SE445465B - PROCEDURE FOR PREPARING A LUBRIC OIL ADDITION BY REACTION OF AN AMINO ACID WITH A METAL COMPOUND AND OIL CONCENTRATE OR OIL CONTAINING THE ADDITIVE - Google Patents

Description

15 20 25 j0 35 I: 0 7910414-7 -2- the ash requirements of the motors being lubricated are not exceeded.

The preparation of conventional additives, which are overbased for obtaining additional acid neutralizing plants, is taught in US-PS 5,126 BUU. The additive described in this patent is prepared by treating a sulfonate dispersant for lubricating oil with an alkaline earth metal oxide and hydroxide and then introducing carbon dioxide and ammonia into the mixture, followed by heating the mixture in the presence of water to convert the ammonium carbate, which formed from carbon dioxide and ammonia, to a alkaline earth metal carbonate. The alkaline earth metal carbonate is the acid neutralizing part of the composition.

U.S. Pat. contains an alkaline earth oxide.

After the catalytic amount of ammonium carbamate is preformed, carbon dioxide is continuously introduced into the reaction mixture, until substantially all of the alkaline earth metal oxide has been converted to the alkaline earth metal carbonate. The metallic carbonate provides the reserve quality of the sulfonate. As a post-treatment step, water is added to the reaction mixture. The addition of water decomposes all the ammonium carbamate still present in the reaction mixture.

US-PS U OBH 037 teaches the preparation of metal carboxylates or N-organic substituted carbamates by reacting a carboxylic acid or carbon dioxide with an amine in the presence of a soluble metal salt. These salts are described as being useful as lubricating oil additives.

The preparation of some alkali and alkaline earth metal salts of N-carboxyamino acids in aqueous and alcoholic systems is known to those skilled in the art. See, for example, the various articles by M. Siegfrid (Z. Physiol. Chem., Ïï, 85 (l905); ÄÉ, H01 (l906); 5U, H36 (l908 », which describe the preparation of barium and calcium salts of N- The mercury salts of N-carboxyamino acids are described in C. Neuberg and J. Kerb, Biochemische Z. gg) H98 (1912).

The sodium salt of N-carboxiglycine is described in A.C. Farthing, J.

Chem. soc. igig, 3213.

A process is now described and claimed for the preparation of a lubricating oil additive, which consists in contacting an alpha-amino acid under the reaction conditions with a basic reacting metal compound. wherein the contacting takes place in the presence of at least one suspending agent for the basic reacting metal compound and in the presence of a hydroxyl-containing promoter. Also apply for patent oil lubricant concentrate and lubricating oil, which contains the additive.

The essential components necessary to generate the metal (Group I and Group II) salts by the process of the present invention are an alpha amino acid, a basic reacting metal compound, a suspending agent for the basic reacting metal compound, and a reaction promoting amount of a hydroxyl-containing promoter.

The Amino Acid The nitrogen portion of the alpha amino acid serves as a source of non-ash-forming basic material in the lubricating oil additives of the present invention. By "amino acid" is meant any organic acid which contains at least one primary, secondary or tertiary amine - (- N ()) group and at least one acidic carboxyl (-COOH) group Mixtures of different amino acids may be used.

The amino acid portion of the final product metal salt will usually have a molecular weight of less than 200 and preferably in the range of from 75 to 160.

Representative amino acids useful in the present invention include: glycine, alanine, valine, leucine, isoleucine, phenylalanine, serine, threonine, tyrosine, methionine, 6-amino-hexanoic acid, tryptophan, histidine, lysine, hydroxylysine, arginine, aspartic acid, asparagine, glutamic acid, glutamine, cysteine, cystine, aminoethylcysteine, iminodiacetic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid.

Particularly suitable are the amino acids which are readily available in commercial quantities, such as glycine, nitrilotriacetic acid, etc.

Numerous methods for producing amino acids are well known to those skilled in the art, and the amino acids of the present invention can be prepared in situ, if desired. For example, glycine can be prepared from the well-known reaction of ammonia, formaldehyde and sodium cyanide, as taught, for example, in U.S. Pat. No. 2,663,713.

