DE2825463A1 - LUBRICANT ADDITIVE - Google Patents

Description

2825 ^ 63

Lubricant additive

The invention relates to basic lubricant additives and, more particularly, to lubricating oil additives.

Lubricating oils, which are used in the harsh conditions of diesel engines, are complex to create a Neutralization of the sulfur in the fuel and the oxidation of hydrocarbons both in the fuel acids derived from the oil, dispersity for the preservation of sludge-forming precursors dispersed in the oil To achieve protection against abrasion and lubricating properties as well as an improvement in other oil properties. Additionally In addition to the requirements normally placed on a diesel lubricating oil, such oils are those used in railroad diesel engines Finding use, the added factor of being non-corrosive or reactive to silver. Become a silver warehouse nowadays mainly used in diesel engines.

The desire for a single addition, the multifunctional one Properties provides is for the efficiency and economy of the manufacture and use of a of such a single additive in comparison to a multitude of additives apparently. Because of the harsh operating conditions, however, among which a lubricating oil has to act in diesel engines, it has often been found that additives, although they do fulfilling a special function in an effective manner, the tendency to breakdown and to promote the formation of Own deposits. Therefore, when interpreting any particular addition, it is essential that this not only fulfills the function or functions for which it has been designed, but that it also performs under the Conditions of use is stable and only slowly degrades to materials which cause deposits to form not promote.

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For a long time, alkaline earth metal phenates were used in Lubricating oils used. Both sulfurized alkyl phenols and Mannich bases have been used in lubricating oils. the U.S. Patents 2,459,114 and 2,459,116 teach the manufacture of Mannich products using polyamines with sulfur-bridged Alkyl phenols. According to US Pat. No. 3,454,497, a Mannich base using methylamine, formaldehyde and alkyl phenols for use in lubricating oils. Other important patents are the US patents 2,810,697, 3,372,118, 3,472,773, 2,527,279, 2,763,616, 3,368 972, 2 410 911, 2 962 442, 3 413 347, 3 429 812 and 3 34Ο 19Ο.

GB-PS 1,352,760 describes and claims a dispersion detergent suitable for use as a lubricating oil additive and the reaction product obtained by neutralizing a sulfurized alkylphenol with at least 4 weight percent sulfur and a Mannich base with at least 2 weight percent nitrogen and a molecular weight of at least 600, prepared from a C ₁ - to C ^ -alkylamine, an alky! phenol and

Formaldehyde, available with an alkaline earth metal oxide or hydroxide contains, the neutralization in the presence of a hydroxylic solvent and at elevated temperature is carried out so that there are molecular bonds between the Mannich base and the sulfurized alkylphenol in addition to form the bridge bonds created by the alkaline earth metal.

In the main patent P (Pat eat anme ldung P 26 46 439.1

of the applicant) is a detergent-dispersant phenate with a low ash content with the same degree of alkalinity reserve described, which was produced by that

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the "G ^ -G ₇ alkylamine used in the preparation of the Maimich base, with which the product described in British Patent 1,352,760 was obtained, has been replaced by an alkylene or polyalkylene polyamine with the following structural formula:

£ - alkylene - IH - ^ - H, (I)

wherein η is an integer from 1 to 10 and the alkylene group Has 2 to 8 carbon atoms.

Furthermore, in the additional patent P (patent application no

application P 27 15 774 ·· 0) of the applicant to the aforementioned Main patent describes a "compound which is suitable for use as a lubricating oil additive and the reaction product contains that by neutralizing a sulfurized Alkylphenols with at least 4 percent by weight sulfur in the Genetic with a Mannich base containing at least 2 percent by weight nitrogen and a molecular weight of at least 600, and of an alkylene or polyalkylene polyanine of the following structural formula:

£ - alkylene - NH - ^ H, (I)

wherein η is an integer from 1 to 10 and the alkylene group Has 2 to 8 carbon atoms, an alkylphenol and formaldehyde was made with an alkaline earth metal oxide or hydroxide was obtained, the neutralization in the presence of a hydroxylic solvent and at increased Temperature was carried out and then the neutralized product was reacted with carbon dioxide.

Compounds which have been prepared by the process including aftertreatment with carbon dioxide have significantly lower viscosities than products which are not

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treated in this way.

Surprisingly, it has now been found that the viscosity of the product can also be reduced by the sulfurized alkylphenol starting material with carbon dioxide treated before neutralization.

