DE3122918A1 - "THIOMOLYBDAEN DERIVATIVES OF AMERIC ACID IMIDES AND LUBRICANE OIL COMPOSITIONS" - Google Patents

Description

Müller, Schupfner & Gauger Karlstrasse 5
Patent attorneys 2110 üuchholz / Nordheide

T-027 81 DE

D 76, y35-6-F (HWA)

06/09/1981

TEXACO DEVELOPMENT CORPORATION

2000 WESTCHESTER AVENUE WHITE PLAINS, N.Y. 10650

UNITED STATES.

Thiomolybdenum derivatives of succinic imides and lubricating oil compositions

I i - L. yj 1 \ J

Thiomolybdenum derivatives of succinic acid imides and lubricating oil compositions

The invention relates to new additives that Lubricating oil compositions are suitable for wear resistance, dispersibility, anti-oxidation and friction reduction properties to rent. ·

Compounds of the type indicated here have not previously been used in lubricating oil compositions. The closest prior art, US Pat. No. 3,010,902, discloses lubricant additives consisting of the reaction of sulfur with an unsaturated alcohol or an organic base with hydrocarbon groups and subsequent reaction of a molar excess of the compound obtained with molybdenum blue ( Mixed oxide of the formula MoO ₂ · ή- MoO- · 6H ₂ O) obtained product. In contrast, the present compounds are prepared either by generating an inorganic thiomolybdenum compound before reacting it with the dispersant or by treating an oxymolybdenum dispersant complex with hydrogen sulfide.

ORiGSIMAL INSPECTED

■ r-7.

According to the invention it was surprisingly found that a composition of matter consisting essentially of the Reaction product of an alkenyl succinic acid imide of the following formula:

I ^> N CH ₀ CH ₀ (NHCH ₀ CH ₀ ) NH,

tn «L

where R = an alkenyl radical with 50-200 carbon atoms

in the chain, and χ = an integer from 0-10,

with 0.1-10 equivalent atoms of molybdenum from either (1) a sulfur-molybdenum compound or (2.) a molybdenum compound and H-S, has excellent properties as a lubricant additive. The starting succinic imide can either be preformed or formed in place.

The invention also provides a lubricant which is between 1 and 55 percent by weight of the aforesaid composition with the remainder being a mineral oil of lubricating viscosity.

° ^{RiG! NAL}

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It is believed that, based on their chemical analysis and their manufacture, the products according to the invention Have structures like the following: 0

N-CH ₂ CH ₂ (NH CH ₂ CH ₂ ) _x NH ₂ (H ⁺ )

MoS

^{1 2} Jn

(-ro)

with η = 1-10 (based on Mo anions in the range from MoO. to a polymolybdate with 10 Mo atoms), 0-10,

ζ
m

3-0 and

1-10, but not greater than x + 1.

Structures of the following type are examples of a second possibility with covalent bonding of Mo to N:

N-

.NH

yV? π

with Z = 1-5, ρ = 0-2 and x, y, ζ and η as before.

ORIGiNAL INSPECTED

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It is also believed that structures exist in which the Mo moiety is covalently attached to two or more alkenyl succinic acid imide moieties is bound.

In the structures listed above, the Mo-containing Units and the ethyleneimine units either randomly or sequentially, and the Mo-containing units Units can also be terminated with the ethyleneimine units located close to the succinic acid imide ring be.

The molybdenum content can either have only one Mo atom or two or more Mo atoms, separated by S or O atoms are connected so that cyclic or polymeric compounds are formed.

The preparation of the reaction product employed in a lubricant composition according to the invention is relative uncomplicated and inexpensive to carry out.