The nitrogen portion of the amino acid serves as a source of non-ash-forming basic material in the lubricating oil additives of the present invention. The alkaline reacting metallic compound The alkaline reacting metallic compound is any metallic compound which reacts under basic conditions, i.e. at a pH greater than 7.0 to form a salt of an organic acid. Typical such metallic compounds are calcium oxide, hydroxide, or methoxide, barium oxide or hydroxide, aluminum hydroxide, sodium hydroxide, lithium hydroxide, sodium alkoxide and the like. Useful alkoxides are low molecular weight alkoxides, such as methoxide, ethoxide, t-butoxide and the like. Suitably the oxide or hydroxide of a Group II metal or the hydroxide of a Group I metal is used.

Suitable lubricating oil additives are prepared from magnesium, barium and calcium oxides or hydroxides, although sodium hydroxide is often desirable in some applications. Most suitable for use in lubricating oil additives are the compositions prepared from calcium or magnesium - containing basic reacting compounds, especially calcium oxide, calcium hydroxide, magnesium oxide or magnesium hydroxide.

The Suspending Agent The suspending agent, which must be oil soluble, is used to keep the alkaline reacting metallic component in solution so that it can be an effective part of the additive composition. Many of the useful suspending agents also have a dispersing effect in the final lubricating oil additive composition. Typical suspending agents include alkali metal or alkaline earth metal hydrocarbyl sulfonates or fatty acid carboxylates, hydrocarbyl succinimides, hydrocarbyl succinates, hydrocarbyl succinic anhydrides, alkali metal or alkaline earth metal alkyl phenol alkenes and mannan alkyl phenyl phenols and earth alkyl. Mixtures of suspending agents are also useful in carrying out the process of the present invention.

The alkali metal and alkaline earth metal hydrocarbyl sulfonates useful in the process of the present invention are well known to those skilled in the art; The hydrocarbyl group must have a sufficient number of carbon atoms to make the sulfonate molecule oil-soluble.

The hydrocarbyl moiety usually has at least 20 carbon atoms and may be aromatic or aliphatic, but is usually alkyl aromatic. Some sulfonates are typically prepared by sulfonating a petroleum fraction with aromatic groups, usually mono- or dialkylbenzene groups, and then forming the metal salt of the sulfonic acid material. Other feed materials used to prepare these sulfonates include synthetically alkylated benzenes and aliphatic hydrocarbons prepared by polymerizing a mono- or diolefin, e.g., a polyisobutenyl group. , prepared by polymerizing isobutylene. The metallic salts are formed directly or by metathes using well known techniques.

Succinimide dispersants are also well known to those skilled in the art and a general method for their preparation is found in U.S. Pat. Nos. 3,219,666, 23,172,892 and 3,272,7U6. These compositions are prepared by attaching an oil-soluble alkyl or alkenyl succinic acid or anhydride to react with a nitrogen-containing compound. The succinimide may be of the type commonly known as a mono- or bis-succinimide. Suitable nitrogen compounds used in the manufacture of the succinimides are those known as the ethyleneamines, and especially suitable are triethylenetetramine and tetraethylenepentamine.

The suitable alkyl or alkenyl groups contain from 50 to 300 carbon atoms and the most suitable compositions are prepared from polyisobutylene. When this type of suspending agent is used, the amine moiety will contribute to the alkalinity value.

The oil-soluble alkyl or alkenyl succinic anhydrides used in the preparation of the succinimides are themselves useful as suspending agents; however, they are most suitable for use as co-suspending agents, especially in combination with a sulfonate suspending agent. Suitably the alkyl or alkenyl moiety contains from 50 to 300 carbon atoms.

The succinate esters are prepared by reacting an alcohol with an alkenyl or alkyl succinic anhydride described above using a procedure such as that described in U.S. Patent Nos. 5,381,022 and 3,522,179. Typically, the alkyl or alkenyl group contains from 50 to 300 carbon atoms.