The invention therefore relates to a compound suitable for use as a lubricating oil additive and the reaction product by neutralizing a sulfurized alkylphenol with at least 4 weight percent sulfur in the mixture with a Mannich base containing at least 2 weight percent nitrogen and a molecular weight of at least 600 and made of an alkylene or polyalkylene polyamine the structural formula

H ₂ N S- alkylene - NH - ^ H, (I)

wherein η is an integer from 1 to 10 and the alkylene group Has 2 to 8 carbon atoms, an alkylphenol and formaldehyde, with an alkaline earth metal oxide or hydroxide was obtained, the neutralization in Presence of a hydroxylic solvent and at increased Temperature was carried out according to patent (patent application P 26 46 4-39-1) »whereby the connection thereby is characterized in that the sulfurized alkylphenol has been reacted with carbon dioxide prior to neutralization.

It is believed that in the process of neutralizing the sulfurized alkylphenol with the Mannich base, molecular bonds are formed between the Mannich base and the sulfurized alkylphenol in addition to the bridging bonds created by the alkaline earth metal .

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The sulfurized alkyl phenols are known materials for Use in lubricating oils. The method of preparation of the sulfurized alkylphenols is not critical to the invention.

The sulfurized alkylphenols can for the most part, and preferably at least 90 %, have the following formula:

, (ID

wherein R is an alkyl group having 8 to 36 carbon atoms, usually 10 to 30 carbon atoms with the average number of carbon atoms ranging from about 10 to 26 is, y is an integer in the range from 1 to 9, more preferably from 1 to 5, the average over the entire composition ranges from about 2 to 4, and η is an integer from 1 to 5, more preferably from 1 to 3. It can be minor Amount, not more than about 10 weight percent, sulfurized phenol with y > 9 are available.

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The sulfurized alkyl phenol can be at least about 4 percent by weight Sulfur and "preferably no more than 20 percent by weight sulfur, more usually about 8 to 18 percent by weight Sulfur, have. The aliphatic hydrocarbon groups denoted by E in structural formula (II) may suitably are in the ortho position or in the para position, however, they are predominantly in the para position, since ortho-substituted phenols act as chain terminators act in the copolymerization of sulfur and alkylphenol. The presence of branched chain alkyl groups results reduced amounts of ortho-substituted phenols, and therefore branched chain alkyl groups are preferred.

Sulfurized alkylphenols can be obtained by combining alkylphenol, sulfur, calcium oxide or calcium hydroxide and Glycol at elevated temperature, driving off the water and hydrogen sulfide and then isolating the sulfurized alkylphenols, see e.g. B. U.S. Patent 2,989,466.

According to the invention, the sulfurized alkylphenol is reacted with carbon dioxide. The reaction is preferably at carried out at elevated temperature, although the pressure is not critical. The carbon dioxide can with the sulfurized Alkylphenol in an amount of 1 to 25 percent by weight and preferably 1 to 15 percent by weight, based on the weight of the sulfurized alkylphenol, are reacted. The carbon dioxide can be conveniently introduced as a gas, in which case it can be blown into the reaction mixture under pressure or it can be added as a solid,

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the introduction as a solid "is preferred.

Although the sulfurized alkylphenol can be reacted with carbon dioxide at any stage following the unification of the reactants at the reaction temperature, in a preferred mode of operation, alkylphenol, sulfur and calcium oxide or hydroxide and glycol are added at an elevated temperature, e.g. B. 14-0 to 150 ⁰ C, put together, water and hydrogen sulfide are driven off, carbon dioxide is introduced into the reaction mixture and finally the glycol solvent is removed under suitable conditions. Alternatively, the carbon dioxide can be introduced after removal of the glycol solvent.

The Mannich base is explained in more detail below. The Mannich bases used can be produced by that an alkylphenol, formaldehyde and alkylene or polyalkylene polyamine of the formula I are brought together at elevated temperatures will. The alkyl phenol can suitably be 4 to 40 carbon atoms, preferably 9 to 25, and even more preferably 10 to 14 carbon atoms in the alkyl group. Of the Formaldehyde can be added in the form of an aqueous solution (formalin) or in polymer form, e.g. as paraformaldehyde. A method for preparing the Mannich bases can be found in GB application 25316/71 (Serial No. 1,345,030). The US PS 3,454,497 describes another method of making Mannich bases using primary amines.

The preferred alkylene polyamines of the formula (I) are the ethylene polyamines, in which the alkylene group has 2 carbon atoms. A preferred ethylene polyamine is diethylenetriamine. Other polyalkylenepolyamines of Formula (I) that can be used include Ethylene diamine, tetraethylene pentamine and triethylene tetramine. Other alkylene polyamines that can be used include, for example, propylene polyamines and butylene polyamines. The alkylene polyamines can be prepared by methods well known in the art.

