DE1123421B - High temperature grease - Google Patents

Description

GERMAN

PATENT OFFICE

ANME LDETAG:

NOTICE THE REGISTRATION AND ISSUE OF EDITORIAL:

S 67013 IVc / 23 c

FEBRUARY 9, 1960

FEBRUARY 8, 1962

In order to meet the requirements of modern technology for high-temperature lubricating greases, which have to maintain their consistency and lubricity even at working temperatures between 200 and 250 ^° C. during the practically relevant periods, special organic compounds and pigments from the class of indogenous compounds, phthalocyanine compounds, are already available , the antraquinones and the azines are used as gelling agents. Particularly suitable for this purpose are lubricating oil-based greases which, as a thickener, are a water-insoluble compound with two units

CO

High temperature grease

Applicant:

Shell International

Research Maatschappij N.V.,

The hague

Representative: Dr. K. Schwarzhans

and Dipl.-Chem. Dr. phil. E. Jung, patent attorneys,

Munich 19, Romanplatz 9

Claimed priority:
V. St. v. America 11 February 1959 (No. 792 462)

contains in the molecule. The group consisting of three rings has at least one carbonyl radical on the middle Ring up the group.

These compounds fall under the well-known »INDANTHREN dyes«. The word »INDANTHREN« is for the company Badische Anilin- und Sodafabrik AG, Ludwigshafen am Rhein, under the number 51 151 protected as a trademark.

In order to achieve a satisfactory grease consistency with this type of thickener, must however, exceptionally high amounts of the substances in question are used, so that such lubricating greases are quite unfavorable from an economic point of view. Also, in some cases, they have the Disadvantage that the service life of bearings treated with it is not always sufficient.

It has now been found that the consistency of greases produced using the above described compounds with three-ring structure, which at least one carbonyl radical on have middle ring, or an indogenous compound or n-acyl-iMO-dihydroxy-M-diaminoanthracenes, n-Acyl-iMO-dihydroxy-l ^ -diaminoanthracenes, n-Acyldiaminoanthraquinones or n-Acylaminophenolen produced as gelling agents by incorporating 1.5 to 20 percent by weight, based on the total lubricating grease, an aliphatic hydrocarbon diamines, preferably an alkanediamines with less than 10 carbon atoms in the molecule, can be significantly improved. Ethylenediamine and 1,6-hexanediamine are preferred representatives of this association Donald Edward Loeffler, Walnut Creek, Calif.

(V. St. Α.),
has been named as the inventor

group. Another unexpected advantage of the present invention is that the presence a larger proportion of an amine in lubricating greases of this special type, the service life of bearings which are lubricated by means of such lubricating greases, increased quite considerably. This appearance is particularly evident at working temperatures above 149 ° C.

Another important advantage that can be achieved according to the invention is the considerable reduction the cost of the greases in question, as the amines in question are proportionate deals with inexpensive materials. Therefore, a decrease in the content of the grease means the thickener as a result of the addition of amine a saving of about 20 times in terms of the cost of the Grease thickener.

It is already known to use other soaps as thickeners for lubricating oil instead of metal soaps, especially if the latter contain certain oxidizable aromatic petroleum fractions, and fatty acid salts derived from monoamines. You can also use special aromatic Use diamines as antioxidants, and

209 508/296

Furthermore, certain aliphatic monoamines also have an antioxidieren.de effect. About suitability of aliphatic hydrocarbon diamines as thickeners in combination with special, aromatic However, thickeners containing condensed ring systems are from this prior art nothing has become known.

Furthermore, greases have been recommended that contain acetylene black as a gelling agent and amines as Contains extreme pressure additives. Practically only aromatic diamines are used for this special purpose or aliphatic monoamines into consideration. It should also be taken into account that the invention concomitantly used aliphatic hydrocarbon diamines per se no thickening effect at all exercise, but only through the presence of the special gelling agents listed above be empowered.

During the commonly used to improve the consistency of the greases in question Amine content between about 1.5 and 20 percent by weight, based on the lubricating grease, can be used for this Suitable proportions are also expressed as equivalents of the amine per 100 g of the lubricating grease will. The greatest effect is achieved when about 0.02 to 0.1 equivalents of the amine per 100 g of the Lubricating grease are used.

Suitable aliphatic diamines are, for example:

A. Acyclic diamines

gen contains 2 units per molecule of the following typical grouping:

1,3-diamino-2-ethylpropane
1,4-diamino-2-propylbutane
1,5-diamino-3-methylpentane
1,5-diamino-3-butylpentane
1,6-diamino-4-ethylhexane

1,1-diaminoethane
1,2-diaminopropane
1,3-diaminobutane
1,4-diaminopentane
1,4-diamine hexane
1,4-diaminoheptane
1,4 diamino octane
2,6-diaminononane
3,6-diaminodecane

1,2-diaminoethane
1,3-diaminopropane
1,4-diaminobutane
1,5-diaminopentane
1,6-diaminohexane
1,7-diaminoheptane
1,8 diamino octane
1,9-diaminononane
1,10-diaminodecane

It should be noted that this three-ring radical has at least one carbonyl radical on having middle ring of the group. Some special representatives of this group, such as the N-dihydro-1,2-1 ', 2'-anthraquinonazine, even contain two carbonyl radicals on the middle ring. Other connections of this type, for example the flavanthrone, contain only one carbonyl radical, while the three-ring group with a second such group by means of nitrogen bonds or in the case of the pyranthrone

ao is linked by means of hydrocarbon bonds. A Another essential feature of this group of compounds is that nitrogen is not a core element occurs in those rings which form the jreiring group.