Alkali metal and alkaline earth metal phenolates are well known to those skilled in the art and are the alkali metal or alkaline earth metal salt of an oil-soluble alkyl substituted phenol. The composition may be treated with sulfur. Typical phenolates are prepared by neutralizing a C8-28 alkylphenol with calcium hydroxide or oxide.

Mannich bases are useful suspending agents. Mannich bases are prepared by reacting an oil-soluble phenolic or alcoholic material, such as alkylphenol, with an aldehyde, such as formaldehyde or acetaldehyde, e.g. a nitrogen-containing compound. Typical Mannich bases contain from about 8 to 128 or more carbon atoms in the alkyl group. Optionally, the phenolic alkaline earth metal salt of the Mannich base can be used as a suspending agent.

Reaction promoter A reaction-promoting amount of a hydroxyl-containing promoter is necessary for the reaction to proceed at an acceptable rate. Typically, from 0.1 to 10% by weight or more of the reaction mixture may be the hydroxyl-containing promoter. The promoter is believed to act as a solubilizer for the alkaline reacting metal compound. The promoter is suitably water or an alcohol having 1 to 6 carbon atoms or an alkanediol having 2 to 6 carbon atoms, such as methanol, ethanol, isopropanol, butanol, ethylene glycol, 1,1-butanediol and the like. Most suitable are water, ethanol and methanol. Mixtures of these promoters can also be used, selected "so that water formed during the reaction is retained in the solution.

Calcogenic reactant Although not an essential reactant, it is convenient that the reaction take place in the presence of a calcogenic compound. Suitable chalcogenic compounds include carbon dioxide, carbon disulfide, carbon monoxide sulfide, sulfur dioxide or mixtures thereof. While the calcogenic reactant is usually added in gaseous form, it may be added in liquid or solid form, for example as dry ice or liquid sulfur dioxide. Carbon dioxide_is the appropriate calcogenic reactant. When a calcogenic reactant is used, the amino acid must contain a primary or secondary amino group. The calcogenic compound is a suitable reactant, as it increases the alkalinity value of the lubricating oil additives by incorporating more of the alkaline reacting metallic compound.

Solvent The reaction is carried out in a suitable solvent. Suitably the solvent is a lubricating oil, so that no removal of the solvent is necessary, before incorporating the additive into the lubricating oil. Other useful solvents are low boiling hydrocarbon solvents such as hexane or hydrocarbon diluents. Mixtures of lubricating oil with hexane or hydrocarbon diluent are also useful. After the preparation is completed, the low-boiling solvents are easily removed by heating, if desired.

Reaction Conditions The process of the present 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 at a temperature of from 0 to 75%, preferably from 20 to 75% and most preferably from 25 to 50 ° C. while the reaction proceeds satisfactorily at atmospheric pressure, higher or lower pressures may be used, if desired.

The ratio of the basic reacting metallic compound to the limestone and the amino acid is such that from about 1/10 to 3 / H of the alkalinity value of the final composition is contributed by the ashless amino-containing material. It is suitably desirable to have at least one equivalent of the basic reacting metallic compound for each equivalent of the amino compound. The ratio will vary depending on the structure of the amino acid used and the amount of alkalinity value desired from the ashless nitrogen portion of the amino acid. For a single amino acid (glycine), at least two equivalents of metallic compound per mole of amino acid are usually used, while for a more complex amino acid (glutamic acid, lysine, nitrilotriacetic acid) usually at least three equivalents are used, although fewer equivalents may be used, if a higher proportion of ashless alkalinity value is desired. Under typical conditions and based on 1 equivalent of the basic reacting metal compound, the reaction mixture would contain from 0.1 to 2.0, preferably from 0.3 to 0.5 equivalents of the amino compound; from O-1, suitably 0.3-0.5 equivalents of chalcogenic compound; and from 2 to 20, preferably H to 10, parts by weight of the suspending agent per part of the basic reacting metallic compound. The hydrocarbon solvent should be present in sufficient quantity to allow good mixing of the reactants and is usually present in from 5 to 50 and preferably 10 to 25 ml per g of basic reacting metallic compound. From 0 to 5, preferably 1 to 2, ml of the promoter per gram of alkaline reacting metallic compound is also used.

