DE2161121A1 - Alkylphenoxides containing basic alkylenamine and sulfur bridges as additives for lubricating oils - Google Patents

Description

Lubricating oils that are to be used under severe conditions in diesel engines must be kept in mind set high requirements and must be able to "fulfill the following tasks, for example: they must allow a neutralization of the acids from the sulfur contained in the fuel used and through Oxidation of hydrocarbons - contained in both fuel and oil - occurs; they have to cause sufficient dispersibility so that the precursors of sludge-forming products are kept in dispersion in the oil; they must provide good wear protection and a good oil lubricating effect and also give the oil other desirable properties. In addition to the Iron c ilts that diesel lubricating oils usually have

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Oils used in railroad diesel engines must be such oils should also have the property that they do not have a corrosive or reactive effect on silver · In the Silver bearings are used in the vast majority of the diesel engines used today.

It is obvious that for practical and economic reasons it is more favorable to use a single multifunctional element To use additive and not to add several different additives which together have the desired effect However, it has been shown that certain additives fulfill certain points well under the severe conditions in diesel engines, but decompose easily and thereby favor the formation of deposits. When building a certain additive as a result, it is not only important that this one or fulfills several functions to the satisfaction, but also remains stable under the expected operating conditions. and only decomposes very slowly into materials that favor the formation of deposits.

It has long been known to use alkaline earth metal phenoxides or phenates in lubricating oil. Also sulfurized alkylphenols and Mannich bases have already been used in lubricating oils. In U.S. Patent Nos. 2,459,114 and 2,459,116 the manufacture is of Mannich products using polyamines and by. Sulfur-bridged alkylphenols described » US Pat. No. 3,454,497 describes the preparation of a Mannich base from methylamine, formaldehyde and alkylphenols, which can be used in lubricating oils. Further patents that are of interest in the present context, U.S. Patents 2,810,697, 3,372,118, 3,429,812, 3 472 773, 2 52.7 279, 2 763 616, 3 368 972, 2 410 911, 2 962 442, 3 413 347 and 3 340 190.

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The invention relates to phenates which can be used as additives with a rinsing and dispersing effect, an alkalinity reserve and have antioxidant activity and by simultaneous neutralization of a sulfurized alkylphenol and a Mannich base derived from a lower alkylamine, an alkylphenol and formaldehyde. The neutralization is at elevated temperatures with an alkaline earth metal base in the presence of a hydroxyÜBChen solvent among such Conditions carried out that the loss of amine nitrogen is as low as possible.

The compounds according to the invention are reaction products of an alkaline earth metal base - oxide or hydroxide -, a Mannich base - made from formaldehyde, alkylphenol and a primary lower alkylamine - and a sulfurized alkylphenol. The reaction is carried out at elevated temperatures, so that between the Mannich base and the sulfurized Alkylphenol in addition to the bridge bonds created by the divalent alkaline earth metal, molecular Bonds are formed.

The product thus formed has (regardless of any diluents present) an alkalinity value according to ASTM-D2896 in mg KOH / g in the range from 130 to 450, usually about 175 to 400. The elemental analysis establishes a calcium content of about 4 to 12, usually about 5 to 10% by weight in the product, of at least about 0.1 to 5, usually about 0.5 to 4% by weight and nitrogen content of sulfur from about 0.8 to 10, usually about 2 to 8 wt .- ^ solids. In a 100 neutral oil (where 100 is the viscosity at 100 ° i ^l Ahren integrated = 38 ⁰ G in SUS means) at an alkaline-earth metal concentration of 0.88 formal (3.5 wt .- # for Ca), the viscosity at 99 ⁰ C usually in the range between about 200 and 3000 SU3 and mostly in the range between 500 and 1500 SUS.

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The products of the invention are complex compounds. Ea is assumed to be a significant part of the product · a corresponds to the following formulas:

(1) (2)

In the formulas (1) and (2) means

CHi-N

λ '

α = 1 to 3; β = 0 to 1; χ = 1 to 20, preferably 4 to 9; j = 1 to 10, preferably 1 to 5, mostly 2 to 4; η = 1 to 5f, preferably 1 to 3;

R is a saturated aliphatic, branched or unbranched Hydrocarbon radical with θ to 36 carbon atoms, preferably 10 to 24 carbon atoms,

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where the average number of carbon atoms in the generally "about 10" to 20;

R is a lower alkyl group, usually 1 to 3 carbon atoms, preferably 1 carbon atom and consists of methyl.

In the total product is the ratio of equivalents of alkylphenol from the Mannich base to equivalent alkylphenol from the sulfurized alkylphenol normally at 0.2 to 5: 1, mostly 0.3 to 3: 1 and preferably 0.3 to 2: 1.

The remaining valences of the oxygen atoms are saturated by an alkaline earth metal. These metals are to calcium or barium, preferably galcium. Both valences of the metal can be saturated by the phenoxide; it however, one valence can also be saturated by the phenoxide and the other valence by an alkoxide or hydroxide, with the group depends on the hydroxylic used Solvent and the amount of used in the reaction Alkaline earth metal changes. Some of the phenoxide groups - no more than 10 mole percent - can be bonded to hydrogen be what from the amount of excess alkaline earth metal present depends.