The most effective thickener for use in high temperature greases according to the invention the compound is N-dihydro-1,2-1 '^' - anthraquinone azine, however, other compounds derived therefrom can also be used. These will be best Thickeners used in amounts between 5 and 35 percent by weight in their non-metallic form, d. H. without the carbonyl groups in these compounds with ions, for example with sodium, Potassium or calcium, have been neutralized. In the context of the present invention, for example also use the following compounds very well:

Flavanthron
Pyranthrone
Viola throne

3,3'-dichloro-N-dihydro-1,2-1 ', 2'-anthraquinonazine

Trichloro-N-dihydro-1,2-1 \ 2'-anthraquinone azine

Another group of thickeners, which

for the production of high-temperature greases according to of the invention are the indogenous compounds having the following general Structure:

B. Alicyclic diamines

1,2-diaminocyclohexane

1,4-diaminocyclohexane

1 - (Aminomethyl) -2-aminocyclohexane

2,2-diamino-1-cyclohexyl propane

The amines are preferably incorporated by homogenizing them together with the finished lubricating grease. However, the amines can also be added together with the thickener at a time where the grease is first made from the remaining components, or it can be used in the lubricating oil base before it becomes the main thickener is added.

A group of the compounds used as gelling agents in the lubricating greases according to the invention

C =

NH

NH

R '

In these formulas, R and R 'denote aryl or alkylaryl radicals which, with adjacent members of the heterocyclic rings are linked by bonds which are in ortho division to one another. These leftovers can be the same or different, and they can be monocyclic or polycyclic radicals, for example phenylene, biphenylene or naphthylene groups. These aryl or alkaryl radicals can also be substituted and contain the most diverse substituents, such as. B. Hydroxy, Carboxy, halogen or nitrogen groups. Examples of such compounds are indigo, isoindigo, 3-ketoindoline, isatide and isatin.

A third class of suitable thickeners are the phthalocyanines, which include not only metal-free but also metal-containing representatives of this class of substances include, such as zinc, nickel, aluminum and especially copper phthalocyanine.

Another class of grease-forming thickeners can be represented by the following general structural formula can be characterized:

OH NH ₂

OH

NH-C-R

In this formula, R represents an alkyl group having 3 to 24 carbon atoms. Acyl derivatives where the radical R contains from 12 to 22 carbon atoms are preferably used.

Acyl derivatives of the type according to the invention under consideration can be prepared by heating the compound 9,10-dihydroxy-1,4-diaminoanthrazen together with the corresponding organic acid to reaction temperatures of about 100 to 25O ⁰ C. Boric acid can be used as a catalyst in this reaction. For cleaning, the product obtained can be suspended in water which contains small amounts of an alkali. However, no protection is claimed for this manufacturing process within the scope of the invention.

Suitable representatives of this class of compounds are, for example:

l-N-stearoyl-l ^ -diamino- ^ lO-dihydroxyanthracene

l-N-dodecoyl-M-diamino- ^ 10-dihydroxyanthracene

l-N-octoyl-1,4-diamino-9,10-dihydroxyanthracene

l-N-Propoyl-l ^ diamino ^ .lO-dinydroxyanthracene

1 -N-heptoyl-1,2-diamino-9,1O-dihydroxyanthracene

l-N-stearoyl-1,2-diamino-9,10-dihydroxyanthracene

l-N-decoyl-1,2-diamino-9,10-dihydroxyanthracene

The corresponding 1,4-diaminoanthraquinones can also be used.

N-acylaminophenols, which are used to manufacture of the non-soap greases according to the present invention have the following general principles Formula:

R '

HO!

H ii

N — C —R

R "

In this formula, R represents an alkyl group having 14 to 22 carbon atoms, which is preferably does not have a benzene-like structure, and R 'and R "represent hydrogen atoms or alkyl groups with 1 to 20 carbon atoms.

According to a preferred embodiment of the invention, compounds with the above are given Structural formula used, where R 'and R "are hydrogen atoms and R is a straight-chain aliphatic Is a group having 14 to 22 carbon atoms. Representatives of this preferred class of compounds are for example N-palmitoyl-p-aminophenol, N-stearoyl-p-aminophenol and N-arachidoyl-p-aminophenol and N-behenoyl-p-aminophenol.

Alkylated acyl-p-aminophenols, which also are characterized by the structural formula given above when R 'and R "are in the same alkyl group with 1 to 20 and preferably between 4 and 15 carbon atoms are also used as thickeners useful for a lubricating oil such as B. N-n-valeryl-4-amino-3-pentadecylphenol, N-n-pentanoyl-4-amino-3-pentadecylphenol, N-n-propanoyl-4-amino-2,6-diter. butylphenol, N-n-hexyl-4-amino-2-hexylphenol.