In a suitable method of carrying out the reaction, a sodium, calcium or magnesium alkyl benzene sulfonate was used as the suspending agent. It is also convenient to use an alkenyl succinimide or an alkenyl succinic anhydride as co-suspending agent. If this combination of solubilizing agent is used, an increased alkalinity value of the product is obtained, when before adding the amino compound and the basic reacting material, preferably an alkaline earth metal oxide or hydroxide, the mixture of components and the solvent is pretreated with a small amount of chalcogen, e.g. With from 1 to 10%, preferably about 5%, of the total amount of calcium.

Lubricant Compositions The lubricant compositions prepared in accordance with the present invention provide a high alkalinity value at a lower ash content than that present in most conventional dispersants and / or acid neutralizing agents used as lubricating oil additives.

The alkalinity value is a method of indicating the degree of overbasicity of the lubricating oil composition. It is also a measure of the acid-neutralizing properties of the composition. The method of determining the alkalinity value commonly used for a composition is described in ASTM Method D-2896. Briefly, the alkalinity value is the total base number given as mg of potassium hydroxide per gram of sample. It is the quantity of potassium hydroxide needed to neutralize the same amount of perchloric acid that 1 g of the sample neutralizes. For example, if a composition has the same acid-neutralizing capacity per g as 10 mg of potassium hydroxide, the composition is given an alkalinity value of 10.

The lower limit of the alkalinity value is 0 for a neutral composition. Values of 200 or more are particularly desirable for use in lubricants which are exposed to the decomposition products of sulfur-containing diesel fuels. Typical alkalinity values for additive compositions of the present invention range from about 30 to 400 or more.

Lubricant compositions containing the additives of the present invention are prepared by mixing by conventional mixing methods the appropriate amount of the additive of the present invention with a lubricating oil. the choice of a special base oil depends on the intended use of the lubricant and on the presence of other additives. Generally, the amount of additive of the present invention used in the lubricating oil will range from 0.1 to H0% by weight and preferably from 2 to 35% by weight. The lubricating oil obtained will usually have an alkalinity value in the range from 1 to 120, preferably 2.5 to 100.

The lubricating oil that can be used in the present invention comprises a wide variety of hydrocarbon oils, such as naphthenic bases, paraffin bases and mixed base oils. The lubricating oils can be used individually or in combination and usually have a viscosity ranging from 50 to 5,000 SUS (Saybolt Universal Seconds) and usually from 100 to 1,500 SUS at 3800. 100 g "7910414-7 I In many cases it may be advantageous to form a concentrate of the additives of the present invention in a carrier liquid.

These concentrates provide a convenient method of handling and transporting the additives of the present invention, prior to their subsequent dilution and use. The concentration of the additives of the present invention within the concentrates may vary from 85 to 10% by weight, although it is convenient to maintain the concentration between about 15% and HO% by weight. The suitable method of obtaining concentrate is to carry out the preparation of the additive in a limited amount of lubricating oil, which will be used in the manufacture of the final diluted lubricating composition. Alternatively, the additive can be prepared in a low boiling hydrocarbon, which is removed by distillation after the addition of a limited amount of lubricating oil.

When desired, the second additive may be included in the lubricating oil compositions of the present invention. These additives include antioxidants or. oxidation inhibitors, dispersants, rust inhibitors, anticorrosives and so on. Other types of lubricating oil additives that can be used include defoamers, stabilizers, anti-stain agents, tackifiers, anti-vibration agents, drip point improvers, anti-knock agents, extreme pressure agents, air-controlling agents and the like.

It has surprisingly been found that the magnesium salts of N-carboxyamino acids are stable in the presence of water at elevated temperatures. This is particularly surprising and unexpected in view of the fact that calcium, barium, strontium and sodium amino acid carbamates are not stable in water. This property is especially useful because water at elevated temperatures comes in contact with lubricating oils during the operation of an internal explosion engine.

The magnesium salts of N-carboxyamino acids have many uses, especially as lubricating oil additives as previously described, chelating agents, as food preservatives and as household detergents, etc.