The compounds according to the invention are produced by the Mannich base and sulfurized alkylphenol uas in an equivalent ratio in a suitable reaction vessel (based on phenol) from 0.2 to 5: 1, preferably 0. “3 to 3: 1 united. In addition to the reactants mentioned, an alkaline earth metal oxide or hydroxide (preferably a hydroxide) and a hydroxylic solvent (common Ethylene glycol) trains.

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The amount of alkaline earth metal base depends on the production method of the sulphurized alkylphenol. To the extent that an alkaline earth metal base was used during the preparation of the sulfurized alkylphenol, the further amount of alkaline earth metal base should lead to a total ratio of at least 1 equivalent of alkaline earth metal per equivalent of alkylphenol, generally a ratio of 1.75 equivalent, better 1 , 5 equivalents of alkaline earth metal per equivalent of phenol should not be exceeded _e

The amount of hydroxylic solvent is based on W the solvent used in the individual case. Ethylene glycol, propylene glycol and methanol are examples of useful solvents. Since ethylene glycol is preferably used, only this solvent is discussed in detail. The ethylene glycol is usually used in an amount of about 5 to 35% by weight, preferably about 7 to 20% by weight, based on the total reaction mixture.

In addition to the ethylene glycol, an inert hydrocarbon can also be present as a diluent. Such Inert diluents can facilitate the handling of the reactants and reduce the viscosity of the reaction mixture and facilitate the isolation of the product. With regard to the use of the compounds according to the invention, liquid mineral oils with lubricating viscosity and the product can be isolated as a solution in a mineral oil. The inert diluent should, if it is present at all, in the reaction mixture generally in an amount of from 3 to 65% by weight, preferably 5 to 50% by weight based on the reaction mixture is present be.

It is beneficial to use a small amount of an anti-foaming agent, i.e. one that suppresses foaming, if necessary Means to use. Such an antifoam agent can be found in the

-3 -5

Reaction mixtures in quantities of 1 χ 10 to 1x10 wt .-%

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be at hand. The antifoam agents used are are customary compounds known to the person skilled in the art.

The reaction is generally carried out by combining the sulfurized alkylphenol, the Mannich base, the alkaline earth metal oxide or hydroxide and the ethylene glycol. As stated earlier, an inert diluent can also be present. The mixture prior to the addition of ethylene glycol is preferably heated to at least 90 ⁰ G, but to a temperature below that at which the reaction is carried out usually under HO ⁰ O.

After the ethylene glycol has been added, the temperature is increased to such an extent that the water formed during the reaction can be distilled off overhead. The temperature is then further increased, but not more than 200 ⁰ C. The pressure is reduced so that the ethylene glycol can be distilled. Typically, the temperature should be during the removal of the water from 125 to 160 ⁰ C, while the temperature during the removal of ethylene glycol to HO to 200 ° 0, preferably from 160 set to 180 ⁰ C. The pressure will vary depending on the temperature and the degree of distillation desired. The pressure prevented can vary from about 0.01 to 0.8 atmospheres.

The removal of the water generally takes about 30 minutes to 3 hours. For the removal of the Ethylene glycol are normally used for about 30 minutes to 9 Hours needed. The duration of the reaction, i.e. the time from the beginning of the removal of the water to practically complete removal of ethylene glycol, can take between about 1 and 6 hours be. The reaction time, which, although not a critical factor, should not be unnecessarily extended, depends on the capacity the equipment, the amount of reactants, the degree of foaming and the possibility of temperature control as well as the speed

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speed with which the distillates pass over.

As soon as no more ethylene glycol passes over, the reaction mixture can be cooled down. Depending on the presence and amount of an inert diluent, the temperature should preferably be kept above about 150 ⁰ C, is carried out until a sufficient dilution with a common solvent _a The mixture can be extremely viscous, so that a solution in a solvent at temperatures becomes difficult below about 15O ⁰ C. All common solvents can be used; In view of the intended use, however, one usually uses carbon and ^one -component lubricating oils as a diluent. Various hydrocarbon lubricating oils can be used depending on the intended end use application. After dilution and after filtering, the product is suitable for use as a concentrate or for the production of finished lubricating oils.

In the following, the various lieactants will be considered. The first and easiest lieaction participant is that Alkaline earth metal oxide or hydroxide. As already mentioned, it can be calcium or barium, preferably calcium Act. Calcium compounds are usually used as a calcium compound

I hydroxide a "

Sulfurized alkyl phenols are commonly used in lubricating oils. The manner in which the sulfurized alkylphenols are prepared is not critical to the present invention. The sulfurized alkyl phenol used should be at least about 4 wt -. ^C / o and not more than about 20 wt .- ^, preferably 8 to 18 wt .- ^ and most preferably at least 0.5 to about 12 wt .- $ sulfur, this amount being based on the weight of the sulfurized phenolic compound present which is either not involved in the formation of bridges or is linked by bridges with at least 3 sulfur atoms. Generally lying

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about 1 to 9 wt .- $ sulfur, the amount being based on the Weight of the sulfurized phenolic compound is based on the in a form suitable for a bridging reaction is present.