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The (undiluted) Mannich base contains at least 2 percent by weight and preferably no more than about 10 weight percent nitrogen. The osmometrically determined mean molecular weight "is at least 600, usually at least 700 and usually does not exceed 5000.

The Mannich base can be in the mono- or bis-form, the special form being due to the ratio of alkylphenol to formaldehyde to amine material in the starting mixture for the preparation is determined.

The alkaline earth metal oxide or hydroxide

The alkaline earth metal oxide or hydroxide is preferably one of calcium or barium, with calcium hydroxide being most common is preferred.

The hydroxylic solvent

Suitable hydroxy solvents include ethylene glycol, Propylene glycol, butanediols and methanol. 1,3-, 1,4- or 1,2-butanediol can be used. The preferred hydroxylic The solvent is ethylene glycol.

The products of the invention are complex in nature. Because of the variety of possible reactions that occur during the Formation of the product can occur, any attempt to define the means by a general structural formula would be meaningless.

Neutralization of sulfurized alkylphenol and Mannich base

The Mannich base and the sulfurized alkylphenol become advantageous in an equivalent ratio (based on phenol) in the range from 0.2 to 5: 1, usually 0.3 to 3: 1, mixed. In addition to the above reaction components, an alkaline earth metal

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metal oxide or hydroxide, preferably ßln hydroxide, and a hydroxylic solvent, usually ethylene glycol, available.

The amount of alkaline earth metal base added depends on the manufacturing process for the sulfurized alkylphenol. The amount of alkaline earth metal base used in the manufacture of the sulfurized Alkylphenol was used, the total added amount of the alkaline earth metal base can be up to one equivalent of the alkaline earth metal make up per equivalent of alkylphenol in the final product. On the other hand, an excess of alkaline earth metal base can be used usually not more than 1.75 and usually not more than 1.5 equivalents of alkaline earth metal per equivalent of alkylphenol im End product going out.

The amount of the hydroxylic solvent varies with the specifically used solvent, and the optimum amount can easily be determined by experiment. Since ethylene glycol is the preferred Is solvent, only its use will be discussed in detail. The amount of ethylene glycol used is normally between about 5 and 35 percent by weight, preferably between about 7 and 20 percent by weight of the total reaction mixture .

In addition to the ethylene glycol, an inert hydrocarbon can also be used be present as a thinner. These inert diluents can facilitate the handling of the reaction components, reduce the viscosity of the reaction mixture and facilitate the isolation of the product. With regard The intended use of the agents according to the invention can use mineral oils of lubricating viscosity and the product can be isolated as a solution in the mineral oil. Normally, the inert diluent in the reaction mixture, if at all, present in amounts from 3 to 65 percent by weight, more usually from 5 to 50 percent by weight of the total reaction mixture be.

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A small amount of an anti-foaming agent or an anti-foaming agent Means can be used conveniently. The suds suppressor is suitable in the reaction mixture in amounts of 1 χ 10 to 1 χ 10 percent by weight IN ANY. Conventional suds suppressors can be used.

In addition, a small amount of a neutral ErJ alkali metal sulfonate is suitable in the reaction mixture for easier dispersion of the alkaline earth metal oxide or hydroxide in the mixture and to improve the rate of the neutralization reaction. The neutral alkaline earth metal sulfonate can be a synthetic one or naturally occurring material and is preferably calcium sulfonate. The amount of alkaline earth metal sulfonate added suitably ranges between 1 and 5 percent by weight.

The reaction can be conveniently carried out by bringing together the sulfurized alkylphenol, Mannich base, alkaline earth oxide or hydroxide and the hydroxylic solvent, e.g., ethylene glycol, and optionally the inert diluent. The mixture is preferably heated to at least 90 ⁰ C prior to the addition of ethylene glycol, but below the temperature at which the neutralization is to be conducted. After the ethylene glycol has been added, the temperature for distilling off the water overhead can be increased to remove the water of reaction; the temperature for removing the water is usually in the range from 125 to 160 ^° C. The time required to remove the water is usually between about 30 minutes and 3 h.

Neutralization of sulfurized alkylphenol and Mannich base precursors

On the other hand, the reaction can be carried out advantageously by first reacting the sulfurized alkylphenol with the precursors of the Mannich base to form a product which

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contains stilfurated alkylphenol and Kannich base, and then the product with the alkaline earth metal oxide or hydroxide in the presence of the hydroxylic solvent, e.g. ethylene glycol, is neutralized.