The type of lubricating oil used to make the lubricating greases of the invention can vary widely. The selected oil should be able to perform the necessary lubricating functions even if it were used as a liquid. For most applications, mineral lubricating oils can be used with a viscosity ranging between about 35 and 200 SUS at 98.9 ⁰ C. Depending on the origin of the crude oil, it can be a mineral oil of paraffinic or naphthenic character. The various distillates accessible by means of the various refining processes can also be used for this purpose.

Synthetic lubricating oils can also be used to make the lubricating greases of the invention. Such oils include, for example, the esters of monobasic acids, such as the ester of C ₈ alcohol from the oxo synthesis and an acid with 8 carbon atoms from the oxo synthesis, and esters of dibasic acids such as di-2-ethylhexyl sebacate and dinonyl adipate. Esters of glycols, for example the C ₁₃ oxo acid diester of tetraethylene glycol and complex esters, can also be used, such as the complex formed in the reaction of 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylcaproic acid. A class of compounds that has only recently been developed, namely diaryldialkylsilanes, for example diphenyldidodecylsilane, can also be used as a lubricating oil base. Esters of phosphoric acid are also suitable, for example the ester formed from 3 moles of monomethyl ether of ethylene glycol and 1 mole of phosphorus oxychloride. Oils consisting of halogen-containing hydrocarbons, such as polymeric chlorotrifluoroethylene, can be used in the same way as alkyl silicone compounds, e.g. B. methylpolysiloxanes and chlorophenol silicones. Suitable sulfuric acid esters are formed when 1 MqI of sulfur oxychloride is reacted with 2 mol of methyl ether of ethylene glycol.

Certain carbonates can also be used for this purpose, such as those formed, for example, in the reaction of a C ₈ -oxo alcohol with ethyl carbonate and subsequent reaction of the half-ester formed with tetraethylene glycol. Mercaptans can also be used as a lubricating oil base. Formal products are also suitable, for example the _{compound formed by the reaction of a C 13} -osoalcohol with formaldehyde. It is also possible to use polyglycols, such as the products formed by the condensation of butyl alcohol with up to 50 units of propylene oxide. Mixtures of the synthetic oils mentioned can also be used in any proportions.

It has been proposed in the field of ionizing radiation lubrication To use polyphenyl ether as a lubricant or lubricant component. The maximum stability is achieved when the polyphenyl ethers in question have no substituents, but will also very stable lubricants are obtained if the ethers concerned have alpha-cumyl or tert-butyl substituents contain. Although the phenyl radicals with one another through ortho, meta or para bonds can be linked, it is preferred that at least 25% of the etheric bonds are to one another are in meta position, Preferably the polyphenyl ether in question should be three to

contain six phenyl radicals per molecule. It has been shown that a combination of the types listed of thickeners with such lubricating oils lead to lubricating greases that are both at temperatures

5 are extremely stable above 177 ⁰ C and under the action of ionizing radiation.

The following examples illustrate the unexpected improvement in the consistency of one with N-dihydro-l ^ -l '^' - anthraquinone azine as thickening

o medium-made lubricating grease, with 28 percent by weight of all of the fat consists of the thickener, while the remainder is a residual mineral oil-based lubricating oil, i.e. H. a bright stock oil is.

Additive Change in W 60 Pen * Weight percent
of the additive Added
Equivalents Change in W 60 Pen *
per equivalent per 100 g Ethylenediamine
Ethylenediamine
1,6-hexanediamine - 71
-105
-111 1.5
4th
2.5 , 050
, 134
, 044 -1420
- 790
-2520

Walk penetration with 60 strokes, measured with a »Va-scaleo cone in a crucible of size» 0 «.

Claims (4)

Patent claims: 1. High-temperature lubricating grease based on lubricating oil, which as a thickener is a water-insoluble Connection with 2 units 35 contains in the molecule or an indogenous compound, an N-acyl-9,10-dihydroxy-1,4-diaminoanthracene, an N-acyl-9,10-dihydroxy-1,2-diaminoanthracene, an N-acyldiaminoanthraquinone or an N-acylaminophenol characterized by a further content of 1.5 to 20 percent by weight of an aliphatic hydrocarbon diamine. 2. High-temperature grease according to claim 1, characterized in that it is the thickener contains in an amount of 5 to 35 percent by weight. 3. High temperature grease according to claim 1 and 2, characterized in that it is an aliphatic Hydrocarbon diamine an alkane diamine with fewer than 10 carbon atoms in the molecule, in particular ethylenediamine or 1,6-hexanediamine contains. 4. High-temperature grease according to claim 1 to 3, characterized in that the lubricating oil base Is polyphenyl ether. Considered publications:
German Patent Nos. 832 032, 832 787, 626; German Auslegeschrift No. 1 006 996;
U.S. Patent Nos. 2,642,397, 2,680,719;
British Patent No. 749 535. Legacy Patents Considered:
German Patent No. 1,062,864. O 209 508/296 1.62