In most cases, the sulfurized alkylphenols have the following formula

ρ
In this formula, R denotes alkyl having 8 to 36, preferably 10 to 24 carbon atoms, the average number of carbon atoms being between about 10 and 20; y is a number between 1 and 9, preferably 1 to 5, the average over the total compound being between about 2 and 4; η is a number between 1 and 5, preferably 1 and 3. Small amounts of sulphurized phenol - not more than about 10% by weight - with y greater than 9 can be present.

ρ The aliphatic hydrocarbon groups R can be in ortho-, meta or para position be present, where the meta or para position prevails. Da branched chain alkyl groups lead to a reduction in the amounts of ortho-substituted phenols, branched-chain alkyl groups are preferred used. To a certain extent, however, alkyl groups are also present in the ortho position, the ortho-substituted phenols act as chain terminators in the copolymerization of sulfur and alkylphenol.

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- Io -

The sulfurized alkylphenol can be prepared by adding an alkylphenol, sulfur, calcium oxide or calcium hydroxide and glycol are combined and then the sulfurized alkylphenol is isolated. In this context, reference is made to the USA patent 2,989,466 referenced. Sulfur monochloride can also be used to make the sulfurized alkylphenols, preferably in conjunction with a Friedel-Crafts catalyst. Different methods of making

of sulfurized alkyl phenols are "in the United States patents 2,362,289, 2,451,345, 2,744,083 and 3,367,867.

The Mannich bases required can be prepared by adding an alkylphenol, formaldehyde and a lower primary alkyl amine, preferably one having 1 to 3 carbon atoms, most preferably methyl amine, combined. A method for the preparation of Mannich bases is described in German patent application P 21 13 916.2. In the U.S. Patent 3,454,497 is another method of making Mannich bases using primary Amines described.

In most cases the Mannich base corresponds to the formula

CH ₃ NCH ₂

in which the individual symbols have the following meanings:

R is a lower alkyl group, generally one having 1-3, preferably one carbon atom, i.e. methyl;

B / is a saturated aliphatic hydrocarbon radical having 8 to 36 carbon atoms, usually 10 to 24 carbon atoms and usually an average number of

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Carbon atoms between 10 and 20;

χ can range from 1 to 19 and “is on average about 4 "to 9. Smaller quantities - less than 10 wt. fo an I. Iannich bases with χ greater than 19 must be present. Of the The average over the total compound should normally be between 3 and 9, with more than 50% by weight of the compound χ = 3 or more.

The Mannich bases are usually prepared from alkyl phenols in which there is less than 25 mole percent, preferably less than 20 mole percent, ortho substitution. According to the invention, less than 20, preferably less than 10, tfo of the amine group in the p-position to the hydroxyl group of the phenol should be linked in the Mannich base.

The undiluted Mannich base should be at least 2 wt .- ^ nitrogen , efocJi jiidit contain more than about 5 wt .- ^ nitrogen, whereby on average the nitrogen content is between about 2.2 and 4.0 wt .- $. The average molecular weight, determined by osmometry, should be at least 600, better at least 700 and normally not exceed about 5000,

In the following examples, which serve to further illustrate the invention, "parts" always refer to parts by weight understood, unless expressly stated otherwise.

example 1

In a reaction vessel, 8,825 parts of a sulfurized Alkylphenol (prepared according to Example A), 10,350 parts of a Mannich base (prepared according to Example B) as 60 wt Solution in anMid-Gontinent-100-Heutralöl, two parts a foam inhibitor DC-200 and 1,640 parts of calcium hydroxide. The mixture is heated to 121 to 135 ° C and

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«12 -

mixed with 5 150 parts of ethylene glycol. Subsequently, the pressure to 508 mm of mercury was reduced and the mixture was heated to 149 ⁰ C 50 to 70 minutes, with water being removed overhead _o As soon as practically all the water was removed, the temperature for about 2 to 3 hours at 191 C was elevated. The pressure was reduced at the same time ₃ so that at the point in time at which the temperature had reached 171 ^° C., the maximum vacuum was reached. The final pressure in the vessel is no more than 50 mm of mercury. As soon as the temperature has reached 188 ⁰ C, this temperature and the maximum vacuum are maintained for 30 minutes:

The mixture is then rapidly cooled to 149 ° C., whereupon nitrogen is introduced into the system until atmospheric pressure is formed. 4500 parts of a 100-neutral oil are then added to the mixture and the resulting solution is mixed for 3 minutes, the temperature being about 121 ⁰ C is held. The product is then isolated.

The product described in the V / else obtained has a calcium content of about 4.2 wt -. ° β> and a viscosity of about 4000 SUS at 99 ° C.

Example A.

In a reaction vessel were 18,100 parts of polypropylphenol (made from polypropylene with about 12 to 15 carbon atoms), 750 parts calcium oxide and 4,620 parts sulfur added; the temperature of the mixture was kept at 104 ° C. Afterward the temperature was raised to 130-135 ° C, whereupon 580 parts Ethylene glycol were added. The onset of an evolution of hydrogen sulfide could be observed, whereupon a slow stream of nitrogen was passed over the reactor. the The temperature was slowly increased to 169 to 171 C and held at this level for 6 hours. At the end of the time the mixture became

to ground on sth.

cooled to about 107 to 121 ⁰ C; the product could be isolated

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~ 13 -

Example B.