Carbonized, sulfurized alkylphenol may suitably be related to the alkylphenol in an equivalent ratio (" on phenol) in the range from 0.2 to 10: 1, preferably 0.2 to 5: 1 and even more preferably about 1: 1 are reacted. The alkylene or polyalkylenepolyamine may suitably be in a Amount of 1 to 3 mol for every 1 to 3 ek> 1 alkylphenol im The reaction mixture is present. The formaldehyde can be present in an amount of 0.75 "to 1.25 moles for every 1 to 3 moles of alkylphenol present in the reaction mixture.

The reaction between the carbonized, sulfurized alkylphenol, the alkylphenol, the alkylene or polyalkylene polyamine and the formaldehyde can be carried out by mixing the reaction components together and heating to a sufficiently high temperature to initiate the reaction. The reaction is preferably carried out in the presence of a solvent. Preferred solvents are the water-immiscible solvents including water-insoluble alcohols (e.g. amyl alcohol) and hydrocarbons. In the range from 50 to 200 ⁰ C boiling hydrocarbons as solvents, z. Benzene, toluene and xylene are the preferred water-immiscible solvents. Most preferred among these is toluene. The solvent can suitably be used in an amount of from 1 to 50, preferably 3 "to about 25 and even more preferably from 5 to 10 percent by weight, based on the total weight of the reaction mixture.

The reaction may be at a temperature in the range of 50 to 150, preferably be carried out from 50 to 130 ⁰ C in a suitable manner. If a solvent is used, it is preferably carried out at the reflux temperature of the reaction mixture. Will eg

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If toluene is used as the solvent, the condensation proceeds appropriately at about 110 to 130 C. Towards the end of the reaction the temperature can be increased to about 150 C to remove the solvent, toluene. That with the reaction formed water is distilled off together with the water-insoluble solvent, which removes it from the reaction zone enables. With this removal of the solvent, the pressure can be lowered. The one required to terminate the reaction Time depends on the reaction components used and the reaction temperature used. Response times from 1 up to 8 hours are usually sufficient.

The complex product thus obtained can be neutralized in the same way as before for the reaction between the sulfurized Alkylphenol and the preformed Mannich base described.

Neutralization in the presence of a carboxylic acid

According to a further embodiment of the invention the neutralization of the carbonized, sulfurized alkylphenol in admixture with the Mannich base or its precursors in the presence of a carboxylic acid.

Even if any carboxylic acid can be present during the neutralization, the presence of a C ₁ to C carboxylic acid is preferred. A particularly preferred carboxylic acid is acetic acid. The carboxylic acid can be present in an amount of from 0.001 to 0.5 mole, preferably from 0.02 to 0.1 mole, per mole of alkylphenol present in the reaction mixture.

Reaction with carbon dioxide

The neutralized product can still be reacted with additional amounts of carbon dioxide. Even if that neutralized Product with carbon dioxide in a later operating stage after removing the hydroxylic solvent can be implemented, it is preferred in

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in the presence of the hydroxylic solvent, ie before removing the solvent, reacted. The carbon dioxide can conveniently be introduced into the neutralized product mixture by injecting it under pressure. The reaction with carbon dioxide is preferably carried out at the temperature used for the neutralization reaction, ie 140 to 150 ^° C., although higher temperatures can also be used if desired. The amount of carbon dioxide added can suitably be in the range from 1 to 15, preferably 1 to 8 percent by weight, based on the total weight of the reaction mixture.

Remove hydroxylic solvent

While the inclusion of a hydroxylic solvent facilitates the preparation of the compound, its presence in the lubricants in which the compound is most advantageously employed is undesirable. Therefore, the hydroxylic solvent is preferably removed after the compound is formed. In the case of ethylene glycol as the solvent, this can be done by increasing the temperature to below 200 ° C. and by lowering the pressure sufficiently for its distillation. Usually, the temperature during the removal of ethylene glycol in the range from 140 to 200 ⁰ C, preferably 160 to 190 ⁰ C, are. The pressure can be varied depending on the temperature and the required rate of distillation. The reduced pressure can vary between about 0.01 and 0.8 at. Ethylene glycol can be removed over a period of 15 minutes to 9 hours. The time, although not a critical factor, should not be unduly elongated and depends on the capacity of the plant, the amount of reactants, the degree of foaming and temperature controllability, and the rate of distillate removal.