The composition according to the invention consists essentially of products obtained by the following reactions will. The reactions listed below illustrate the use of commercially available or easy to prepare hexavalent molybdenum compounds,

however, molybdenum compounds of lower value can also be used without adversely affecting the properties of the products obtained. [% -

In a manufacturing process, a thiomolybdate derivative of an alkenyl succinic acid imide of a polyamine with the Formula given above in which, in particular, R = polyisobutenyl with a molecular weight of

approx. 700 - 3000 (preferably approx. 1200), and χ = 1 - 10 (preferably 2 - 4)

are, with an ammonium or amine salt of a molybdenum thioic acid with 1 to 4 sulfur atoms per molybdenum atom such as is prepared as follows: ti) reaction of an aqueous solution with 0.1-10 (preferably 1-2) molar amounts of in particular ammonium tetrathiomolybdate with 1 mol of the alkenylsuccinic acid imide in a hydrocarbon solvent;

(2) Separating the water by azeotropic distillation with simultaneous separation of ammonia and a smaller part of the sulfur than hydrogen sulfide;

(3) filtering; and (k) stripping off the organic solvent under reduced pressure. The product has dispersibility in lubricants, anti-oxidation properties and exceptionally good friction reducing properties.

In a second manufacturing process, a thiomolybdenum derivative is used of an alkenyl succinic acid imide prepared as follows: (1) conversion of 0.1-10 (preferably 1-2; equivalent

ORiGfNALINSPECTED

atoms of Mo from an aqueous "molybdanic acid" solution % - (produced by non-reducing acidification of aqueous Na-MoO.) with an alkenyl succinic acid imide of a polyamine with the definition given above, which in a mixed solvent of a hydrocarbon and an ether based on ethylene glycol, which has either terminal kydroxylalkylether or arylether groups is dissolved, (2) treating the molybdenum-succinic acid imide reaction intermediate with approx. k mol HS per mol Mo, (3) separating the water by azeotropic distillation, (4) filtering and (5) Stripping off the solvents under reduced pressure. The resulting product has dispersibility, is wear-retardant and has very good friction-reducing properties.

The second manufacturing process can be modified by (1) using a small percentage of a non-volatile polyglycol derivative (alkylphenyl ether) instead of the ether solvent and (2) only about 1-2 moles of H _? S per mole of Mo are added. The polyglycol is preferably an alkylphenyl ether of ethylene glycol or a polyethylene glycol or a monononylphenyl ether of ethylene glycol or a polyglycol with 2-10 oxyethylene units. The product obtained by this modified process is antioxidant, has dispersibility and very good friction-reducing properties.

ORIGINAL INSPECTED

In a further modified production process, thiomolybdenum derivatives of an alkenyl succinic acid imide can be used can be prepared from an ammonium thiomolybdate intermediate formed in situ by mixing the alkenyl succinic acid imide with an aqueous solution of an ammonium salt of oxymolybdic acid, followed by treatment with hydrogen sulfide using a molar ratio from hydrogen sulfide to molybdenum from 1: 1 to 4: 1.

In another modification of the manufacturing process, the thiomolybdenum derivatives are obtained when the aqueous Solution of an ammonium salt of oxymolybdic acid by reacting molybdenum trioxide with at least 1 mol of aqueous Ammonium hydroxide is generated.

Another modification is to form the sulfur molybdenum compound in situ by contacting the succinic acid imide with water, molybdenum trioxide and less than the stoichiometric amount of ammonium hydroxide, preferably 0.1-0.5 moles NH.OH per mole molybdenum, followed by a treatment with hydrogen sulfide using a molar ratio of H _? S: Mon from 1: 1 to 4: 1.

These modifications can be varied by adding (1) a minor Percentage of a non-volatile polyglycol ether used becomes, (2) the volatile hydrocarbon solvent

ORIGINAL

is omitted, (3) water by heating under one
Inert gas separated to 100-150 ⁰ C and optionally the
Separation of the water is terminated by applying reduced pressure at the elevated temperature.

As mentioned above, the reactions to be carried out in the process are carried out in the absence of a catalyst,
but usually in the presence of a solvent
or diluent or a mixture thereof carried out in order to simplify the reaction. Solvents are removed in the later stages of the process; the thinners or non-volatile ether components are compatible with lubricating oils.