60.4 parts of polypropylphenol (made from polypropylene with about 12 to 15 carbon atoms) were placed in a reaction vessel, whereupon the system was evacuated and flushed with nitrogen, after the end of the flushing it was 17.9 parts. Isobutyl alcohol and 14.5 parts paraformaldehyde were added while the mixture was stirred. Finally, 7.2 parts of liquid methylamine were added to the mixture, the addition taking 3 hours. The temperature was kept at 49 to 66 ^{° C. during the addition.}

After the addition of the methylamine was complete, the mixture was stirred for an additional 15 minutes; then the vessel was vented. The temperature was raised to 88 ⁰ C, the vessel was sealed and the temperature was further increased to 127 ° C and left for 7 hours on this height, the pressure was 1.4 kg / cm. To isolate the product, it was washed with water and the isobutyl alcohol was distilled off.

If necessary, it is possible to dilute the product with an inert diluent in order to make it easier to handle can. The product is then on in vacuo for about 30 minutes 149 C, whereupon it is "ready for use in the final reaction".

Example 2

In a reaction vessel was 8,643 g of a sulfurized alkylphenol (not filtered), 9,255 g of a Mannich base as a 66% strength by weight solution in 100% neutral oil and 1,618 g of calcium hydroxide given; this mixture was then still with 5,122 g of ethylene glycol and 4 g DC-20Ü added as an antifoam agent.

The sulfurized alkylphenol was that described in Example A. Way was produced and filtered and possessed the following characteristics

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data (pure): the alkylphenol consisted of polypropylene phenol with alkyl groups of 12 to 15 carbon atoms; the degree of alkalinity in mg KOH / g was 63.6; Calcium content $ 2.27; Sulfur content 14.99 i> \ Viscosity at 99 ° G 2 740 SUS.

The Mannich base was made from polypropylene alkylphenol (polypropylene with 12 to 15 carbon atoms) described in dep in Example B. v / iron made. The product was found to be 66.7% by weight Solution in a Mid-Continent 100 neutral oil, the following characteristics • on: N = 2.74 #; Degree of alkalinity in mg KOH / g = 109; viscosity at 99 ° C = 425 STJS.

The mixture was ^{heated quickly to 130 °} C. and placed under a vacuum of 254 mm Hg; The water and hydrogen sulfide were removed overhead. Thereafter, the pressure was reduced and the temperature was increased over 4 hours and 20 minutes so that the end temperature was 193 ° G and the ultimate vacuum was about 48 mm Hg. During this time the water and ethylene glycol were withdrawn overhead. The mixture was then cooled to 135 ⁰ C, the vacuum was released by introducing nitrogen and after lowering of the temperature were set at about 127 ° 0 5092 g of a Mid-Gontinent-IOO neutral oil added as a diluent.

* The product in the form of an oil solution wijSB tätsgrad a Alkalini or alkalinity value of 147 mg KOH / g, a nitrogen content of 0.75 foj a sulfur content of 3.2 and a calcium content of ^ _4? 2 i on. After some difficulty, the product could be diluted with more Mid-Continent 100 neutral oil and filtered using a mixture of Gelite 573 and Gelite 545. The filtered product weighed 15,457 g and showed the following fourths: 0.60 fo F, 3.35 fo Ca and 3.12 f, S.

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2101121

Example 3

A reaction vessel was charged with 4-27 g (1 »28 equivalents) of sulfurized alkylphenol and 454 g (0.93 equivalents) of the Mannich base described in Example 2 as a 66.7 weight percent active solution; the mixture was then heated to 95 ⁰ C and treated with 253 g ethylene glycol and 80 g (2.16 equivalent) OaIeiumhydroxid. The pressure was reduced to 254 dim; Water could be collected overhead when the temperature rose to 125 ^° C. The temperature was then raised in the course of 55 minutes further at 15O ⁰ C, after which the pressure was slowly reduced to 25 mm Hg, while the temperature was slowly further raised to 182 ⁰ C. The temperature was left at this level for 15 minutes; the reaction mixture was then allowed to cool and the vacuum was released by introducing nitrogen. The product was diluted with 300 g of a Mid-Continent-100-Ueutralöl. The oil solution was filtered through oil; the filtered product weighed 1,105 g and had the following analytical values : fo Ga: 4.43; 4.24; 1 ° H: 0.82; 0.82; # S: 3.56; Degree of alkalinity in mg KOH / g: 152.5; 151.4.

The sulfurized alkylphenol used had been prepared in the manner described in Example A and had the following characteristics on: 14.9 # S; Alkalinity value mg KOH / g = 62.7; Calcium content = 2.16 #; Viscosity at 99 ° C = 2,435 SUS.

In the manner described in Example 3, further examples were carried out, in each case only the ratio of sulfurized Alkylphenol was changed to Mannich base. Both the sulfurized alkylphenol and Mannich base were used made in the same approach. The following table shows the quantities of materials used and the characteristics of the End product specified. All characteristics relate to a product with 63% by weight of active material in a Mid-Continent 100% neutral oil.

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Table I.

