were tested in a Caterpillar LG-2 test in which a single-cylinder diesel engine with 13 cm bore and 16.5 cm stroke is allowed to operate under the following conditions: : 8; braking, average pressure average: 9.9 kg / cmz; braking power: 31.3 KW; thermal power: 6180 KJ / min; speed: 1800 r.p.mÄ; air pressure, absolute: 135 cm Hg; air temperature in: 107 ° C; water temperature out: 88 ° C; sulfur content in the fuel: 0.4% (weight) At the end of each 12-hour period, the crankcase is emptied of a sufficient amount of oil to allow the addition of 1.1 liters of new oil. In the oil test of this invention, the I-G test is run for 60 hours. After each 60-hour period, the engine is disassembled and assessed for purity according to the Institute of Petroleum Test No. 247/69 states as a merit system for wear and cleanliness of engines, and which has been accepted by ASTM, API and SAE as a grading system for engines. The total purity of the engine is noted as WTD, which is a summation of the above figures. Lower values represent cleaner engines.

The base oil used in the test is a Citcon 350 neutral oil containing the specified amount of additive.

Each oil was formulated to give an alkalinity value of 10. 23 7910374-3 ßwm mH.o fi. w.æHN | m.æ> H | m.o fl H mama wa.N fl m.omN | m.mH <| o.moH ßn fifl æ «.« w.mw ~ | w. fl m fi | æm.om max xuo fi muoä uwwuøw> <H AJ fl m .vwla.om | æ.æmN | o.ww o.NmH | m.æHm | o.omNlo.mw o.amH | mo.mm | o.omN | o.Nw uoawwwm JAN FN ammåmxw I:

Claims (9)

7910374-3 214 Patent claims Process for the preparation of lubricating oil additives, characterized by the step of combining in a solvent at a temperature suitable for reaction: (at least one ash-free nitrogen-containing compound selected from the group of compounds comprising ammonia and ammonium salts and organic substances containing only (l) hydrogen and nitrogen having at least one NH group, (b) an alkaline reacting compound (C) at least one suspending agent having the component: hl and (d) a calcogenic compound selected from k ~ l§1dk | d, k «ldi> nl {i¿, kd- _ loxy sulphide and sulfur dioxide ~ aml hlandnzngnr thereof, I where the ratios between the reactants (al, chi, te »ech 1 * are such that Cza l / 5-3 / J of alkallnilelsvürdel hu- tilsatßk mpe- citionen derives from the a> k-free part of said companion. 2. A process according to claim 1, characterized in that component 1a) is an aliphatic amine, a niphatic polyamine, ammonia or ammonium bicarbonate, and component 1c) is an alkali metal or alkaline earth metal hydrocarbonylsulfonylsulfonyl carbonyl sulfonyl hydroxycarbonyl , a hydrocarbyl succinic anhydride, an alkali metal or alkaline earth metal alkylphenol, a Mannich resin or an alkaline earth metal salt or a Mannich resin or mixtures thereof. 3. A process according to claim 2, characterized in that component (b) is a hydroxide of an alkali metal or an oxide or hydroxide of a Group 2 metal. A process according to claim 3, characterized in that component (c) is an alkali metal or alkaline earth metal hydrocarbyl sulfonate, a hydrocarbyl succinimide, a hydrocarbyl succinic anhydride or mixtures thereof. Process according to Claim 4, characterized in that component (a1 is ammonia, a C1-5 SO4 alipharian monoamine, methylenediamine, a polymethylene polyamine, an ethyleneamine or a propyleneamine) component (d1 is carbon dioxide, and the reaction is carried out). in the presence of a promoter which keeps any water present in solution. 6. A process according to claim 5, characterized in that component (b1 is an oxide or hydroxide of barium, calcium or magnesium, and said promoter is a C 1-6 alkanol or a C 1-4 alkanediol. 6 A process according to claim 0, characterized in that component (c1 is a hydrocurbyl sulfonate of an alkali or alkaline earth metal in combination with an alkyl or alkenyl succinimide or with an alkyl or alkenyl succinic anhydride, wherein each nx »dgdn nlkyl or alkenyl groups contain SU-Enn carbon atoms. 8. A composition according to claim 1, wherein component ahr is calcium oxide or hydroxide and said promoter is ethanol. 9. Förfurnnd: according to krnr S, k ü n n e t e C k n u t thereof, nt! component ln- is dmmunxnk, methylnmin or ethylenediamine. lll. lïlrlïnwlndc 'enlligl krnxfen 7, 8 and 9, k n n e t e c k - n n 1 thereof, that component (cl and said promoter is combined with a portion of the carbon dioxide before the addition of components (a) and lb) and nter> toden carbon dioxide. ll. Lubricating oil concentrate or lubricating oil composition, characterized in that the concentrate resp. The composition consists nx an oil of lubricating viscosity and a product, prepared according to the process of claims 1-10, of a content of 90-40% by weight and 0.1-40% by weight, respectively.