NL7909160A - METHOD FOR PREPARING A LUBRICATING ADDITIVE, AND LUBRICATING OIL PREPARATION - Google Patents

Description

N.O. 28,566

Process for preparing a lubricating oil additive, as well as a lubricating oil preparation.

The present invention relates to a process for preparing metal salts of group I or group II of amino acids, in particular the magnesium salts of N-carboxy amino acids, lubricating oil additives containing these salts, in particular overbased lubricating oil additives, on the additives themselves and to lubricating oil preparations containing the additives.

With the increasing severity of the operating conditions of the engines, partly due to the damaging quality of fuels for these engines, there is a need for compositions which can lubricate and maintain the purity of the engine while at the same time containing large amounts of acids neutralized, resulting from the use of fuels with an increased sulfur content. Conventional lubricating oil additives used to neutralize base contain ash-forming ingredients, generally metal salts. Since increasing amounts of the acid neutralizing ingredients are used in formulations, the amount of ash in the formulation often exceeds the amount of ash fairy for which the engine is designed.

New additives are required which can maintain the purity of the engine 20 and neutralize the large amounts of acid generated from the increased use of high sulfur fuel, while at the same time not exceeding the shaft requirements of the engines, which be lubricated.

The preparation of conventional additives, which are overbased to obtain additional acid neutralizing efficiency, is taught in U.S. Pat. No. 3,126,340. The additive described in this patent is prepared by treating a lubricating oil sulfonate dispersant with an alkaline earth metal oxide and hydroxide and then introducing carbon dioxide and ammonia into the mixture, followed by treating the mixture in the presence of water to form the ammonium carbamate , formed from the carbon dioxide and ammonia, to convert to an alkaline earth metal carbonate. The alkaline earth metal carbonate is the acid neutralizing part of the preparation.

U.S. Patent 3,524,814 teaches the preparation of an overbased alkaline earth metal sulfonate by introducing a mixture of carbon dioxide and ammonia in an amount of 7909160% to form a catalytic amount of ammonium carbamate, in a lubricating oil with suspension a neutral alkaline earth metal sulfonate containing an alkaline earth metal oxide. After the catalytic amount of ammonium carbamate is preformed, carbon dioxide is continuously fed into the reaction mixture until substantially all of the alkaline earth metal oxide has been converted to the alkaline earth metal carbonate. The metal carbonate provides the reserve alkalinity in the sulfonate. As a post-treatment step, water is added to the reaction mixture. The addition of water decomposes any ammonium carbamate still present in the reaction mixture.

U.S. Pat. No. 4,034,037 teaches the preparation of metal carboxylates or N-organically substituted carbamates by reacting a carboxylic acid or carbon dioxide with an amine in the presence of a soluble metal salt. Heze 15 salts are described as suitable as lubricating oil additives.

The preparation of some alkali metal and alkaline earth metal salts of N-carboxy amino acids in aqueous and alcoholic systems is known. See, for example, the various articles 20 by M. Siegfried (Z. Physiol. Chem. 44, [1905] 85 »A§.i [1906] 401; 54» [1908] 436), in which the preparation of barium and calcium salts of N-carboxy amino acids are described. The mercury salts of N-carboxyamino acids are described in C. Neuberg and J. Kerb, Biochemische Z., 40, (1912) 498. The sodium salt of N-caboxyglycine 25 is described in A. C. Farthing, J. Chem. Soc. 1950, 3213 ".

The present invention relates to a process for the preparation of a lubricating oil additive, characterized in that an amino acid and a basic reacting metal compound are contacted under reaction conditions, which contact 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. The invention also relates to the magnesium salts of N-carboxy amino acids and lubricating oil preparations, which contain the alkali metal and alkaline earth metal salt and of amino acids.

The essential ingredients necessary to prepare the Group I and Group II metal salts of the periodic table by the method of the present invention are an amino acid, a basic reacting metal compound, a suspending agent for the basic reacting metal compound and a reaction 7909160 3 promoting amount of a hydroxy group containing promoter.