Example sulfurized Mannich ethylene calcium mid-continent alkylphenol, Base, glycol, hydroxide, 100- ρ g g g g neutral oil

4,334

5 1002

ο 6 334

P 7 334

"T 8 668

500 229 72.5 238 ■ 500 458 145 650 1500 458 ' 145 332 1000 344 109 278 500 344 109 449

4.07
4.07 3 at t <3 Alkalinity
Degree,,
mg KOH / g ^ 1.07
1.06 4.36
4.33 3.30
3.23 155.7 0.42 3.74
3.74 4.60 140.1 1.64
1.63 3.78
3.79 1.61
1.50 170.6 1.43
1.39 4.32
4.36 1.98
1.98 162.8 0.61
0.61 3.76
4.04 143.7

= 66.7 wt% active material in mid-continent 100-e neutral oil.

= added after the end of the reaction.

= Analysis carried out on the diluted product.

Example 9

In a reaction vessel was added 427 g of a sulfurized alkylphenol filled in, which was produced as follows:

in a suitable reaction vessel was charged with 3011 g of polypropylene phenol heated (polypropylene with 12 "to 15 carbon atoms) at 66 ⁰ C with 125 g of calcium oxide was added. The temperature was then raised to 132 ° C, whereupon 768 g of sulfur, and then 96 g iithylenglykol added The mixture was refluxed for about 10 minutes, during which hydrogen sulfide was released. The temperature was continuously increased until it had reached 171 ° C. and then held at this level for 6 hours bubbled in nitrogen to create an inert atmosphere, the resulting product weighed 3,666 g and a portion of the product was removed for analysis and filtered.

Analysis: 14.57 ° β> S; Alkalinity value in mg KOH / g = 61.39, which corresponds to a calcium content of 2.19 i °.

To the 427 g of the sulfurized alkylphenol were added 454 g of the Mannich base described in Example 2; the mixture was heated to 93 ° C. and then 80 g of calcium hydroxide and 253 g of ethylene glycol were added. The temperature was then increased in Terlauf of about 1 hour and 15 minutes at 182 ⁰ C while allowed to slowly drop to a final pressure of 40 mm Hg pressure. Baeh ^ em temperature and pressure had been maintained at the specified values for about 10 minutes, the mixture was allowed to cool to 121 ⁰ C, formed a nitrogen atmosphere, and added to 300 g of a Mid-Continent-100 iIeutralöles. The final product weighed 1,185 g. Analysis: f Jl-. 0.71; 0.72; ° / o S: 3.19 » $ Oa: 4.01; Alkalinity value in mg KOH / g: 134.9; 133.9.

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A number of additional sulfurized alkyl phenols were prepared in the manner described in Example A, with the ratio Sulfur to alkylphenol was changed in each case. "These products were then prepared according to Example B. Mannich base combined, essentially in the manner indicated in Example 1. These are in the following table The ratio of sulfur to alkylphenol, the analytical values of the product, the analytical values of the Mannich base and the analytical values of the end product are given

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Table II

Sulfurized alkylphenol example

Reactant product AV ² Sulfur, parts #, S mg KOH / g 81.2 269 4.32 76.5 384 7.69 72.8 576 11.07 67.4 768 18.6 68.1 960 20.1 76.5 384 7.69 76.5 384 7.69 67.4 768 18.6

") Notes on page

Table II continued

Combination of sulfurized alkylphenol and Mannich base example

10 11 12 13 14 15 16 17

sulfurized Mannich base alkylphenol, Reile ^ Parts

3)

Annotations page analysis'
% Approx

378 475 0.84 0.82 4.18 386 475 0.81 0.82 4.35 407 475 0.87 0.88 4.17 427 475 0.82 0.78 4.28 448 475 0.85 0.83 3.91 386 475 0.85 0.85 4.30 604 505 0.47 0.48 4.46 604 505 0.50 0.53 4.35

ς ₁ O

1.31 1.70 2.76 3.17 3.94 1.41 2.14 3.51

A.V. mg KOH / g

152

158

154

147

147 j

156

144

The footnotes listed in Table II have the following meanings:

¹ With the sulfur were 125 parts of OaO, 2900 parts of alkylphenol (alkyl = polypropylene with 12 to 15 carbon atoms) and

96 parts of iithylene glycol combined.

² AV : Degree of alkalinity or alkalinity value (ASTM D-2896).

Prepared according to Example B. 66.7% by weight of active material in 100% neutral oil; Nitrogen content = $ 2.77>.

In addition to the sulfurized alkylphenol and Mannich base, there were 253 parts of ethylene glycol, 80 parts of calcium hydroxide and 300 parts of a Hid Continent 100 hay oil used.