The suitable magnesium compounds of the present invention may be formed from the reaction of carbon dioxide with a basic reacting magnesium compound and an amino acid of structural formula I below. The suitable products are the magnesium salts of N-carboxyamino acid, which are represented by the structural formula II, below. 7910414-7 / R R5 f R R -X; C c -.-- c coon I \. S '= c \ Ita? I ål \ m N \\ n 145 H f -s' I É * f _ f. - [x) \ c c- + 5: -'- coo fi Il S Ä a? wherein R, R, H5, R 1 to 20 carbon atoms, a carboxyalkyl group having 2 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, an aryl having E to 10 carbon atoms , an aminoalkyl group having 1 to 20 carbon atoms and having hydrogen or alkyl having 1 to 6 carbon atoms on the nitrogen atom, or an aminocarboxyalkyl group having 2 to 20 carbon atoms, and R independently represents hydrogen, an alkyl of B1 and R2 may be joined directly or through an atom O, S or N to form a 5 or 6 membered ring; R 3 represents hydrogen, an alkyl having 1 to 20 carbon atoms, an aryl having 6 to 12 carbon atoms, an alkaryl having 7 to 20 carbon atoms, an aralkyl having 7 to 20 carbon atoms, a carboxyalkyl having 2 to 20 carbon atoms, a hydroxyalkyl having 2 to 20 carbon atoms, an aminoalkyl having 2 to 20 carbon atoms, a polyaminoalkyl having till to 20 carbon atoms and 2 to 10 amino groups; n denotes 0 to 6, m denotes 0 to 6, s denotes 0 or 1; R 5 and R 5 may be joined to form a 5- or 6-membered heterocyclic ring having from 0 to 1 additional heteroatoms, consisting of 0, S, NR, wherein R represents an alkyl group having 1 to 6 carbon atoms. atoms, \ Y | R5 and R6 may be joined directly or with an atom 0, S or N to form a 5- or 6-membered ring.

X represents a linking diradical, which consists of -O-, -S-, -SS-,% CH 2 ep, wherein p represents 1 to 6 and _ 11 _. = NR R 8 represents hydrogen, an alkyl having 1 to 20 carbon atoms, a hydroxyalkyl having 1 to 20 carbon atoms, an aryl having 6 to 12 carbon atoms, an alkaryl having 7 to 20 carbon atoms, an aralkyl having 7 to 20 carbon atoms, an aminoalkyl having 1 to 20 carbon atoms, a carboxyalkyl having 2 to 20 carbon atoms , a carboxy group, an amino group having 0.1 or 2 substituents, defined as for nš, and wherein X does not represent phenyl, R 8 may have the same structure as that attached to the opposite end of the -X linking group.

The appropriate magnesium N-carboxyamino acid salts are conveniently prepared by reacting the corresponding amino acid with a basic reacting magnesium-containing compound and carbon dioxide in the presence of a suspending agent for the basic reacting magnesium compound and in the presence of a reaction-promoting compound. the amount of a hydroxyl-containing promoter. For the preparation of the appropriate magnesium salts, the amino acid may be any organic acid which contains at least one basic amino (-NH) group and at least one acidic carboxyl - (- COOH) group. Particularly suitable are the glycine and the alpha-amino acids. Mixtures of different amino acids can be used. Other suitable reaction conditions for this suitable embodiment of the present invention comprise, based on 1 equivalent of the basic reacting magnesium compound, from 0.5 to 1.5 equivalents of the amino compound; from 1.5 to 2.5 equivalents of carbon dioxide; and from H to 10 parts by weight of the suspending agent per part of the basic reacting magnesium compound.

The appropriate N-carboxyamino acid salts can also be prepared by reacting the basic reacting magnesium compound, the amino acid and carbon dioxide in water or mixtures of water and other hydroxyl-containing solvent. The resulting solution of the N-carboxyamino acid magnesium salt can be dispersed by means of a dispersant in the desired hydrocarbon solution and the water is then removed -u-øw-U. uv 10 15 20 25 30 35 H0 _ 12 _ 7910414-7 by dehydration to form a dispersion of the salt or the aqueous solution obtained can be evaporated to dryness, the solid obtained is ground to a finely divided state and dispersed by means of the dispersant in the desired hydrocarbon agent. .