The nitrogen portion of the amino acid serves as a source of supply of non-ash-forming basic material in the lubricating oil additives of the present invention. By "amino acid" is meant any organic acid containing at least one primary, secondary or tertiary amine (-N <) group and at least one acidic carboxyl (-C00H) group. Mixtures of different amino acids can be used. The amino acid portion of the metal salt end product will generally have a molecular weight of less than 200 and preferably in the range of 75 to 160.

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

Especially preferred are the amino acids, which are readily available in commercial amounts such as glycine, beta-alanine, nitrilotriacetic acid, etc. Also particularly preferred are the α or β amino acids.

Numerous methods for the preparation of amino acids are known, and the amino acids of the present invention can be prepared in situ if desired. For example, glycine can be prepared from the known reaction of ammonia, formaldehyde and sodium cyanide, as described, for example, in U.S. Patent 2,665,713.

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 basic reacting metal compound is any metal compound which reacts under basic conditions, that is, at a pH greater than 7.0, to form an organic acid salt.

Characteristic of such metal compounds are calcium oxide, hydroxide or methanolate, magnesium oxide, hydroxide or methanolate, barium oxide or hydroxide, aluminum hydroxide, sodium hydroxide, lithium hydroxide, sodium alcoholate and the like. Suitable alkoxides are the low molecular weight alkoxides such as methanolate, ethanolate, tert-butoxide and the like. Preferably 7909160. · 4 <· the oxide or hydroxide of a Group II or Group I methanol is used.

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

The suspending agent, which must be oil-soluble, is used to keep the basic reacting metal component in solution, so that it can be an active part of the additive composition. Many of the conventional suspending agents also have a dispersant in the final lubricating oil additive formulation. Common 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 phenyls, Mannich bases of the alkyl phenol. Mixtures of the suspending agents are also suitable for practicing the method of the present invention.

The alkali and alkaline earth metal hydrocarbyl sulfonates suitable for the process of the present invention are known. The hydrocarbyl group must contain a sufficient number of carbon atoms to make the sulfonate molecule soluble in oil. Ordinary ± 1/3 the hydrocarbyl portion contains at least 20 carbon atoms and may be aromatic or aliphatic. but is usually alkyl aromatic. Certain sulfonates are usually prepared by sulfonating a petroleum fraction with aromatic groups, usually mono- or dialkylbenzene groups, and then forming the metal salt of the sulfonic acid product. Other feeds used for the preparation of these sulfonates include synthetic alkylated benzenes and aliphatic hydrocarbons prepared by polymerization of a mono- or diolefin, for example, a polyisobutenyl group prepared by polymerization of isobutylene. The metal salts are formed directly or by metathesis using known methods.

Succinirnide dispersants are also known, and a general method for their preparation is found in U.S. 7909,160%.

V

patents 5,219 * 666, 3 * 172,892 and 5,272,746. These preparations are prepared by reacting an oil-soluble alkyl or alkenyl succinic acid or anhydride with a nitrogen-containing compound. The suceinimide can be of the type known as a mono- or bis-suceinimide. Nitrogen compounds which are preferably used in the preparation of the succinimides are those known as the ethylene amines and particularly preferred are triethylene tetraamine and tetraethylene pentamine. The preferred alkyl or alkenyl groups contain from 50 to 300 carbon atoms and the most preferred preparations are prepared from polyisobutene. When this type of suspending agent is used, the amine portion will contribute to the alkalinity value.

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

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

Alkali metal and alkaline earth metal phenates are known and are the alkali or alkaline earth metal salts of an oil-soluble alkyl-substituted phenol. The preparation can be sulfurized. Conventional phenates are prepared by neutralizing an alkyl phenol of 8 to 128 carbon atoms in the alkyl group with calcium hydroxide or oxide.

Mannich bases are suitable suspending agents. Mannich bases are prepared by reacting an oil-soluble phenolic or alcoholic product, such as an alkyl phenol, with an aldehyde, such as formaldehyde or acetaldehyde, and a nitrogen-containing compound. Conventional Mannich bases contain from 8 to 128 or more 35 carbon atoms in the alkyl group. If desired, the alkaline earth metal metal salt of the phenolic type Mannich base can be used as a suspending agent.

