DE1060079B - Lubricants containing molybdenum - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

PATENT DOCUMENT 1060

REGISTRATION DAY:

NOTICE
THE REGISTRATION
AND ISSUE OF
EDITORIAL:

ISSUE OF
PATENT LETTERING:

DBP 1060079 kl. 23 c 1/01

INTERNAT. KL. C 10 IU

4 JULY 19 5 6

JUNE 25, 1959 DECEMBER 3, 1959

AGREES WITH EDITORIAL

1 060 079 (A 25244 IVc / 23 c)

The invention relates to molybdenum-containing lubricants based on mineral or lubricating oils synthetic origin.

It is known that a content of molybdenum sulfur compounds significantly increases the compressive strength of lubricants. In particular, it is known that molybdenum disulphide (MoS ₂ ), which occurs naturally as molybdenum luster, is an excellent solid lubricant when it is thoroughly cleaned, especially freed from all abrasive substances and finely divided. These cleaning and disintegrating processes are very costly. In addition, there are limits to the degree of division of the molybdenum disulfide because if the particle size becomes too small, it suffers strong oxidation even at room temperature, which severely affects the lubricity of the molybdenum disulfide and can even cause harmful effects because the oxidation products of molybdenum disulfide, namely molybdenum trioxide and sulfur dioxide cause corrosion on the materials of the lubrication points. Highly purified molybdenum disulfide of optimal particle size is used as a lubricant in a wide variety of ways, including as an additive to lubricating oils.

However, in order for the molybdenum disulphide to take effect from the lubricating oils under boundary friction conditions to let it be stably suspended in the lubricating oils; because molybdenum disulfide, which is found in lubricating oils settles is worthless because it does not get to the critical lubrication points and can even cause blockages can. Obtaining stable suspensions of molybdenum disulfide in lubricating oils is difficult, in itself because of the high specific weight of molybdenum disulfide (about 5) and because, as already explained, the particle size downward limits are set because of the oxidation that occurs.

In order to achieve a reasonably stable molybdenum disulphide lubricating suspensions, the addition of Surface-active substances are required, but this may also be used in addition to stabilizing the suspension can cause other undesirable effects, e.g. B. too extensive solvotation of the molybdenum disulfide particles, whereby these are enveloped in so dense liquid skins that even under boundary friction conditions no contact is made between the surfaces to be lubricated and the molybdenum disulfide particles comes.

To circumvent these difficulties, it has already been proposed that the lubricating oils be oil-soluble or by means of Solubilizers add soluble substances to the lubricating oils, which form the components for molybdenum-sulfur compounds contained in a two-substance or in a one-substance system.

For example, in French patent specification 1 099 953, the molybdenum-containing lubricant

Patented for:

The Alpha-Molykote Corporation, Stamford, Conn. (V. St. A.)

Dr. Günter Spengler, Dr. Hannsheinz Mockery

and Dipl.-Chem. Josef Gänsheimer, Munich, have been named as the inventor

Manufacture of molybdenum blue compounds described, but only together with oxo alcohols, which here serve as solubilizers, can be used in lubricating oils. As with the ones described there Molybdenum phosphoric acid esters still require lubricants containing such additives further additives, namely of oil-soluble sulfur compounds, because only then are these molybdenum additives effective will.

If you have these types of molybdenum blue, that is, with the help of diethylaminodidodecyl phosphate or by means of a Oxo alcohols, together with organic sulfur compounds (alkyl or aryl sulfides, If alkyl or aryl disulfides or xanthates) are mixed with a mineral lubricating oil, an increase can be achieved the pressure resistance of lubricating oils when tested on the four-ball apparatus (VKA) can reach 60 kg.

Another way out of the lubricating oils under pressure and temperature conditions, such as those at lubrication points prevail to obtain the desired protective layer of molybdenum sulphides on the surfaces in adding oil-soluble thiomolybdates of organic nitrogen bases or molybdoalkoxyxanthates to the lubricating oils, which increases the pressure load on the VKA by 50 to 70 kg.

It has now been found that lubricants with lubricating oils of mineral or synthetic origin an increase in the pressure resistance on the VKA by 170 to 180 kg was achieved and quite surprisingly Also at the AWM there is an increase in the pressure load capacity of 1200 kg, for example with one Lubricating oil with an AWM value of 300 kg to 1500 kg when the endurance run at 1500 kg load is passed, when according to the invention reaction products of

909 663/295

Molybdenum blue with sulfurized unsaturated alcohols and / or sulfurized organic, optionally hydroxyl groups containing nitrogen bases, preferably in addition to heat stabilizers such as oil-soluble higher Contain fatty acids or their reaction products with organic nitrogen bases.