If no more ethylene glycol passes over, the reaction mixture can be cooled. In this case, an inert compound is preferred

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added thinners. Depending on the presence and the amount of inert diluent already present in the reaction mixture, the temperature is preferably kept above about 150 ° C. before sufficient dilution is carried out with a suitable diluent. The mixture can be extremely viscous, and the Inlösunggehen in a diluent is difficult below a temperature of about 150 ⁰ C. Any suitable diluent can be used, but a hydrocarbon-based lubricating oil will normally be used as the diluent in view of the intended end use. Various hydrocarbon lubricating oils can be employed depending on the ultimate use. Whether or not further diluent is added, undesired insoluble compounds are preferably filtered off.

The product according to the invention

The product, as it is formed (regardless of a diluent), has an alkali number (ASTM Test D 2896) in mg KOH / g in the range from 100 to 450, usually from about 175 to 400. The product gives an elemental analysis of about 2 to 12, usually from about 3 to 7 weight percent alkaline earth metal, at least about 0.1 to 5, usually about 0.5 to 4 weight percent nitrogen and about 0.8 to 10, usually about 1 to 8 weight percent sulfur. In a neutral 100-01 (100 is the viscosity at 100 ⁰ F or 38 ⁰ C in SUS) at a 0.88 molar concentration of alkaline earth metal (3.5 percent by weight for Ca) the viscosity is at 99 ⁰ C (210 ⁰ F) usually in the range of about 200 to 3000 SUS, usually in the range of 200 to 1500 SUS.

Preparation of products according to the invention

The diluted product is to be used as a finish concentrate of lubricating oils or other conventional additional compounds can be added.

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The invention therefore additionally offers a concentrate which is suitable for the production of finished lubricating oils, with a smaller one A proportion of a hydrocarbon-like lubricating oil and a major proportion of an additional amount derived from that of the hydroxylic Solvent-free compound, obtained as previously described, consists or contains.

The amount added can be completely derived from that of the hydroxylic solvent free compound, as previously described, in an amount up to 95 w / w%, based on the total weight of the Concentrate. Alternatively, the amount added may be at least 5% w / w of that free from the hydroxylic solvent Compound as described above and up to 90% w / w of other additives, based on the total weight of the concentrate, contain. The further additives can, for example, agents for improving the viscosity index (VI), agents for Pour point depressants, anti-foaming agents, antioxidants, extreme pressure agents, or any of the other commonly used additives used in lubricating oil formulations.

According to a further aspect of the invention, a finished Lubricants are offered, the main part of which is a base lubricating oil and the minor part is the concentrate described above contains.

The base lubricating oil can be a mineral oil derived from petroleum or a synthetic oil, e.g. based on esters, originates.

Conventional lubricant additives can be used in the finished lubricant to supplement any additives already present in the concentrate.

Although the compounds according to the invention have a similar alkalinity reserve like conventional additives, their ash content is much lower.

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The invention is explained in more detail using the following examples, only Examples 1 and 2 were carried out according to the invention,

Example A.

in mixture of 834- g of a C ^ o-alkyl phenol prepared by alkylation of phenol with Propylentetrameia, 55 "5 ε calcium hydroxide and 24-0 g of sulfur were charged into a 2-1 flask and heated to 125 ⁰ C. Then 32 g of ethylene glycol were added. The Heaktionstemperatur was raised to 150 ⁰ G, and the pressure was reduced to 210 mm Hg and maintained at this value. 1

The temperature was then further increased to 190 ° C (base temperature) and the pressure was reduced to 50 mm Hg for a period of 2 hours, during which time all of the ethylene glycol was removed. The product was then cooled to 120 ⁰ C, there were added 396 g 10OSH engine oil and the product filtered.

The product was shortened to its alkalinity or its alkali number AZ and measured according to the US-Horm ASTM D 2896 and its S content analyzing and? Measured the viscosity at 98 9 ⁰ C. The values are compiled in Table I below.

Example B.

The procedure of Example A was repeated with the exception that after the reaction ^{temperature had been increased to 150 °} C. and the pressure had been reduced to 50 mm Hg for 1 hour, the mixture was reacted with 4-5 g of carbon dioxide.

The AZ value, the S content and the viscosity at 98.9 ⁰ G are also listed in Table I.