The following examples serve to illustrate the invention

example 1

Production of thiomolybdenum derivatives of an alkenyl succinic acid imide from ammonium tetrathiomolybdate

A suspension (partial solution) of 13.50 g (approx. 0.05 mol)
(NH ^) ₂ MoS ^ in 50 ml of water was in a solution of 340.0 g (0.06 mol) of a 50 % oil concentrate of a polybutenylsuccinic acid imide of triethylenetetramine in 200 ml
Cyclohexane stirred in. This mixture was under N-,

heated to reflux and the water was removed by azeotropic distillation into a Dean-Stark receiver. After 2 hours at 78-100 ⁰ C, the anhydrous reaction mixture was filtered at room temperature and then distilled to remove the solvent to, up to 100 mm C at about 10 degrees. The yield was 346 g of a clear, deep brown product with the following analysis: % Mo = 1.04, % N = 0.90, % S = 0.83. From these analyzes, the S: Ho atomic ratio was calculated to be 2.40.

Example 2

Preparation of a thiomolybdenum derivative of an alkenylsuccinic acid imide via an in-situ prepared thiomolybdate intermediate

A solution of 24.20 g (0.1 mol) of Na ₂ MoO ^. 2H ₂ O in 25 ml of water was mixed with 10.0 g (0.1 mol) of concentrated H ₂ SO. treated, followed by the addition of 100 ml of diethylene glycol dimethyl ether (diglyme). A solution of 583.3 g (approx. 0.1 mol) of the polybutenylsuccinic acid imide of triethylenetetramine used in the previous example in 500 ml of cyclohexane was added to the resulting solution of this "molybdic acid". After stirring for 0.5 h at ambient temperature, the mixture was left with sulfur water for 2 h

ORIGINAL INSPECTED

Gush substance through the mixture at a rate of 75 ml / min (approx. 0.2 mol / h). The deep orange mixture was heated to reflux and the water was removed by azeotropic distillation at 78-93 ° C. over 2.5 hours. The mixture was cooled and filtered to remove the Na 1 SO 4 by-product and other insolubles. The filtrate was stripped off in order to separate off solvents, specifically up to 80 ^° C. at about 10 mm, so that 609 g of the product were obtained. The analyzes were as follows: % Mo = 1.53 (= theoretical), % N = 0.82, % S = 1.10 and % Na = 0 _; 17. The S: Mo atomic ratio was calculated to be 2.16 (versus 4: 1 for the insert).

Example 3

Preparation of a thiomolybdenum derivative of an alkylene succinic acid imide via an in situ prepared thiomolybdate intermediate in the presence of an ethoxylated phenol compound

The same materials and steps were used as in Example 2, except that (1) the "diglyme" cut. medium was replaced with 12.0 g Surfonic N-60 (a polyethoxylated nonylphenol from Oefferson Chemical Co.) and

(2) only half the amount of H ₂ S was added, using the previous throughput, but only for 1 hour (instead of 2 hours). The product yield was 594 g; the analyzes were as follows: % Mo = 1.36, % S = 0.87, % H = 0.93 and% Na = 0.16. The S: Mo molar ratio was calculated to be 1.9: 1, which was essentially the same as the use ratio.

Example 4

Improved Process for the Preparation of a Thiomolybdenum Derivative of an Alkenyl Succinic Imide

This method differs from the previous example in that there is no volatile organic Solvent is used and that water is separated off by blowing N ~ in at a higher temperature.

■ ι it. ... ic: ·. '. «' -., ι · Lo: .JiHj um .; ic filled in the reaction caps. The agitated mixture made H _? S with a through

rate of 75 ml / min (approx. 0.2 mol / h) at 80-90 ⁰ C for 2 h. The _{flow of H 2} S was turned off and N ~ was bubbled through the mixture while it was heated to 150 ° C. so that the water was separated. After 2 h at 150 C, a vacuum of approximately 10 mm for 0.5 h at 150 ⁰ C is applied. Then the reaction mixture was at approx. 120-130 ⁰ C filtered to separate the Na ^ SO by-product. 524 g were obtained. The analyzes were as follows: % Mo = 1.5, 1.6, % N = 0.90, % S = 1.24 *, 1.40 and % Na = 0.24. The molybdenum conversion was essentially quantitative and the S: Mo molar ratio was calculated from the analyzes to be 2.44: 1.