^ The γ / analysis was carried out on the diluted product. Example 18

Into a flask equipped with a nitrogen inlet tube, 100 g of 2,2'-bis (1-hydroxy-4-polypropylenephenyl) disulfide (polypropylene having 12 to 15 carbon atoms) was added as a 75% by weight solution in Oil and 150 g of the Mannich base prepared according to Example B as a 66.7 wt .- ^ solution in a Mid-Continent 100 Itfeutralöl (alkalinity value in mg KOH / g = 108; <fo Ή = 2.74) given and the mixture ^{heated to 100 0} G in a nitrogen atmosphere. 18 g of calcium hydroxide, 29 g of ethylene glycol and 1 drop of DC 200 were then added to the reaction mixture. The temperature was increased to 150 ^° D and the pressure was lowered to 200 mm Hg; these conditions were maintained for 30 minutes. Thereafter, the pressure was reduced to 50 mm Hg and the temperature increased to 180 C; these conditions were maintained for 15 minutes. At the end of time, the mixture was cooled to 100 ⁰ C and filtered through a 5O / 5O mixture of Celite 512 and Dicalite 573rd The filtration was slow. Analysis: Ή = 1.20 #; Ca = 3.52 $> \ AV = 147 mg KOH / g.

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The compounds according to the invention can be used in particular in lubricating oils which not only have a rinsing effect and have a dispersibility, but also an ability to neutralize acid and have an antioxidant effect should.

The compounds according to the invention can be used in various base oils which are used as lubricating oils. Suitable oils as lubricating oils generally have viscosities between about 35 and 50,000 SUS (Saybolt Universal Seconds) at 38 ⁰ C. The oils which are used according to the invention generally have P viscosities at 99 ° C. in the range from about 20 to 150 SUS, preferably about 60 to 120 SUS. The hydrocarbon lubricating oils used can be of natural origin, namely paraffinic, naphthenic and / or asphaltic oils. It is also possible to use synthetic hydrocarbon oils.

The compounds according to the invention can also be used in synthetic non-hydrocarbon oils such as esters, silicates and the like will. The different oils can also be used together, if they are miscible with each other or after they have been made miscible with the aid of mutual solvents.

The compounds according to the invention are usually used in concentrates from about 15 to 70, preferably from about 30 to 60 Grew .- $.

In special formulations, the amount of the respective compounds is generally about 5 to 400, mostly about 8 to 75 mmol / kg, based on metal, depending on the individual case. at For a railroad lubricating oil formulation, the alkalinity value should be at least 5 »better at least 6 and no more than about 15 mg KOH / g are «

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Various other additives can also be added to the lubricating oils. The use of sulfurized aliphatic hydrocarbons together with the additives of the invention is of particular interest. Compounds of this type are well known to those skilled in the art and generally have about 16 "to 50 carbon atoms and between about 15 and 25% by weight of sulfur. Such additives can be present in an amount from 0.05 to 0.75 wt. ^C / o .

In addition to the sulfurized hydrocarbons, they are advantageously used also ash-free washing-up liquids (detergents) and dispersants, so that products with a low ash content are produced » These ashless rinse dispersants are mainly aliphatic polyols with 2 to 6 hydroxyl groups or alkylene polyamines (alkylene with 2 to 3 carbon atoms), containing 3 to 5 amine nitrogen atoms, which either directly to an aliphatic hydrocarbon group with about 30 to 200 carbon atoms, preferably 50 to 125 carbon atoms or indirectly to an acyl group such as succinyl, Phosphoryl, carboxyl, etc., with the acyl group having a hydrocarbon substituent, and with alcohols Forms ester or polyester, and an amide or imide linkage, e.g. a succinimide linkage to the alkylene polyamine contain. In this regard, see U.S. Patents 3,522,179, 3,331,776, 3,219,666, and 3,220,768, in which polyisobutenyl succinimides of alkylene polyamines (polyisobutenyl having 50 to 200 carbon atoms; Alkylene polyamines: alkylene having 2 to 3 carbon atoms and polyamine having 2 to 5 nitrogen atoms; buccine groups to alkylene polyamines = 1-2: 1) are described. Such ashless detergents are generally available in amounts of about 2.5 to 10 wt .- ^, preferably about 3 to 8 wt .- ^ present ",

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In addition, other additives may also be present in small amounts, for example other ash-forming detergents such as sulfonates (neutral and overbased), phosphonates (also neutral and overbased), corrosion inhibitors, agents which improve the "oiliness", pour point depressants, viscosity index improvers, etc.

To show the effect of the compounds according to the invention: a number of laboratory tests and engine tests were carried out; the results of these experiments are shown below Table III compiled.

The first series of tests involved an oxidation test which was used to determine the anti-oxidation effect. 25 g of the oil to be tested a solution · _r were 0 Z6 ml offset, the 2268 ppm copper, 6236 ppm iron, manganese ^ 56-7 ppm 4535 ppm 4535 ppm lead and chromium, each in the lorrn llaphthenate, contained, so that The result was a distribution of the metals which experience has shown is also present in a used crankcase oil in a diesel engine of the General Motors D_? 1 type. The oil sample to be tested was stirred at 171 ° C. in an oxygen atmosphere and the percentage increase in viscosity at 38 ° C. in 10 hours was determined.

The compounds according to the invention were with a 70 V.I.3AE-40-Cl combined to simulate a commercial preparation. In the oil was 59 mM / kg, based on calcium, of the test compound, 6 wt .- $ of a bis (polyisobutenyl succinimide) of tetraethyl enpentamine (mixed polyisobutenyl with an average Molecular weight of about 640 and 1000), 22 mM / kg, based on calcium, calcium mahoganysulfonate (1.67 wt .- ^ Ca), 0.3 wt .- ^ sulfurized paraffin with 17.5 wt .- ^ sulfur and 0.025 wt .- ^ terephthalic acid used.