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Salary (%) Table I. viscosity
at 98.9 ⁰ C (cS) Ex. S- 10.98
10.58
C. AZ value
(mg KOH / r) 52.5 A.
B.
example 55.7
51.0 Manufacturing

A mixture made from 278 g (1 mol) of a C 1-10 alkyl phenol by alkylation of phenol with propylene tetraniers, 51.5 g (0.5 mol) diethylenetriamine, JO g (1 mol) paraformaldehyde and 2 liters of toluene were heated to reflux and the water removed via a Dean-Stark trap.

11 V / ater was added to the mixture and then removed along with the toluene solvent. Then, a Haximaltemperatur of 160 ⁰ C for 1 h was maintained at a pressure of 40 mm Hg.

example 1

346 g of 74% · active Mannich base from Example C and 255 Z of sulfurized alkyl phenol of Example B, ie of the sulfurized Alky! Phenol which has been reacted with carbon dioxide "were mixed together at 125 ⁰ C. There were 46.3 S calcium hydroxide and 150 g Ithylenglykol then added. the pressure was reduced to 500 mm Hg, and the temperature was maintained at 125 ⁰ C for 15 minutes, then the temperature was raised to 15Ο ⁰ C, at this value it was maintained for 1 h The material was then vacuum stripped to 185 ° C and 50 mm Hg pressure and maintained at these conditions for 15 minutes The product was cooled and diluted with 67 g of 100SN motor oil prior to filtration.

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The viscosity measured at 9S, 9 ° C, the alkali number, the The calcium and nitrogen contents of the product are given in Table II.

Example p

The procedure of Example 1 was repeated with the exception that instead of using the sulfurized alkylphenol obtained according to Example B, the one obtained in Example A, sulfurized alkylphenol; d. H. not with carbon dioxide converted sulfurized alkylphenol was used.

The measured at 98.9 ⁰ C viscosity, the alkali number of the calcium and the nitrogen content of the product, are also in the labeile II 'indicated.

Table II

E.g. Visc
at
(c3) AZ
(mg EOE / g) Ca content N content 1
B. 207
185 4.15
3.63 2.12
1.96 : osity
98.9 ⁰ C 4-92
602

From the values in Table II it can be seen that the reaction of the sulfurized alkylphenol with carbon dioxide prior to neutralization gives a product with lower viscosity.

Example Ξ

C 2344- (S mol) of a C ^ ^ alkyl phenol, 512 g (16 mol) and Schvrcfel 1'77,6 g (2.4 mol) of calcium hydroxide were heated to 125 ⁰ C, and there were 99 g of i-thylenglykol added . The temperature was raised to 15Ο ⁰ C and the pressure at 300 nn Uc reduced, and these conditions were maintained h for 1 hour.

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The product was then at a base temperature of 190C and a pressure of 50 mm Hg for 2 h in vacuo.

Leg cooling to 120 ⁰ C, the vacuum was raised, and it was 682 g 100SN engine oil added. The product was then filtered.

The product was analyzed sulfur content of calcium and and the viscosity was measured at 98.9 ⁰ C. The results are given in Table III.

Example F

The same relationships between the participants and the same manufacturing technique as described in Example E. ben was, was repeated with the exception that the reaction mixture before vacuum stripping with 3 percent by weight, based on total reactants, solid carbon dioxide was carbonized at atmospheric pressure.

The product was analyzed sulfur content of calcium and and the viscosity was measured at 98.9 ⁰ C. The results are also shown in Table III.

Table III

E.g. sulfur content ($ e) calcium content (%) viscosity at

98.9 ⁰ C CcS)

3.29 328

3.30 133.8

E. G 9 , 03 F. 9 , '+ 3 example

703 SC _i2 -alkylphenol, 742 g sulfurized alkylphenol from Example E, 250 g 100SK motor oil, 206 g diethylenetriamine

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tand 90 g of paraformaldehyde was heated to I30 h ⁰ C for a period "of 1, and maintained at this temperature for an additional hour. The water formed was removed by normal distillation techniques.

Then 248 g of ethylene glycol and 148 g of calcium hydroxide were added and the temperature was increased to 175 ° C. "at this value was held for 1 h. The product was then at a base temperature of 200 C and a pressure of 20 mm Hg stripped for 0.5 η in vacuo.

After cooling to 125 ⁰ C 227 g 100SN engine oil were added and the material was filtered.

The product was analyzed for calcium and nitrogen content, and the alkali number and viscosity at 98.9 ° C were measured. The results are given in Table IV.

Example 2

The preparative procedure of Example G was repeated with the same amounts of reactants except that 754 g of the sulfurized alkylphenol from Example J ^{1 were used} instead of the sulfurized alkylphenol from Example E, and that 224 g of 100SH "motor oil were used were added to the completion of manufacture.