Example 5

Production of thiomolybdenum derivatives of an alkenyl succinic acid imide from an in situ generated ammonium thio-

'molybdate intermediate

A solution of ammonium molybdate was prepared by adding 12 ml (ca. 0.18 mole) of concentrated ammonium hydroxide to a moving mixture of 10.60 g (0.075 mol) of molybdenum trioxide and 20 ml of water with stirring for 15 minutes set at 55-65 ⁰ C . The solution obtained was a preheated (to 65 ⁰ C) mixture of 420 g (0.075 mol) of one

50% oil concentrate of a polybutenyl succinic acid imide of triethylenetetramine and 8, A- g "Surfonic N-60" (a polyethoxylated vinyl phenol from Jefferson Chemical Co.) was added. Then the reaction mixture was heated to 80 C, and hydrogen sulfide was at a rate of 56 ml / min (about 0.15 mol / h) for 1 h at 80-85 ⁰ C. The mixture bubbled. The HS power was turned off and N _? was bubbled through the mixture with heating to 150 ° C. so that the water, ammonia and a small amount of HS were separated. After further bubbling of nitrogen at 150 ⁰ C for 2 h, the almost clear product was filtered at about 120-150 ⁰ C; the yield was 387 g of a clear brown product. The analyzes were as follows: % Mo = 1.26, % N = 1.00 and % S = 0.77. The S: Mo molar ratio was calculated from the analyzes to be 1.83: 1.

Example 6

This example describes the preparation of thiomolybdenum derivatives of an alkenyl succinic acid imide from an in-situ formed ammonium thiomolybdate intermediate in a one-pot process, with a significantly less than stoichiometric amount of ammonium hydroxide is used.

ft »β ■ * #

tt Ti * ft ο -

ο ac% ♦ · ■ ■ »

The same materials were used as in Example 5, but 4-0 ml of water and only 1.0 ml (approx. 0.015 mol) concentrated ammonium hydroxide were used. This procedure differs from Example 5.

The mixture of alkenylsuccinic acid imide and polyethoxylated alkylphenol was heated to 65 ° C., then 35 ml of water and the MoO ^ were added one after the other. This mixture was heated to 80 ° C. for more than 1 hour, then a solution of 1 ml of concentrated NH.OH and 5 ml of water was added. Hydrogen sulfide was bubbled through this mixture and the mixture was stripped under nitrogen as in Example 5. The product has been well filtered at 120-150 ⁰ C, and it gave a clear product. The analyzes were as follows: % Mo = 1.22, % S = 1.00, % N = 0.76 (probably an error in the analysis; approx. 1.0 % N is to be expected). The molar ratio of S: Mo was calculated from the analyzes to be 2.4-6: 1.

Example 7

This example describes the preparation of thiomolybdenum derivatives of an alkenylsuccinic acid imide from an ammonium thiomolybdate solution, which is obtained by reacting a

aqueous ammonium sulfide solution was formed with molybdenum trioxide. This procedure differs from Example 1 in that a crude ammonium thiomolybdate with an average stoichiometry of approx. 2: 1 S: Mo would be prepared by adding 10.80 g (0.075 mol) of molybdenum trioxide to a solution of 19.6 g (approx. 0.15 mol) of a concentrated ammonium sulfide (52-60 %) solution and 35 ml of water. The resulting solution / suspension was added to a mixture of 525 g (about 0.094 mol) of a 50 % oil concentrate of a polyisobutenyl succinic acid imide of triethylenetetramine and 10.5 g of polyethoxylated alkylphenol. The reaction final mixture wurce for 1 h at 75 C stirred before N- wurce blown by heating to 150 ⁰ C, so that water, ammonia and a small amount of hydrogen sulfide were deposited. After 2 hours at 150 ° C. the mixture was filtered at 120-150 ° C. and a clear brown product was obtained. The analyzes were 1.14 % Mo, 0.96 % N and 0.91 % S. The atomic ratio of S: Mo was calculated from the analyzes to be 2.39.

Example 8

This example describes a method for making a thiomolybdenum derivative of an alkenyl succinic acid imide using a molybdenum oxo acid and hydrogen sulfide as the only other reagents.