Examples The following examples are presented to illustrate the present invention and are not to be construed as limiting the scope of the present invention in any way.

Example 1 To a 1 liter 3-necked flask is added 180 g of a 67% concentrate of a calcium alkylated aromatic sulfonate in hydrocarbon diluent, 400 ml of a hydrocarbon diluent, 10.3 g (0.25 mol) of magnesium oxide (Maglite). A ", Merck, 200 m 2 (g), 18.8 g (0.25 mol) of glycine and 10.0 ml of water. The mixture was stirred at room temperature and warmed to 0 ° C and then 3 g of carbon dioxide was added over a 25 minute period at a temperature from H0 to U5 ° C. Then 10 ml of 10% ethanol was added and 2 g of carbon dioxide were added over a 20 minute period at temperatures ranging from H5 to 55 ° C. An additional 5 ml of 100% ethanol was added and a further 8 g of carbon dioxide were added over a period of 76 minutes at 5500. The reaction mixture was then centrifuged for 20 minutes at 12,000 rpm and then filtered through a pad of diatomaceous earth.The filtrate was freed from volatility at 11000 at 2 .66 kPa The mixture yielded 1H2 g of product with a t alkalinity value of 189.8 and contained 3.22% magnesium, 1.33% calcium and 1.2U% nitrogen.

Example 2 To a 5 liter, 3-necked flask was added 670 g of a 67% concentrate of a calcium alkylated aromatic sulfonate in hydrocarbon diluent, 2330 g of a hydrocarbon diluent, H7 ml of water, 75 ml of 95% ethanol, 50, 5 g of magnesium oxide and 90.0 g of glycine.

The mixture was stirred and heated to 4000. 56 g of carbon dioxide were added over 2 hours and 15 minutes, while the temperature ranged from 38 to 4700. The reaction mixture was filtered through a pad of diatomaceous earth. The filtrate was freed from volatility at 110 ° C and 266 kPa. The mixture gave in yield 826 g of product with an alkalinity value of 203.6 and containing 3.08% magnesium, 1.38% calcium and 1.39% nitrogen.

Example 3 To a 1 liter 3-necked flask was added 150 g of a 67% concentrate of a calcium alkylated aromatic sulfonate in hydrocarbon, H 50 ml of a hydrocarbon diluent, 20 ml of methanol, 10 ml of water, 37.5 g of glycine (0.5 mol) and 20.6 g of magnesium oxide. The mixture was stirred and heated to 5 ° C and 25 g of carbon dioxide was added over 5 hours and 13 minutes, while the temperature ranged from 35 ° C to 48 ° C. The reaction mixture was filtered through a pad of diatomaceous earth. The filtrate was freed from volatility at 110 ° C and 2.66 kPa. The mixture yielded 18U g of product with an alkalinity value of 282.4 and contained 9.9% magnesium, 1.27% calcium and 1.6% nitrogen.

Example U To a 500 ml Erlenmeyer flask was added H03 g (1.0 mol) of magnesium oxide ("Velsicol"), 60.0 g of a 67% concentrate of a calcium alkylated aromatic sulfonate in hydrocarbon diluent 200 ml of a hydrocarbon diluent, 5 ml of water and 10 ml of ethanol The mixture was then stirred and 1.2.7 g of nitrilotriacetic acid was added, the mixture was then stirred vigorously at room temperature overnight, then a small portion was centrifuged for 50 minutes at 11,000 rpm. The resulting clear supernatant had an alkalinity value of 1.08U.

Example 5 To a 500 ml Erlenmeyer flask was added H.03 g of magnesium oxide (0.1 mol) ("Velsicol"), 60.0 g of a 67% concentrate of a calcium alkylated aromatic sulfonate in hydrocarbon binder and 200 ml of a hydrocarbon diluent. The mixture was then stirred and 11.6 g (0.05 mol) of ethylenediaminetetraacetic acid were added.