Sulfurized unsaturated alcohols with 8 to 20, preferably 14 to 18, are advantageous C atoms, such as B. sulfur-containing tetradecenol, hexadecenol, octadecenol, and as sulfurized organic, nitrogen bases optionally containing hydroxyl groups, in particular those with 8 to 20, preferably 14 to 18 carbon atoms, such as sulfur-containing octylamine, Dehydroabietylamine, hexadecylaniine, 1-oxyethyl-2-heptadecyl-glyoxalidine, Oleylamine, 1-oxyethyl-2-heptadecenyl-glyoxalidine, contain. The sulphurized unsaturated alcohols or the sulphurized alcohols can also be used organic nitrogen bases, optionally containing hydroxyl groups, preferably in sulfur Molar ratio of alcohol or nitrogen base to. Contain sulfur like 1: 1.

The most lubricating organic sulfur-molybdenum compounds are obtained by reacting Unsaturated sulfur, preferably in a molar ratio of organic compounds to sulfur = 1: 1, containing Hydroxyl-containing organic nitrogen bases with one according to the known method of Zinzadze produced molybdenum blue. The sulfur-containing, unsaturated, hydroxyl-containing organic Nitrogen bases can be obtained in particular by reacting higher unsaturated fatty acids with amino alcohols, such as B. l-oxyethyl-2-heptadecenylglyoxalidine

N -CH ₂

CH ₃ - (CH ₂ ) ₇ -CH = CH- (CH ₂ ), -C _s

CH ₂ OH

from oleic acid and condensed ethanolamine and subsequent sulphurisation. Also the conversion products of saturated higher fatty acids with amino alcohols or of ethylene oxide with organic nitrogen bases, z. B. Ethylene oxide with Octadecylaniin

CH ₂ -CH ₂ -O-CH ₂ OH

Ch ₂ -CH ₂ -O-CH ₂ -O-CH ₂ -CH ₂ OH

Ethylene oxide with dehydroabietylamine lead to hydroxyl groups Nitrogen compounds, which after their sulphurization in the molar ratio nitrogen compound to sulfur = 1: 1 with molybdenum blue result in lubricant additives according to the invention.

It is of course also possible, in particular to increase the amount of sulfur, that more per se than Lubricant additives already known oil-soluble organic sulfur compounds, e.g. B. benzyl sulfide, dibenzyl sulfide and the like, preferably in amounts of 0.5 to 5 percent by weight, based on the amount of lubricant or sulfur-containing base oils are used. If you put the alcohol-sulfur-molybdenum compounds, Amine-sulfur-molybdenum compounds or nitrogen base-sulfur-molybdenum compounds the usual lubricants in amounts of preferably 0.5 to 5, in particular 2 to 3 percent by weight, so the VKA values are increased by 170 to 180 kg and Above all, the AWM values have been decisively improved. If the reaction products between molybdenum blue, organic sulfur-containing compound are not oil-soluble are like the z. B. in the case of the dissolution product of sulfurized em l-oxyethyl-2-heptadecenyl-glyoxalidine is the case with molybdenum blue, you can still get clear mineral oil solutions by using sufficient amounts dissolving and possibly self-lubricating, z. B. sulfur-containing saturated and / or unsaturated Alcohols with 8 to 20 carbon atoms, preferably

ίο with 10 to 18 carbon atoms, such as B. decanol, decenol, Dodecanol, dodecenol, hexadecanol, hexadecenol, or by using mixtures of such alcohols or similar solubilizers. To regulate the Temperature resistance of the lubricant additives described in the lubricant is preferred Oil-soluble higher fatty acids, in particular unsaturated fatty acids such as oleic acid, ricinoleic acid, or their oil-soluble ones Reaction products with organic amines, such as octylamine, decylamine, l-oxyethyl-2-heptadecenylglyoxalidine, added. Additions of fatty acids were found in amounts of 0.5 to 3, especially 1 to 2 percent by weight or their reaction products in amounts of 2 to 6, especially 2.5 to 3.5 percent by weight, based on the lubricant, as advantageous.

example 1

In 17.5 g of l-oxyethyl-2-heptadecenyl-glyoxalidine 1.6 g of sulfur are dissolved at 130 to 150 ° C and 9.6 g of this reaction product in a Sch. R.