ORIOINAL INSPECTED

In carrying out this procedure, a mixture of 42O g (0.075 mole) of a 50 % oil concentrate of a polybutenyl succinic acid imide of triethylenetetramine (a polybutenyl group derived from an olefin having a molecular weight of ~ 1300) and 8.4 g of a polyethoxylated nonylphenol was placed in a reaction flask heated to 65 ^{° C. under N-.} Then 30 ml of water and 10.80 g (0.075 mol) of molybdenum trioxide were added, and the mixture was ^{stirred for 0.5 h at 65 °} C., followed by heating to 80 C. Then hydrogen sulfide gas was introduced at a rate of 56 ml / min (~ 0.15 mol / h) by the moving mixture at 80-85 ⁰ C for 1 h bubbled the HPS flow was stopped, and N- was blown at a rate of 50 ml / min through the mixture, while this was ^{heated to 150 °} C., water and excess HS being separated off. After 2 h at 150 C, the hot mixture was filtered (at 150-120 ⁰ C), remove the small amounts of insolubles to. This is in contrast to Example 4, which also requires large amounts of sodium sulfate by-product to be separated.

The filtered product of this example had the following analysis: 1.50 % Mo, 0.94 % N and 1.09 % S. The conversion of Mo was 93%, and the atomic ratio of S: Mo was determined from the analyzes to be 2, 18: 1 calculated.

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Example 9

This example describes a modification of the method according to Example 1, in which the surfactant, a polyoxyethylated nonylphenol, is omitted. The same materials were used in carrying out this procedure as in Example 8, except that the polyethoxylated nonylphenol was omitted. After carrying out the same reaction, a filtered product is obtained which has the following analyzes: 1.52 % Mo, 1.08 % S and 0.99 % N. These results correspond essentially to those of the product of Example 8.

Example 10

This example illustrates a "one pot" method for preparing a derivative of a Thiomolybdän Alkenylbernsteinsäureimids, wherein the alkenyl succinimide is prepared in situ at 110 ⁰ C. To a mixture of 10.95 g (0.075 mol) of triethylenetetramine and 138 g of diluent oil (100 Pale Oil E HF), which was stirred at 60 ⁰ C was 199.0 g (0.083 mole) of a polybutenyl succinic anhydride having a molecular weight of about IA -OO (the approximately 18% diluent oil contained) during a period of 0.5 h at 60-80 ⁰ C was added. The reaction mixture was blowing in N- with a throughput of about 50 ml / min

ORIGINAL INSPECTED-

heated to 110 ° C., the water of reaction being separated for the most part. After 2 h at 110 ^° C., the mixture was left
cool the gel concentrate of the alkenyl succinic acid imide so produced while (1) 7.0 g of polyethoxylated
Nonylphenol, (2) 30 ml of water (heated to 100 ⁰ C) and
(3) 10.80 g (0.075 mole) molybdenum trioxide was added. This mixture was stirred ^{at 95 ° C. for 0.5 h,}
after which hydrogen sulfide with a throughput of
56 ml / min (0.15 mol / h) was blown through ^{at 95 ° C. for 1 h.}

The filtered product had the following analysis values: 1.68 % Mo, 1.03 % N and 1.04 % S. The Mo conversion was 86 % y and the atomic ratio of S: Mo was 1.86.

Example 11

This example describes a modification of the previous procedure using the alkenyl succinic acid imide
is produced in-situ at 95 ° C.

The same materials (and amounts) were used as in Example 10, and the procedure was identical,
However, the starting mixture of amine, diluent oil and alkenylsuccinic anhydride is kept at 95 ° C. for 2 h

(instead of at 110 ⁰ C) was heated. Then the water and MoO _{3 were added} at 95 ^° C. and the last part of the process was ended exactly as in example 10.

The filtered product of this example had the following analytical values: 1.68 % Mo (identical to Example 9), 1.06 % N, and 1.38 % S. The Mo conversion was 86% and the S: Mo atomic ratio was 2.46.

Lubricant compositions according to the present invention contain at least one of the aforementioned products in an amount which is in a range of about 0.01-55.0 % ; between 0.1 and 15.0% by weight, in particular at least 0.5-10.0% by weight, are preferably used. Alternatively, the preferred quantity ranges are between about 0.01 and 5.0% by weight of molybdenum, 0.03-0.15% by weight and 0.05-0.08% by weight.