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The second test to be explained is the so-called silver pressure washer test. In this test, a piece of Eröbe made of .fine silver, $ 99.9 pure, which is welded to a back made of mild steel, is used. The silver plate and the back reinforcement are each 3 _? 2mm, 33mm OD, and 25.4mm ID. In the silver surface there are three incisions that are equidistant from one another and are made with the aid of a 19: mm face milling cutter, which is beveled at the lower end 30. An egg, 25 mm deep and 0.8 mm wide, is buried right through the middle of each of the three raised silver surfaces.

The oilber- ^ destplatte becomes, after! Processing and after each Use annealed to avoid any hardness in the silver. The annealing is done in half a Taei 343 C Hour, after which it is allowed to cool slowly to rairart temperature. After tempering, the surfaces of both sides are pcliert, so that you get a smooth flat surface with a surface finish from about 9 to 12 microinches.

The steel test sample is used to double the metallurgy of the Steel pivot pin in the EMD locomotive engine, the material is AlSI steel No. 8620H. The heat treatment to a minimum hardness of 58 Rockwell C consists of carburizing to a finished layer depth of 0.04 to 0.05 (pit-cold), reheating to 802 ° 0 and quenching in oil as well as a final 8-hour tempering at 204 ° C. Both sides are final Polished to a finish of 3 to 5 microinches. The nominal dimensions are 38.1 mm OD, 22.9 mm ID and 5 mm thick.

To achieve the oscillating movement on the test surfaces A motor driven device is used. A 20 cubic centimeter sample of the fresh oil is taken used in the oil tank; After assembling the apparatus, the oscillating movement is started. After expiration the 10 minutes will last 35 minutes down to a temperature of

209 828/1 17.5

177 ⁰ G, followed by another 15 minutes of operation at a constant temperature of 177 ° 0. The load on the treads is kept continuously at 301 kg / cm during the test with the aid of a calibrated leather. The wattage is recorded during operation at constant temperature as an indication of workload. In addition, the weight loss in silver is determined (the A + sign indicates an increase in weight).

Another test arrangement was used to determine the sediment size, _k formed on the addition of sulfuric acid. Since diesel fuels contain sulfur and form sulfuric acid, it is desirable that only minimal amounts of sediment form when neutralized with sulfuric acid. The alkalinity value is determined on the sample to be tested and the amount of concentrated HpSO., Which is required to neutralize the sample, is calculated. 150 ml of n-heptane are added to a 50 g sample and the mixture is stirred in a Waring mixer. Sulfuric acid is then added dropwise over 5 minutes in an amount sufficient to neutralize the base present; then the mixture is homogenized for 10 minutes. After this time, the solution is divided into 2 calibrated 100 ml centrifuge tubes and centrifuged for 0.5 hours at 2,200 revolutions per minute. The amount of sediment is read and the two readings are averaged. The results are recorded as ml sediment per 10 mg KOH / g of sample and ml sediment per 10 mg KOH / g of sample due to the amine nitrogen.

The oil of the composition given above was used for the oxidizer B test and the silver pressure washer test. ] For the sediment test, a sample was used which had been prepared as a 3% solution of the active material in a 100-liter neutral oil. The results of the tests are compiled in the following table.

209828/1175

N) O CD CO ISJ CO

Oxidation text
^ Viscosities too
would take in 10 hours. Table III 165 165 Sulfuric acid sediment,
per 10 AV per 10 AV,
based on H. 0.71 example 42 165 160 0.74 2 58.5 oilber pressure washer
Weight watt
loss 45 min 60 min. 177
177 175
180 0.14 2.1 3 56.5 177 162 0.20 2.4 4th 73.5 +0.9 165 162 0.25 2.8 VJl 14.7 +0.4 180 145 0.94 2.1 6th 25.8 0.9
2.3 0.98 0.28 7th 64.7 1.2 182
170 192
170 0.35 8th 0.9 202
175 197 '
167 0.59 9 35.3 2.1 167 177 0.55 10 36.6 185 192 0.55 12th 31.1 1.1
0.6 0.22 13th 23.9 2.2
0.4 0.22 14th 1.0 0.7

In order to show the effect of the compounds according to the invention under severe conditions in a diesel engine, a 180 BMEP test was carried out. The used one-cylinder diesel engine had a cylinder inner diameter of 13.02 cm and a stroke of 16.51 cm _o amounted The braking force 55 PS and the motor ran at 1881 kcal per minute and 1880 revolutions per minute at a Air temperature of 124 ° C, a temperature of the outflowing cooling water of 88 ⁰ O, a Cl storage temperature of 96 ° C and with a fuel that had a content of 1.0 wt .- ^ sulfur. Using the oil described above, the test was carried out for 120 hours; the following results were achieved:

Table IV - 1 - 0.8 fields 70 - 55 Underside of the head example Hillen ¹ - 0.5 - 0.8 285 - 20th - 20th 3.1 2 77-9.5 - 0.5 - 0.5 65 - 45 - 40 2.4 3 90 - 2.2 - 1.2 - 0.7 235 - 205 -125 4.3 6th 92-8.6 - 0.6 - 0.9 55 - 100 - 81 6.2 8th 64-3.9 - C, .5 - 0.5 310 - 35 - 10 4.1 9 * 94-14 50 - 8.4 16+ 17 - 2.8

| * JTur performed for 118 hours. The Cl contained

0.5 wt .- ^ of a sulfurized paraffin with $ 13 sulfur,

+ Results obtained after 60 hours.