The reaction promoting amount of a hydroxyl group-containing promoter is necessary for the reaction to proceed at an acceptable rate. Generally, 0.1 to 10% by weight of 7909180 * 6 or more of the reaction mixture may be the hydroxyl "containing promoter. The promoter is believed to act as a solubilizing agent for the basic reacting metal compound. The promoter is preferably - water or an alkanol of 1 to 6 carbon atoms or an alkanediol of 2 to 6 carbon atoms such as methanol, ethanol, isopropanol, butanol, ethylene glycol, 1,4-butanediol, etc. Most preferred are water, ethanol and methanol. Mixtures of these promoters can also be used, chosen to keep the water formed during the reaction in solution.

Although not an essential reagent, it is preferred that the reaction take place in the presence of a chalcogen compound. Suitable chalcogen compounds include carbon dioxide, carbon disulfide, carbon oxysulfide, sulfur dioxide or mixtures thereof. While the chalcogen reagent is usually added in gaseous form, it can also be added in liquid or solid form, for example as dry ice or liquid sulfur dioxide. Carbon dioxide is the preferred chalcogen reagent. When a chalogen reagent is used, the amino acid should contain a primary or secondary amino group. The chalcogen compound is a preferred reagent since it increases the alkalinity value of lubricating oil additives by incorporating more of the basic reacting metal compound.

The reaction is carried out in a suitable solvent. Preferably, the solvent is a lubricating oil, so that no removal of the lubricant is necessary before incorporation of the additive into the lubricating oil. Other suitable solvents are low boiling hydrocarbon solvents such as hexane or a hydrocarbon diluent. Mixtures of lubricating oil with hexane or hydrocarbon thinner are also suitable. After the preparation is complete, the lower boiling solvents are easily removed by heating, if necessary.

The process of the present invention can be carried out at any temperature from the freezing point of the mixture to its boiling point. Usually the reaction is carried out at a temperature of 0 to 75 ° C, preferably 20 to 75 ° C, most preferably 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 metal compound to the chalcogen and the amino acid is such that about 10/10 to 790916® 7 3/4 of the alkalinity value of the final composition is contributed by the ashless amino-containing product.

It is preferably desired to have at least one equivalent of the basic reacting metal 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 desired alkalinity value from the ash-free nitrogen portion of the amino acid. For a simple amino acid (glycine, beta-alanine), generally at least two qui val ents £ The language compound uses 10 per mole of amino acid, while for a more complex amino acid (glutamic acid, lysine, nitrilotriacetic acid), generally at least three equivalents are used, although fewer equivalents can be used when a greater ash-free alkalinity value ratio is desired. Under usual conditions and based on 1 equivalent of the basic reacting metal compound, the reaction mixture will contain 0.1 to 2.0, preferably 0.3-0.5 equivalents of the amino acid compound; 0-1, preferably 0.3-0.5, equivalents of chalcogen compound and 2 to 20, preferably 4 to 10 parts by weight of the suspending agent per part of the basic reacting metal compound. The hydrocarbon solvent should be present in an amount sufficient to allow proper mixing of the reagents and is usually present as 5 to 50 and preferably 10 to 25 ml per gram of basic reacting metal compound. 0 to 5, preferably 1 to 2 ml of the promoter per gram of basic reacting metal compound is also used.

In a preferred method of carrying out the reaction, a sodium, calcium or magnesium alkyl benzene sulfonate is used as the suspending agent. It is also preferable to use an alkenyl sucin cimide or an alkenyl succinic anhydride as a co-suspending agent. When this combination of solubilizing agents is used, an increased alkalinity value for the product is obtained when, prior to the addition of the amino compound and the basic reacting product, preferably an alkaline earth metal oxide or hydroxide, the mixture of ingredients and the solvent pretreated with a small amount of chalcogen, for example 1 to 10%, preferably about 5%, of the total amount of chalcogen.

The lubricant compositions prepared according to the present invention provide a high alkalinity value at a lower ash content of 40 than is present in the most common dispersants and / or 7909160 * '. 8 acid neutralizing agents such as used as lubricating oil additives.