The specified compositions can also be a combination contain other known additives in amounts necessary to achieve the specific effects of each additive sufficient.

Lubricating oil compositions according to the invention contain a major amount of any of the known oils with lubricating

viscosity as suitable base oils. They include hydrocarbon or mineral lubricating oils or naphthenic, paraffinic and mixed naphthenic and paraffinic Species. Such oils can be prepared by any of the conventional methods, e.g. B. by solvent and acid refining, be refined. Synthetic hydrocarbon oils from Alkylene polymer type or those made of coal and shale can also be used. Alkylene oxide polymers and their derivatives such as the propylene oxide polymers and their ethers and esters, in which the hydroxyl end groups are modified are also suitable. Dicarboxylic acid ester type synthetic oils including dibutyl adipate, di-2-ethylhexyl sebacate, Di-n-hexyl fumarate polymer, dilauryl celate and the like can be used can also be used. Synthetic alkylbenzene types Oils such as tetradecylbenzene, etc. are also included.

The oil blends of the products of the preceding examples were tested by various tests. With the bench VC test the turbidity was measured; the lower the haze values given below, the better the dispersibility. This test is carried out using exact volumes of the test oil, a synthetic one Blowby agent and a mineral oil thinner in an examination bottle be mixed. The bottle is then placed on a shaker and kept at 137.7 ° C. for 4 hours shaken. After heating, the sample is diluted with more mineral oil, cooled to room temperature, and then

check the turbidity of the sample with a Lumetron opacimeter measured, which has a 700 mu filter. The synthetic blowby agent is a hydrocarbon fraction, which has been oxidized under certain conditions. This material simulates the oxidation compounds, which penetrate past the piston rings into the crankcase of an internal combustion engine.

The Bench-L-38 test simulates the conditions in an axle box that were used in the engine test Federal Method No. 791a, Method 34-05.1 (US test method) and forms a way of investigating the corrosion properties of copper and lead bearings Motor oils. The copper strip test is based on ASTM Method D-130; a polished copper strip is used immersed in a certain amount of pure oil and in oil with the additive to be examined and on a Temperature and time characteristics of the examined material heated. At the end of this period the copper strip becomes removed, washed and tested to ASTM copper strip corrosion standards compared.

The third test was that disclosed in U.S. Patent 3,384,588 Four Ball Wear Test, in which the wear is detected that a lubricating oil allows under engine test conditions with and without additives to be tested. The greater the wear and tear, the worse it is

Ability of the oil composition under study to produce such a Prevent wear and tear. This wear is measured in the form of the wear scar diameter. The test was carried out for 2 hours at 600 rpm / 93.3 ° C / 40 kg load. The coefficient of friction was recorded at the end of the test after the anti-friction film had fully developed.

The small engine friction test is a test with a single cylinder engine, whereby the frictional properties of an oil are measured. The values given in Table I. are based on the torque required to drive a motor containing the oil under test. The results of this test complement each other with field tests using a large fleet of vehicles different driving conditions on the road, such as the percentage change in torque with a percentage Change in fuel consumption is correlated.

The Bench IIID test measures the oil thickening tendencies of engine oils under high temperature conditions. In the experiment, an oil sample is oxidized in the presence of air with an iron and copper catalyst at 171.1 ° C. After 24, 48 and 72 hours, the percent viscosity increase at 4-0 ⁰ C and the evaporation losses are determined in ml of the oxidized oil. After 24 and 48 hours, fresh top-up oil is added to the oxidized oil.