The product was analyzed for calcium and nitrogen content, and the alkali number and viscosity at 98.9 ° C were measured. The results are also given in Table IV.

Table IV

E.g. calcium content nitrogen content alkali number viscosity at (*) i%} (mg ΕΌΗ / κ) 98.9 ° C CcS)

G 4.04 3.55 232 884

2 3.89 3.23 237 689

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Claims (1)

Pat ent calls Compound suitable for use as a ski oil additive and containing the reaction product which by neutralizing a sulfurized alkyl phenol with at least 4 weight percent sulfur in the mixture with a Mannich base containing at least 2 weight percent nitrogen and a molecular weight at least 600 and from an alkylene or polyalkylene polyamine of the structural formula -f- alkylene - KH (D where η is an integer from 1 to 10 and the alky lengruppe has 2 to 8 carbon atoms, an alkylphenol and! formaldehyde was produced with a 809851/091 IWSPECTSD 2825ΛΒ3 Alkaline earth metal oxide or hydroxide was obtained, the neutralization being carried out in the presence of a hydroxylic solvent and "at elevated temperature, according to patent (patent application P 26 46 4-39 * 1)" characterized in that the sulfurized alkylphenol prior to neutralization with
Carbon dioxide has been converted. 2. A compound according to claim 1, characterized in that at least 90 % of the sulfurized en alkylphenol from sulfurized alkylphenols of the structural formula where R is an alkyl group with 8 to 36 Eohlen material atoms, y is an integer in the range from 1 to 9 and η is an integer from 1 to 5. Connection according to claim 2, characterized in that in the sulfurized alkylphenol of formula (II) R is Is an alkyl group of 10 to 30 carbon atoms, the average number of carbon atoms in the range from about 10 to 26, y is an integer in the range from 1 to 5, on average over the total Settlement is in the range from 2 to 'from 1 to 3. and η is an integer 809851/0918 4-. A compound according to any one of claims 1 to 3, characterized characterized in that the sulfurized alkylphenol A- "bis Contains 20 weight percent sulfur. 5. A compound according to any one of claims 2 to 4-, characterized ρ
characterized in that R in the sulfurized alkylphenol composition of the formula (II) is predominantly in the p-position. 6. A compound according to any one of claims 1 "to 5» thereby characterized in that the sulfurized alkylphenol has been reacted with carbon dioxide at an elevated temperature is. 7 · Connection according to claim 6, characterized in that the carbon dioxide with the sulfurized alkylphenol in an amount of 1 to 25 percent by weight based on the weight of the sulfurized alkylphenol, has been converted. 8. A compound according to claim 7 *, characterized in that the carbon dioxide has been reacted with the sulfurized alkylphenol in an amount of 1 to 15 percent by weight is. 9 · Connection according to one of claims 6 to 8, characterized characterized in that the carbon dioxide has been added as a solid. 10. Compound according to one of the preceding claims, characterized in that alkylphenol, sulfur, calcium oxide or hydroxide and glycol were combined at a temperature in the range from 140 to 150 ⁰ C, that water and hydrogen sulfide was driven off, that carbon dioxide was introduced into the reaction mixture and that finally the glycol solvent has been removed. 809851/0918 11. A compound according to any one of the preceding claims, characterized in that the Mannich base consists of one
Alkylphenol containing 9 "to 25 carbon atoms in the alkyl group. 12. A compound according to any one of the preceding claims, characterized in that the Mannich base 2 "to 10
Has nitrogen percent by weight and has an osmometrically determined molecular weight in the range from 600 to 5000. 1Y. Compound according to one of the preceding claims, characterized in that the alkylene polyamine with the
Formula (I) is an ethylene polyamine. 14. A compound according to claim 13, characterized in that the ethylene polyamine is diethylenetriamine. 15. A compound according to claim 13, characterized in that the ethylene polyamine is ethylene diamine, tetraethylene pentamine or triethylenetetramine. 16. A compound according to any one of the preceding claims, characterized in that the alkaline earth metal is calcium
or barium. 17. A compound according to claim 16, characterized in that the alkaline earth metal hydroxide is calcium hydroxide. 18. A compound according to any one of the preceding claims, characterized in that the hydroxylisehe solvent is ethylene glycol in an amount in the range from 5 to