The alkalinity value is one method of specifying the degree of over-alkalization of the lubricant 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 preparation is illustrated in ASTM Method D-2896. Briefly, the alkalinity value is the total base number, given as milligrams of potassium hydroxide per gram of sample.

It is the amount of potassium hydroxide required to neutralize the same amount of perchloric acid that neutralizes 1 g of the sample. For example, when a formulation has the same acid neutralizing power per gram as 10 mg of potassium hydroxide, the formulation will have an alkalinity value of 10. The lower limit of the alkalinity value is 0 for a neutral formulation. Rates of 200 or more are particularly desirable by use in lubricants exposed to the decomposition products of sulfur-containing diesel fuels. Usual 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 the appropriate amount of the additive of the present invention with a lubricating oil by conventional mixing techniques. The choice of a particular 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 lubricant will range from 0.1 to 40% by weight and preferably from 2 to 35% by weight. The resulting lubricating oil will usually have an alkalinity value in the range of 1 to 120, preferably 2.5 to 100.

The lubricating oil which can be used in the present invention includes a wide variety of hydrocarbon oils such as naphthenic, paraffinic and mixed oils. The lubricating oils can be used individually or in combination and generally have a viscosity ranging from 505 to 5000 SUS (Saybolt Universal Seconds) and usually 100 to 1500 SUS at 3B ° C.

In many instances, it may be effective to form concentrates of the additives of the present invention with a liquid carrier. These concentrates provide an effective method for 7909160 9-- Λ.

handling and transporting the additive of the present invention before subsequently diluting and using it. The concentration of the additives of the present invention in the concentrates can range from 85 to 10 wt%, although it is preferable to maintain a concentration between about 15 and 40 wt%. The preferred method for obtaining concentrates is to prepare the additive in a limited amount of lubricating oil, as will be used in preparing the final dilute lubricant composition. Also, the additive can be prepared in a low boiling hydrocarbon, which is removed by distillation after adding a limited amount of lubricating oil.

If desired, other additives may be included in the lubricating oil compositions of the present invention. These additives include antioxidants or oxidation inhibitors, dispersants, rust inhibitors, anti-corrosion agents, and so on. Other types of lubricating oil additives that can be used include anti-foaming agents, stabilizers, anti-discolouring agents, adhesives, anti-vibrating agents, dropping point improvers, anti-grinding agents, extreme pressure agents, odor control agents and the like.

It has surprisingly been found that the magnesium salts of H-carboxy amino acids are stable in the presence of water at elevated temperatures. This is particularly surprising and unexpected in view of the fact that the calcium, barium, strontium and sodium amino acid carbamates in water are not stable. This property is particularly suitable since water comes into contact with lubricating oils at elevated temperatures when using an internal combustion engine. The magnesium salts of N-car-30 boxyamino acids have many uses, in particular as lubricating oil additives as described above, gelling agents, as food preservatives and as household laundry detergents, etc.

The preferred magnesium compounds of the present invention can be formed by the reaction of carbon dioxide with a basic reacting magnesium compound and an amino acid of the structural formula 1. The preferred products are the magnesium salts of H-carboxy amino acids represented by the structural formula 2.

In these structural formulas, the symbols have the following meanings: 40 7909160