TABEL

Test oils Test oil preparation ^ Amber
acid imide
Wt% Kupferstr, - Bench IIID
Test, % Vis- 4-ball test . Frictional
coefficient Bench Bench Small engine with Prod,
from Bei
game no. Mon addition
Weight- «(56 Mo) 8.0 Correction test
148.8 ° C / 3 h kosher
after 72 h Lock
mm 0.095 VC
test L-38-
Te st
mg BWL Friction test
% Friction reduction nothing 0 IA too viscous,
to measure 0.41 0.075 2.0 26.6 0 ± 2 1 8.0 (0.085 3.0 IB 91 0.37 0.079 5.0 - 25th 2 5.2 (0.07 2.0 IA - 0.34 - 4.0 24.5 21st 3 5.9 (0.08) 2.0 IA 94 - 0.071 3.5 17.6 20.17 4th 5.9 (0.08) - 2A 95 0.33 - - - - 5 2.0 - - - - - 21.3 6th 6.16 (0.08) _ IA 4.5 15th 7th _- 18.9

(1): The test oils were IOW-40 grade oils that also contain a succinic acid imide dispersant,

a zinc dialkyldithiophosphate, an overbased calcium sulfonate, an aromatic secondary amine,
an ashless rust preventive, a viscosity index improver
Pour point depressants and an anti-foaming agent included.

ro co oo

From Table I it can be seen that the additives according to the invention are effective in improving the properties of lubricating oils. Thus, the product from Example 1 improves the oxidation resistance of the test oil in the Bench IIID test, improves the ability of the test oil to prevent wear by approximately 10 % in the -ball test and reduces friction by 25 %. The additives from Examples 3 and 4, which give the oils approximately the same (0.08 %) Mo content, although they are used in lower total percentages by weight, and the additive from Example 2, which has only one Mo content of 0.07% all show essentially the same results in most tests and have the same effect in the 4-ball test. The results of the copper strip corrosion test and the Bench-L-38 test show that these sulfur-containing molybdenum additives do not decrease (and possibly improve) the corrosion resistance of the prepared oils. It should be noted that the test oils were completely prepared oils with the additives according to footnote (1); However, the data show that even fully formulated oils can still be improved with regard to wear prevention, friction reduction and oxidation resistance through the incorporation of the additives according to the invention. This is surprising and not to be expected.

TABLE II

Mode of action of additives as oxidation and corrosion inhibitors compared to conventional additives

Oil mixture A B C D

Composition (% by weight) Additive according to Example 4 (% Mo /% N) PIB succinic acid imide from TETA {% N) zinc dialkyldithiophosphate arylamine (oxidation inhibitor) phenolic antioxidant

Bench IIID oxidation test

% Increase in viscosity (after 72 h)

L-38 corrosion test, (mg BWL)

(1): The test oils (10W-30 degrees) also contained 0.22 % Ca from an overbased calcium sulfonate + 6.75 & a dispersant as a viscosity index improver + 0.05% of a pour point depressant in a solvent-neutral basic oil.

349 - 4.2 (0.06 / 0.04) 4.2 4.2 0 22 0 (0.0 ' - - 0.2 ο, 5 0.5 0.5 0.2 - - 0.2 17th - - 0.2 5.6 42 0 3 17.5 7.2

The test results of Table II show that the thiomolybdenum derivative of an alkenyl (PIB) succinic acid imide of triethylenetetramine (TETA) according to Example h exhibits oxidation and corrosion prevention properties in the absence of the additives normally used for these purposes.

The oil mixtures A and B compare the effects of the additive according to Example 4 compared to the parent amber acid imide in the absence of the usual antioxidants. The data show that the additive according to Example 4 · has a very good antioxidant effect. In mixture C, the added antioxidant had the expected effect. In the mixture D, in which the zinc dialkyldithiophosphate was omitted, surprisingly, the oxidation and the corrosion prevention ability still very good.

Claims (12)