¹ 0-100, 100 = completely filled.

² 0-800, 800 = completely black. 0-10, 10 = completely clean.

The above results show the excellent effect of the compounds according to the invention under very different conditions. The compounds of the invention only give

209828/1 1 75

small amounts of sediment "in the case of IT neutralization in sulfuric acid. They also lead to a" remarkable reduction in the loss of wear and tear "in the case of Sil" b. It is also important that under extremely difficult conditions "at high temperatures in diesel engines, they can permanently ensure only small amounts of deposits. They" also have an excellent antioxidant effect, reduce the increase in viscosity in lubricating oils and are distinguished by the ability to to neutralize large amounts of acid.

209828/1175

Claims (1)

(D Claims The reaction product from (1) a Mannich base of the formula 2181121 CHaNCH in which R * is a lower alkyl group with t to 3 carbon atoms, R is a saturated aliphatic hydrocarbon group with 8 to 36 carbon atoms and
χ ¹ a number from 1 to mean (2) a sulfurized alkylphenol of the formula in which B is an alkyl group with 8 to 36 carbon atoms, η a number τοη 1 to 5 and y ^{1 is} a number τοη 1 to 9 mean, 209828 / t! 75 _ 4L "_ (3) an alkaline earth metal base in which the metal consists of barium or calcium, the ratio of equivalent of alkylphenol in the Mannich base to equivalent of alkylphenol in the sulfurized alkylphenol over the entire reaction product being 0.2 to 5: 1, a total of 1 to about 1.75 equivalents of alkaline earth metal base per equivalent of alkylphenol being used and the solution of the reaction product comprising in a 100 neutral oil at a calcium or barium concentration of 0.88 formally a viscosity at 99 ⁰ C in the range of about 200 to 3000 SUS. The reaction product according to claim 1, characterized in that the alkaline earth metal is calcium, the reaction product has an alkalinity 130-450, 4 to 12 wt. -Fi calcium and containing from 0.1 to 5 parts by fa nitrogen. The reaction product according to claim 1, characterized in, that R is methyl. The reaction product according to claim 1, characterized in, that R is methyl, the ratio is 0.3 to 3: 1 and the alkaline earth metal is calcium consists. The reaction product according to claim 1, characterized in, that the alkaline earth metal base consists of calcium hydroxide, R is methyl and the reaction product an alkalinity value of 175 to 400 mg KOH / g, one Nitrogen content of 0.5 to 4 wt .- ^, and one Sulfur content of 2 to 8 wt .- ^ and in solution in a 100% lieutral oil with a Ca concentration of 0.88 formally has a viscosity at 99 ° C in the range of about 500 to -1500 SUS. 209828/1175 6. The reaction product according to claim 5, characterized in that the ratio of equivalents of alkylphenol in the Hannich base to equivalent alkylphenol 0.3 "to Is 2: 1. 7. The reaction product according to claim 6, characterized 2 3 records that R and R are polypropyl at about 12 "to 15 Mean carbon atoms and the alkaline earth metal base consists of Ca (OH) p. ψ 8. Reaction product according to claim 1 from (1) a Kannich base of the formula I, where R is the has given meaning, R is polypropyl with about 12 to 1 is 15 carbon atoms and χ is a number from 4 to 9 means (2) a sulfurized alkylphenol of formula II, 2
where R is polypropyl with about 12 to 15 carbon 1 1 means atoms and η and y are each a number mean between 1 and 5 and (3) a Galcium Base, where the ratio of equivalent alkylphenol in the P. Mannich base to equivalent alkylphenol in the sulfu-. ated alkylphenol is 0.3 to 3: 1 over the entire reaction product, a total of 1 to 1.75 equivalents of calcium base per equivalent of alkylphenol are used and the solution of the reaction product in a 100% neutral oil at a calcium or barium concentration of 0.88 formally a Viscosity at 99 ° C in the range of about 500 to 15C- ¹ O üUo. 9. uchmieröl, characterized by a content of 5 to 400 nil-i / kg, based on OaIcium or barium, duo Reaction limits according to Annn-'ucii 1 or 3. 2 0 9 8 28/117 5 10. Lubricating oil, characterized by a content of 8 to 75 mM / kg, based on calcium, of the reaction product according to claim 1 or 8. 11. Lubricating oil, which is particularly suitable for use in railroad diesel engines, marked by a content of the reaction product according to claim 1 in such an amount that an alkalinity value from about 5 to 15 mg KOH / g, and a content of 2.5 to 10 wt .- / S of a polyisobutenyl succinimide an alkylene polyamine as a lubricating oil detergent and 0.05 to 0.75 wt% of a sulfurized aliphatic Hydrocarbons with 16 to 50 carbon atoms. For Ghevron Research Company, San Francisco, CaI., Y. St.A, Lawyer 209828/1175