SO

"10 1256 7 R, R, R, R and R are independently each other hydrogen, an alkyl group of 1 to 20 carbon atoms, a carboxyalkyl group of 2 to 20 carbon atoms, a hydroxyalkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 10 carbon atoms, an aminoalkyl group of 1 to 20 carbon atoms with hydrogen or alkyl of 1 to 6 carbon atoms on the nitrogen atom or an amino carboxyalkyl group of 2 to 20 carbon atoms, 1 2 10 R and R can be directly or via a 0, S or N atom to form a 5- or 6-ring, R 1 is hydrogen, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkaryl group of 7 to 20 carbon atoms, an aralkyl group of J to 20 carbon atoms , a carboxyalkyl group with 2 to 20 carbon atoms, a hydroxyalkyl group with 2 to 20 carbon atoms, an aminoalkyl group with 2 to 20 carbon atoms, a polyaminoalkyl group with 4 to 20 carbon atoms and 2 to 10 amino groups, n is 0 to 6.0 ml s 0 to 6.25 s is 0 or 1, 3 5 R and R may be joined to form a 5- or 6-membered heterocyclic ring with 0 or 1 additional heteroatoms selected from 0, S, KR, wherein R is an alkyl group having 1 to 6 carbon atoms, 5 6 R and R may be joined directly or through an 0, S or N atom 30 to form a 5 or 6 ring, X is a linking diradical selected from the group -0 -, -S-, -SS-, - (ΌΗρ ·), where p represents 1 to 6, and the group of formula 3 »R8 is hydrogen, an alkyl group of 1 to 20 carbon atoms, a hydroxyalkyl group of 1 to 20 carbon atoms an aryl group with 6 to 12 carbon atoms, an alkaryl group with 7 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, 7909160 i.

11 a. aminoalkyl group with 1 to 20 carbon atoms, a carboxyalkyl group with 2 to 20 carbon atoms, a carboxyl group.

an amino group with 0, 1 or 2 substituents as defined 7 5 for Ir,

Q

and when s is not phenyl, E may have the same structure as bound at the opposite end of the X linking group.

The preferred magnesium ε-carboxyamino acid salts are preferably 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 amount of a hydroxyl group-containing promoter. For the preparation of the preferred magnesium salts, the amino acid may be any organic acid containing at least one basic amino (-EH) group and at least one acidic carboxyl (-C00H) group. Especially preferred are glycine and the α-amino acids. Mixtures of different amino acids can be used. Other preferred reaction conditions for this preferred embodiment of the present invention include, based on 1 equivalent of the basic reacting magnesium compound, from 0.5 to 1.5 equivalent of the amino compound, from 1.5 to 2.5 equivalents of carbon dioxide and from 4 to 10 wt.

25 parts of the suspending agent per part of the basic reacting magnesium compound.

The preferred E-arb oxyamino acid salts may also be prepared by reacting the basic reacting magnesium compound, the amino acid and carbon dioxide in water or 50 mixtures of water and another hydroxyl-containing solvent.

The resulting solution of the E-carboxyamino acid magnesium salt can be dispersed by means of a dispersant, in the desired hydrocarbon solution, and then the water is removed by dehydration to form a dispersion of the salt or the resulting water solution can be evaporated to dryness, the resulting solid dust ground to a finely divided state and dispersed with dispersants in the desired hydrocarbon medium.

7909160

12 Example I

180 g of a 67% concentrate of a calcium were alkylated in a 1 liter three-necked flask.

aromatic sulfonate hydrocarbon diluent, 400 ml of a hydrocarbon diluent, 10.3 g (0.25 mol) magnesium 2 oxide (Maglite A, Merck, 200 m / g), 18.8 g (0.25 mol) glycine and 10.0 ml of water were added. The mixture was stirred at ambient temperature, then heated to ^0 ° 0 and then 3 g of carbon dioxide were added over 25 minutes at a temperature of 10 kO to 55 ° 0. Then, 10 ml of 100 percent ethanol were added and 2 g of carbon dioxide were added over a 20 minute period at temperatures ranging from k5 to 55 ° C. An additional 5 ml of 100% ethanol was added and an additional 8 g of carbon dioxide was added over a period of 76 minutes at 55 ° C. The reaction mixture was then centrifuged at 12,000 rpm for 20 minutes and then filtered through a layer of diatomaceous earth. The filtrate was stripped at 2.7 kPa at 110 ° C.

The mixture gave 142 g of product with an alkali pickling value of 20 189.8 and contained 3 22% magnesium, 1.33% calcium and 1.2% nitrogen.