35 percent by weight of the total reaction mixture. 809851/0918 19 · Compound according to one of the preceding claims, characterized in that the reaction product by Neutralization of the Mannich base and sulfurized alkylphenol in admixture "at an equivalent ratio (based on phenol) in the range from 0.2 to 5: 1 has been. 20. A compound according to any one of the preceding claims, characterized in that the reaction product by Addition of a total of up to one equivalent of alkaline earth metal per equivalent of alkylphenol present in the end product resulting amount of alkaline earth metal oxide or • hydroxide has been obtained. 21. A compound according to any one of claims 1 to 19, characterized in that the reaction product is added a total of less than 1.75 equivalents of alkaline earth metal per equivalent of alkylphenol present in the final product resulting amount of alkaline earth metal oxide or hydroxide has been obtained. 22. A compound according to any one of the preceding claims, characterized in that an inert solvent, the is a mineral oil of lubricating viscosity, in the reaction mixture in an amount ranging from 3 "to 65 percent by weight of the total reaction mixture is present is. 23. A compound according to any one of the preceding claims, characterized in that the reaction product is obtained by mixing the sulfurized alkylphenol, the Hannicii base and the alkaline earth metal oxide or hydroxide and heater. to a temperature of 90 to 14-0 ⁰ C before the addition of the ethylene glycol has been obtained as a hydroxylic solvent. 809851/0918 Compound according to Claim 23, characterized in that, after the addition of ethylene glycol, the temperature has been increased to a value in the range from 125 to 160 ⁰ C in order to remove the reaction water. 25. A compound according to any one of claims 1 to 22, characterized characterized in that the reaction product by reacting the cax "boned, sulfurized alkylphenol with the Precursor compounds of the Hannich base to form a carbonized, sulfurized alkylphenol and Mannich base containing product and then neutralizing the product with the alkaline earth metal oxide or hydroxide has been obtained in the presence of the hydroxylic solvent. 26. A compound according to claim 25, characterized in that the carbonized, sulfurized alkylphenol with the alkylphenol in an equivalent ratio (based on phenol) in the range from 0.2 to 5: 1 in the presence of the alkylene or polyalkylenepolyamine in an amount of 1 to 3 bk) 1 and has been reacted in the presence of the formaldehyde in an amount of 0.75 "to 1.25 mol for every 1 to 3 mol of alkylphenol present in the reaction mixture. 27. A compound according to any one of claims 25 or 26, characterized in that the reaction is carried out in the presence of a hydrocarbon solvent with a boiling point in the range from 50 to 200 ^{0 in an amount of 1 to 50 percent by weight, based on the total weight of the reaction mixture} C has been carried out. 28. A compound according to any one of the preceding claims, characterized in that the reaction product is neutralized of the carbonized, sulfurized alkylphenol in 809851/0918 2825 / -S3 Mixture with the Mannich base or the leading end compounds thereof in the presence of a C 1 -C 4 carboxylic acid in an amount of 0.001 to 0.5 mol / mol in the reaction mixture existing alkylphenol has been obtained. 29. A compound according to claim 28, characterized in that the carboxylic acid is acetic acid. JO. Compound according to any one of the preceding claims, characterized in that the neutralized product further reacted with additional amounts of carbon dioxide in the presence of the hydroxylic solvent has been. 31. A compound according to claim 30, characterized in that the additional amount of carbon dioxide in the range of 1 to 15 percent by weight based on the total weight of the reaction mixture, has been added. 32. Compound according to one of the preceding claims, characterized in that the hydroxylic solvent has been removed from the reaction product. 33 · Connection according to claim 32, characterized in that that an inert diluent in the form of a hydrocarbon-containing lubricating oil to the reaction product has been added after removal of the hydroxylic solvent. 34-. Connection according to one of claims 32 or 33 »thereby characterized in that undesired, insoluble compounds after removal of the hydroxylic solvent have been filtered off. 809851/0918 2 8 2 b /, β 3 35 · Concentrate for preparing finished lubricating oils with a minor proportion of a hydrocarbon lubricating oil in a major proportion of an additive amount, "consisting of" from or containing the hydroxylic solvent-free compound according to any one of claims 32 "to 34- · 36. Concentrate according to claim 35 »characterized in that the amount added from the hydroxylic solvent free compound in an amount "up to 95 w / w%, "based on the total weight of the concentrate". 37 · concentrate according to claim 35 _s characterized in that the amount of addition contains at least 5 Gew./Gew.-% free of hydroxylic solvent compound and up to 90 Gew./Gew.-% of other additives. 38. Finished lubricant composition containing a major proportion of a base lubricant and a smaller portion of the concentrate according to any one of claims 35 to 37. 809851/0918