The mixture was then stirred at room temperature overnight and the reaction mixture was filtered through a pad of diatomaceous earth. The clear filtrate obtained had an alkalinity value of 10.07.

Example 6 To a 5 liter, 3-necked flask was added 900 g of a 67% concentrate of a calcium alkylated aromatic sulfonate in hydrocarbon diluent, 2300 ml of a hydrocarbon diluent, 120 ml methanol, 120 ml water, 210 g ( 2.8 mol) of glycine and 153.2 g (3.8 mol) of magnesium oxide. The mixture was stirred for 5 minutes at room temperature and then 266 g of carbon dioxide and 30 ml of water were added over 8 hours with the temperature ranging from 280 to # 1 ° C.

The reaction mixture was filtered through a pad of diatomaceous earth. The filtrate was released from volatility at 115 ° C and 2.66 kPa. The mixture yielded in exchange 1,188 g of product with an alkalinity value of 332.6 .mu.l, and contained 5.98% of magnesium, 1.05% of calcium and 2.05 .mu.s of nitrogen. .

Example 7 To a 1 liter, 5-necked flask was added 160 g of a 67% concentrate of a calcium alkylated aromatic sulfonate in hydrocarbon diluent, 400 ml of a hydrocarbon diluent, 15 ml of methanol, 8.0 g (0.2 mol ) magnesium oxide and 7.9 g of ammonium bicarbonate. Then slowly over a 10 minute period 9.8 g (0.2 mol) of sodium cyanide and 16.2 g of a 37% formaldehyde solution were added. The mixture was warmed to HO OC and stirred for 3 l / h.

Then 2 ml of 37% formaldehyde and 1 ml of water were added and the mixture was stirred for another 95 minutes. Then 11 g of carbon dioxide were added over a period of 66 minutes at temperatures ranging from 50 to 55 ° C. The reaction mixture was released from volatile to 150 ° C (bottom), 55 ° C (overhead). The product was filtered through a pad of diatomaceous earth. The filtrate was freed from volatility at 110 ° C and 2.66 kPa. The reaction mixture gave in yield 182 g of product with an alkalinity value of 120.0 and which contained 1.41% magnesium, 1.12% calcium, 1.27% nitrogen and 1.60% sodium.

Example 8 To a 2 liter, 5-necked flask was added 37.5 g (0.5 mol) of glycine and 1,000 ml of water. The resulting solution was cooled to 15 ° C and purged with a total of 283 g (6.4 moles) of carbon dioxide over a 3 hour period.

During this time, a total of 20.9 g (0.52 mol) of magnesium oxide was added to the mixture in several portions. The resulting clear solution was allowed to stand at room temperature overnight, then filtered to give 106.3 g of filtrate, which had an alkalinity value of 70.9 (57% yield).

A portion (H1.9 g) of the filtrate was evaporated to dryness to yield white solids, which had an alkalinity value of 100l, , 56 ß Calculated for c H Noumgz fi zo ß c 20.3 z H 3.95,% N 7.90, ß r / Ig 13.7; alkali value 9H9.

Example 9 To a 250 ml Erlenmeyer flask was added 7.9 g (0.1 mol) of ammonium bicarbonate, 2.01 g (0.05 mol) of magnesium oxide, 100 ml of distilled water, 0.9 g (0, 1 mol) sodium cyanide. The mixture was stirred and 8.1 g (0.1 mol) of a 37% solution of formaldehyde was added dropwise over 2 minutes. The mixture was stirred and allowed to stand overnight. Then an additional 50 ml of water and 2.0 g of magnesium oxide were added while bubbling carbon dioxide through the mixture. A total of 11.5 Å of H The mixture was filtered and the filtrate was evaporated to near dryness on a hot plate. A crude product of magnesium glycine carbamate was obtained (11.52 g) with an alkalinity value of 69 DEG and containing 6.2% of magnesium, 885 ppm of calcium, 1.7% of sodium and 15 DEG to 9.8% of nitrogen.

Example 10 In each of three 50-ml beakers was placed 20 ml of distilled water. In beaker No. 1 were placed 50 mg of magnesium oxide and 60 mg of glycine.