Example II

To a 5 liter three-necked flask were charged 67 µg of a 67 percent concentrate of a calcium alkylated aromatic sulfonate in hydrocarbon diluent, 2330 g of a hydrocarbon diluent, k7 ml of water, 75 ml of 95 percent ethanol, 50.5 g of magnesium oxide and 9100 g of glycine added. The mixture was stirred and heated to 50 ° C. 56 g of carbon dioxide were added over 2 hours and 15 minutes, while the temperature ranged from 38 to * 7 ° C. The reaction mixture was filtered through a layer of diatomaceous earth. The filtrate was stripped at 2.7 kPa at 110 ° C. The mixture gave 826 g of product with an alkalinity value of 203.6 and contained 3-8% magnesium, 1.38 calcium and 1.39% nitrogen.

Example III

150 g of a 67% concentrate of a calcium alkylated aromatic sulfonate in hydrocarbon, 50 50 ml of a hydrocarbon diluent, 20 ml of methanol, 10 ml of water, 37 g 5 g of glycine kO (0) were added to a 1 liter three-necked flask. .5 mol) and 20.6 g of magnesium oxide are added. The mixture was stirred and heated to 150 ° C and 90 g of carbon dioxide was added over 5 hours and 13 minutes, the temperature ranging from 33 to 48 ° C. The reaction mixture was filtered through a layer of diatomaceous earth. The filtrate was stripped at 2.7 kPa at 110 ° C.

The mixture gave 18½ g of product with an alkalinity value of 232.5 and contained% magnesium, 1.27% calcium and 1.8% nitrogen.

Example IV

To a 500 ml Erlenmeyer flask were added 0.03 g (0.10 mol) of magnesium oxide (Velsicol), 60.0 g of a 6% by weight concentrate of a calcium alkylated aromatic sulfonate in hydrocarbon diluent, 200 ml of a hydrocarbon diluent, 5®1 water and 10ml of methanol are added. The mixture was then stirred and 12.73 g of nitrilotriacetic acid were added. The mixture was then stirred vigorously overnight at ambient temperature. A small amount was centrifuged at 11,000 revolutions / minute for 30 minutes. The transparent top layer obtained had an alkali value of 10.8½.

Example V

20 grams of magnesium oxide (0.1 mol) (Velsicol), 60.0 g of a 67 percent concentrate of a calcium alkylated aromatic sulfonate in hydrocarbon diluent and 200 ml of a 500 ml Erlenmeyer flask were added. hydrocarbon diluent added. The mixture was then stirred and 14.6 g (0.05 mol) of ethylenediamine tetraacetic acid were added. The mixture was then stirred at ambient temperature overnight and the reaction mixture was filtered through a layer of diatomaceous earth. The resulting transparent filtrate had an alkali value of 10.07.

Example VI

900 g of a 67 percent concentrate of a calcium alkylated aromatic sulfonate in a hydrocarbon diluent, 2300 ml of a hydrocarbon diluent, 120 ml of methanol, 120 ml of water, 210 g (2.8 mol) were added to a 5-liter three-necked flask. glycine and 153 µg (3.8 mol) of magnesium oxide. The mixture was stirred at ambient temperature for 5 minutes and then 126 g of carbon dioxide and 30 ml of water were added over 8 hours, the temperature ranging from 28 to M ° C.

The reaction mixture was filtered through a layer of diatomaceous earth.

The filtrate was stripped at 115 ° C and 2.7 kPa. The mixture 7909160 t * * «β Η gave 1.88 g of product with an alkalinity value of 332.6 and contained 5.98% magnesium, 1.04% calcium and 2.05% nitrogen.

Example VII

To a 1 liter three-necked flask, 5 160 g of a 67 percent concentrate of a calcium alkylated aromatic sulfonate hydrocarbon diluent, 400 ml of a hydrocarbon diluent, 15 ml of methanol, 8.0 g (0.2 mol) of magnesium oxide and 7 .9 g of ammonium hydrogen carbonate added. Then 9.8 g (0.2 mol) of sodium cyanide and 16.2 g of a 37% formaldehyde solution were added slowly over 10 minutes. The mixture was heated to 40 ° C and stirred for 3.25 hours. 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 in 66 minutes at temperatures ranging from 50 to 55 ° C. The mixture was stripped at 130 ° C (bottom product), 95 ° C (top product). The product was filtered through a layer of diatomaceous earth. The filtrate was stripped at 110 ° C and 2.7 kPa. The reaction mixture gave 182 g of product with an alkalinity value of 120.0 and contained 1.41% magnesium, 1.12% calcium, 1.27% nitrogen and 1.60% sodium.