Zinzadze (Z. Pflanzenernahrung, Düngung A 16, 1930, p. 134) _{dissolved i-butanic molybdenum blue solution prepared from 6 g MoO 3} , washed twice in water, dried over sodium sulfate. The i-butanol is then distilled off at about 12 mm Hg on a water bath and 2.7 g of the 1-oxyethyl-2-heptadecenyl-glyoxalidine-sulfur-molybdenum blue compound remaining after the distillation is dissolved in 100 g of mineral oil (raffinate 17/50). brought into solution with the aid of a mixture of alcohols of chain length C ₁₄ to C _18.

While the base oil (Raffinat 17/50) has a VKA value of 130 to 140 kg and on the AWM a Has a load capacity of 300 kg, the following VKA and AWM values were determined for the oil containing molybdenum

VKA value 300 to 320 kg,

AWM value 1500 kg.

At the AWM, the endurance test was passed even with a load of 1500 kg.

Example 2

The mineral solution from Example 1 (100 g of raffinate 17/50 + 2.7 g of 1-oxyethyl-2-heptadecenyl-glyoxalidine-sulfur-molybdenum blue compound + 2.7 g alcohol as a solubilizer) is in the drying cabinet for 12 hours held at 95 ° C. After just one hour, you can see the excretion of a black, blotchy one Precipitation. Tested after standing in the drying cabinet at 95 ° C for 12 hours on the VKA and on the AWM, this is how the values of the base oil are obtained, namely:

VKA value 130 to 140 kg,

AWM value 300 kg.

If 1.5 g of oleic acid are added to the same mineral solution from Example 1, it remains even after 36 hours Store in a drying cabinet at 95 ° C completely clear, and the test on the VKA and the AWM gives the following Values:

VKA value 300 to 320 kg,

AWM value 1500 kg (endurance run).

45

The same test values are obtained if 3 g of the reaction product of oleic acid with l-oxyethyl-2-heptadecenyl-glyoxalidine are used instead of 1.5 g of oleic acid. ^l

Claims (6)

Patent claims: 1. Lubricants containing molybdenum based on mineral or synthetic materials, if necessary Sulphurous lubricating oils, characterized by a content of reaction products of molybdenum blue with sulphurized unsaturated alcohols and / or sulfurized organic nitrogen bases, optionally containing hydroxyl groups. 2. Molybdenum-containing lubricant according to claim 1, characterized in that the sulfurized unsaturated Alcohols those having 8 to 20, preferably 14 to 18 carbon atoms, such as. B. sulphurous Tetradecenol, hexadecenol, octadecenol, and the sulfurized organic, optionally hydroxyl groups containing nitrogen bases those with 8 to 20, preferably 14 to 18 carbon atoms, such as sulfur-containing Octylamine, dehydroabietylamine, hexadecylamine, 1 - oxyethyl - 2 - heptadecyl - glyoxalidine, oleylamine, l-oxyethyl-2-heptadecenyl-glyoxalidine. 3. Molybdenum-containing lubricant according to claim 1 and 2, characterized in that the sulphurized unsaturated alcohols or the sulfurized organic, optionally containing hydroxyl groups Nitrogen bases contain sulfur, in a molar ratio of alcohol or nitrogen base to sulfur such as 1: 1. 4. Molybdenum-containing lubricant according to claim 1 to 3, characterized by a content of solvents in the form of sulfur-containing saturated and / or unsaturated alcohols, in particular with 8 to 20 carbon atoms, such as sulfur-containing decanol, dodecanol, decenol, dodecenol, hexadecanol. 5. Molybdenum-containing lubricant according to claim 1 to 4, characterized by a further content of known heat stabilizers, especially oil-soluble higher fatty acids such as oleic acid, ricinoleic acid, preferably in amounts of 0.5 to 3 percent by weight, and / or their reaction products with organic nitrogen bases, such as ocetylamine, decylamine, 1-oxyethyl-2-heptadecenyl-glyoxalidine, preferably in amounts of 2 to 6 percent by weight, based on the amount of lubricant. 6. Lubricant according to claim 1 to 5, characterized by a further content of as lubricant additives oil-soluble organic sulfur compounds known per se, in particular benzyl sulfide, dibenzyl sulfide, preferably in amounts of 0.5 to 5 percent by weight, based on the amount of lubricant. Considered publications:
German Auslegeschrift D 16 953IVc / 23c (published on June 14, 1956); Patent No. 2291 of the Office for Inventions and Patents in the Soviet Zone of Occupation in Germany;
French patents nos. 1 099 953, 1 099 955.