In beaker No. 2, 50 mg of magnesium oxide was placed. In cup no. 3, 50 mg of magnesium oxide and 60 mg of glycine were placed. The mixtures in all the nags were stirred. Carbon dioxide was added to beaker No. 1 GCI * - the reading was almost complete after 0.5 hours. No carbon dioxide was added to beaker No. 2 and the solids were still suspended after 1 hour.

Carbon dioxide was then added to beaker No. 2 for 0.5 hours with no apparent difference in the suspended solids. There was no change in beaker No. 3 after 0.5 hours of stirring and then carbon dioxide was added and all the magnesium oxide was dissolved after 0.5 hours to give a clear solution.

From the above was drawn the final stone, that the reaction of magnesium oxide was greatly favored by glycine. Thus, the magnesium glycine reaction product was refluxed on a hot plate and did not surprisingly form a precipitate.

Claims (13)

7910414-7 -16- Batentkrav 1. A process for the preparation of a lubricating oil additive, characterized in that an alpha-amino acid is brought into contact with a basic reactive metal compound under the reaction conditions, the contacting taking place in the presence of at least one suspending agent for the basic reacting material and in the presence of a hydroxyl-containing promoter. 2. A process according to claim 1, characterized in that the amino acid is an alpha-amino acid, optionally having 1 to 5 hydroxyl groups, preferably glycine. 3. A composition according to claim 1, characterized in that the benzene-purified metal compound is a metal hydroxide with counterpart from group 1 or a metal oxide or hydroxide with mctzlllcll frazi gxwlpp II. 4. A process according to claim 1, characterized in that the suspending agent is an alkali metal or alkaline earth metal hydrocarbyl sulfone, a hydrocarbyl succinimide, a hydrocarbyl succinate, a hydrocarbyl succinic anhydride, an alkali metal alkene metal alkene alkene alkene metal base or alkaline earth metal a Mannich base, or mixtures thereof. 5. A process according to claim 4, characterized in that the suspending agent is an alkali metal or alkaline earth metal hydrocarbyl sulfone, a hydrocarbyl succinimide or a hydrocarbyl succinic anhydride or mixtures thereof. Process according to Claim 1, 2, 3, 4 or 5, characterized in that the amino group contains a primary or secondary amino group and in that the contacting takes place in the presence of carbon dioxide, carbon disulfide, coloxy sulphide or sulfur dioxide. 7. A method according to claim 6, characterized in that the contact ringing takes place in the presence of carbon dioxide. 8. A process according to claim 1, characterized in that the hydroxyl-containing promoter is water, methanol, ethanol or mixtures thereof. 9. A process according to claim 1, characterized in that the amino acid is produced in situ. 10. A process according to claim 9, characterized in that the amino acid is glycine and is prepared in situ from the reaction of ammonia, formaldehyde and sodium or potassium cyanide. 11. ll. Process for the preparation of a lubricating oil additive, characterized in that it is subjected to reaction- GÉSD-J \ f- ~ .- r.- ...... ß fi ci *. .Liz-Z xur-Ax; 7910414-7 conditions an alpha-amino acid, consisting of glycine, alpha-alanine, cystine, methionine or lysine, in contact with a basic reacting metal compound consisting of calcium oxide or hydroxide, magnesium oxide or hydroxide, lithium or sodium hydroxide, the contacting taking place in the presence of at least one suspending agent for the basic reacting compound, at least one calcogenic compound consisting of carbon dioxide, carbon disulfide, carbon monoxide or sulfur dioxide, and in the presence of a promoted amount of a hydroxyl-containing promoter. 12. l2. Process according to claim 11, characterized in that the amino acid is glycine, the basic reacting metal compound is calcium hydroxide or magnesium oxide and the calcone is carbon dioxide. 13. Lubricating oil concentrate and lubricating oil, known from the fact that the concentrate resp. the lubricating oil comprises an oil with a lubricity viscosity and from 90 to 40% by weight resp. from 0.1 to 40% by weight of a product prepared according to the process of claims 1-12.