Example VIII

37.5 g (0.5 mol) of glycines and 1000 ml of water were added to a 2-liter three-necked flask. The resulting solution was cooled to 15 ° G and flushed with a total of 283 g (6.4 moles) of carbon dioxide over a 3 hour period. During this period, a total of 20.9 g (0.52 mol) of magnesium oxide were added to the mixture in various portions. The resulting transparent solution was left overnight at ambient temperature, then filtered to give 1063 g of filtrate, which had an alkali value of 70.9 (yield 87%). A portion (41.9 g) of the filtrate was evaporated to dryness to yield 2.84 g of white solids having an alkalinity value of 1001.4 and containing 12.7% Mg, 8.58% N , 20.51% C and 4.36% H. Calculated for 35 03Η0 ^2.2Η20% C 20.3; % H 3.95; % N 7.90; Mg 13.7; alkalinity value 949

Example IX

To a 250 ml Erlenmeyer flask were added 7.9 g (0.1 mol) ammonium hydrogen carbonate, 2.01 g (0.05 mol) magnesium oxide, 100 ml distilled water and 4.9 g (0.1 mol) sodium cyanide. 7909180 15 joined. The mixture was stirred and 8.1 g (0.1 mol) of a 37 percent formaldehyde solution were added dropwise over 2 minutes. The mixture was stirred and left overnight. Then 50 ml of water and 2.0 g of magnesium oxide were added while carbon dioxide was bubbled through the mixture.

A total of 11.5 g of carbon dioxide were added. The mixture was filtered and the filtrate evaporated to almost dryness on a hot plate. A crude product of magnesium glycine carbonate was obtained (11.52 g) with an alkalinity value of 1069% containing 6.2% magnesium, 855 ppm calcium, 1.7% sodium and 9.6% nitrogen.

Example X.

20 ml of distilled water were placed in each of three 50 ml beakers. 50 mg of magnesium oxide and 60 mg of glycine were placed in beaker 1. 5 ° mg of magnesium oxide were placed in beaker 2. 50 mg of magnesium oxide and 10 mg of glycine were placed in beaker 3. The mixtures in all beakers were stirred. Carbon dioxide was added to beaker 1 and the solution was almost transparent after 30 minutes. No carbon dioxide was added to beaker 2 and the solids were still suspended after 1 hour. Carbon dioxide was then added to beaker 2 for 30 minutes without any significant change in the suspended solids.

There was no change in beaker 3 after stirring for 30 minutes and then carbon dioxide was added and all the magnesium dissolved to a transparent solution after 25 minutes.

From the foregoing, it was concluded that the reaction of magnesium oxide was greatly enhanced by the glycine.

Also, the magnesium glycine carbate reaction product was refluxed on a hot plate and, surprisingly, did not form precipitate.

7909160

Claims (19)