Claims 1. Thiomolybdenum derivative of succinic acid imide by reacting an alkenyl succinic acid imide of the formula: wherein R is an alkenyl radical having 5 to 200 carbon atoms in the chain, and χ is an integer from 0 to 10, with 0.1 to 10 equivalent atoms of molybdenum of a sulfur-molybdenum compound or a molybdenum compound and hydrogen sulfide for a period of time sufficient to complete Sufficient conversion, removal of any volatile by-products and recovery of the reaction product. 2. Thiomolybdenum derivative, produced by reacting the alkenylsuccinic acid imide, which in particular was produced in situ in a manner known per se, with an ammonium or amine salt of a molybdenum thioic acid having 1 to k sulfur atoms per molybdenum atom. 3. thiomolybdenum derivative according to claim 1 or 2, prepared by reacting an aqueous solution with approximately equimolar amounts of ammonium tetrathiomolybdate and the Alkenyl succinic acid imide in a hydrocarbon solvent, Removal of the water by azeotropic distillation or under reduced pressure and stripping of the organic solvent under reduced pressure. 4. Thiomolybdenum derivative according to claim 1 or 2 prepared by reacting approximately equimolar amounts of (NH.J ₂ MoS ^ with an oil concentrate of the alkenylsuccinic acid imide, in particular of the polybutenylsuccinic acid imide of triethylenetetramine in an inert solvent, heating the mixture obtained under reflux, removing the water formed, filtering the anhydrous reaction mixture and distilling off the solvent under reduced pressure. 5. thiomolybdenum derivative according to claim 1, prepared in that the sulfur-molybdenum compound was obtained in situ, by reacting the alkenyl succinic acid imide with a molybdenum oxyacid and the intermediate product obtained with hydrogen sulfide in a molar ratio H-SzMo has been treated from at least 1: 1 to over 4: 1. 6. Thiomolybdenum derivative according to claim 1 or 5, prepared by reacting an aqueous molybdic acid solution with an approximately equimolar amount of the alkenylsuccinic acid imide dissolved in a volatile solvent mixture consisting of a hydrocarbon and an ether based on ethylene glycol, in particular diethylene glycol dimethyl ether, treatment of the resulting oximolybdenum with about 2 to 4, in particular k mol of sulfur hydrogen per mole of molybdenum, removal of water by azeotropic distillation or under reduced pressure, filtration and stripping of the solvent under reduced pressure. 7. thiomolybdenum derivative according to claim 6, prepared by Implementation of the alkenylsuccinic acid imide, dissolved in a solvent mixture that consists of one Hydrocarbon, a non-volatile alkyl phenyl ether of ethylene glycol or a polyethylene glycol instead of the volatile ether, in particular with monononylphenyl ether of ethylene glycol or a polyglycol ether with 2 to 10 oxyethylene units, the non-volatile Ether remains in the final product. 8. thiomolybdenum derivative according to any one of claims 1 and 5 to 7, prepared by the reaction of about equimolar amounts of an aqueous solution of Na_MoO. · 2H ~ 0 and concentrated sulfuric acid under Formation of molybdic acid, reaction of molybdic acid with approximately equimolar amounts of an alkenyl succinic acid imide, in particular of polybutenyl succinic acid imide of triethylenetetramine in an inert solvent, passing through hydrogen sulfide, refluxing the resulting mixture, removing the water formed, removing solids and distilling off of the solvent under reduced pressure. 9. thiomolybdenum derivative according to one of claims 1 and 5 to 8, produced by the reaction of approximately equimolar amounts of an oil concentrate of a polybutenylsuccinic acid imide of triethylenetetramine and molybdic acid at less than 100 ⁰ C and atmospheric pressure, then alternately bubbling through with hydrogen sulfide and nitrogen while heating the reaction mixture to a temperature sufficient for removal the water, heating at this temperature under reduced pressure and filtering off the isolated product. 10. thiomolybdenum derivative according to claim 5, prepared by Reaction of the alkenylsuccinic acid imide with an aqueous solution of an ammonium salt of an oxymolybdic acid and then treating with hydrogen sulfide using a molar ratio of H ₂ S: Mo from 1: 1 to 4: 1. 11. thiomolybdenum derivative according to claim 5, characterized through the in situ production of the sulfur-molybdenum compound by reacting alkenyl succinic acid imide with water, molybdenum trioxide and 0.1 to 0.5 mol of ammonium hydroxide per mol of molybdenum followed by treatment with hydrogen sulfide using a molar ratio from H-S: Mo from 1: 1 to 4: 1. 12. A lubricating oil composition containing 0.01 to 55% by weight, in particular 0.1 to 15% by weight of a thiomolybdenum derivative according to one of the preceding claims and a larger amount of a mineral oil with lubricating oil viscosity, wherein the thiomolybdenum derivative contains 0.01 to 5.0 wt .-%, preferably 0.03 to 0.15 wt .-% molybdenum.