1. Process for the preparation of a lubricating oil additive, characterized in that an amino acid and a basic reacting metal compound are contacted under reaction conditions, which operation takes place in the presence of at least one suspending agent for the basic reacting metal compound and in the presence of a promoter containing hydroxyl groups » 2. Process according to claim 1, characterized in that an α-amino acid is used as the amino acid. 3. Process according to claim 2, characterized in that an α-amino acid with 1 to 5 carboxyl groups is used as the α-amino acid. k. Process according to claim 3, characterized in that glycine is used as the amino acid. The process according to claims 1 to A, characterized in that the basic reacting metal compound is a hydroxide of a metal of group I of the periodic system or an oxide or hydroxide of a metal of group II of the periodic system. 6. Process according to claims 1 to 5f, characterized in that as suspending agent an alkali metal or alkaline earth metal hydrocarbon sulfonate, a hydrocarbon succinimide, a hydrocarbon succinate, a hydrocarbon succinic anhydride, an alkali or alkaline earth metal alkphenate, a Mannich alkaline earth metal salt of a Mannich base or mixtures thereof. 7. Process according to claim 6, characterized in that the suspending agent used is an alkali metal or alkaline earth metal hydrocarbon sulfonate, a hydrocarbon succinimide or a hydrocarbon succinic anhydride or mixtures thereof. 8. Process according to claims 1 to 7, characterized in that an amino acid is used which contains a primary or a secondary amino group and that the contacting is carried out in the presence of carbon dioxide, carbon disulfide, carbon oxysulfide or sulfur dioxide. Method according to claim 8, characterized in that the contacting is carried out in the presence of carbon dioxide. 7909160 Process according to claims 1 to 9, characterized in that the promoter containing hydroxyl groups is water, methanol, ethanol or mixtures thereof. 11. Process according to claims 1 to 10, characterized in that an amino acid is used which has been prepared in situ. 12. Process according to claim 11, characterized in that the amino acid used is glycine, which is prepared in situ from the reaction of ammonia, formaldehyde and sodium or potassium cyanide. A process for preparing a lubricating oil additive, characterized in that under reaction conditions an amino acid such as glycine, a- or β-alanine, cystine, methionine or lysine and a basic reacting metal compound such as calcium oxide or hydroxide, magnesium oxide or contacting hydroxide, lithium or sodium hydroxide, which operation takes place in the presence of at least one suspending agent for the basic reacting compound, at least one chalcogen compound such as carbon dioxide, carbon disulfide, carbon oxysulfide or sulfur dioxide, and in the presence of a hydroxyl group-containing promoter in an amount suitable for the promoter activity. 1½. Process according to claim 15, characterized in that glycine is used as the amino acid, calcium hydroxide or magnesium hydroxide as the basic reacting metal compound and carbon dioxide as the chalcogen. Lubricating oil preparation characterized by the presence of an oil of lubricating viscosity and 0.1 to b% by weight of product obtained / according to claims 1 to 7, 13 or 1½. Lubricating oil concentrate, characterized by the presence of 10 to 60% by weight of an oil of lubricating viscosity and 90 to% by weight of a product according to claim 15 17 · Se magnesium salts of N-carboxy amino acids. 18. A compound according to claim 17, characterized in that the salt is the magnesium salt of an α-amino acid. Compound according to claim 17, characterized in that the amino acid is glycine, α- or β-alanine, cysteine, mthionine, sarcosine or lysine. 20. A compound according to claim 19, characterized in that the salt is the magnesium salt of N-carboxyglycine 7909160 * 21 Lubricating oil preparation characterized by the presence of an oil of lubricating viscosity and 0.5 to 50% by weight of the preparation according to claims 17 to 20. Lube oil concentrate characterized by the presence of 10 to 80% by weight of an oil of lubricating viscosity and 90 to 20% by weight of a composition according to claims 17 to 20. 23. Lubricating oil preparation. characterized by the presence of an oil with lubricating viscosity and 0.1 to wt% of the alkali metal or alkaline earth metal salt of an amino acid. 2½. Lubricating oil concentrate characterized by the presence of 10 to 80% by weight of an oil of lubricating viscosity and 90 to 20% by weight of an alkali or alkaline earth metal salt of an amino acid. 25. Preparation according to claim 23 or 2 * 1, characterized in that the acid is an N-carboxyamino acid. 26. A composition according to claim 23 or 2, characterized in that the amino acid part of the salt has a molecular weight in the range of 75 to 160. ****** ** 7908160 £ / r6 \ f Az \ e (\ / 1 \ I / IVR ° -fx-l — r C HC-hC-KOOH V Λ V 1 y Vi y \ r7 L Vr1 / \ Z "1 N \ Λ / \ R3 H _z . / r6 \ r5 / r2 \ g / \ / 1 \ I / I \ Rö —rX -T - {- CJ ~ C-kC-t — COOH V ys \! y I \\, \ R7Z I \ R1 / \ N \ / n Λ R3 COOH 3. y ~ ^ = NR 7909160