DE1276853B - Oil mixture - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

ClOm

German class: 23 c -1/01

Number: 1276 853

File number: P 12 76 853.5-43 (G 43567)

Filing date: May 11, 1965

Open date: September 5, 1968

Oil mixtures are known to be used as lubricants, hydraulic fluids, damping and brake fluids, Dielectrics and heat transfer media used.

You must meet certain requirements for this, e. B .:

1. They must · be liquid under the conditions of use and have the ability to respond to to form a lubricating film on a wide variety of materials, especially on metals,

2. they have to be less volatile and largely resistant to heat,

3. They should not have a corrosive effect and, above all, should not form any acidic decomposition products,

4. they are to retain their properties over a possible ^'5 wide temperature range, that is, its viscosity should be as independent as possible of temperature,

5. They should have a freezing point that is as low as possible and, on the other hand, as high as possible Have boiling point.

It has now been found that imides of the formula

CH CO

NO

in which R 'and R "are each hydrogen or together an alkylene radical with 1 or 2 carbon atoms, in particular the methylene radical, and R a straight-chain Co to Ci «-, preferably Cs to Ci2 alkyl radical means having particularly advantageous properties.

The imides according to the invention are known and they can be prepared by processes known per se will. Likewise, the utility of cyclic N-alkylimides as lubricants in the Literature mentioned: for example, in Belgian patent specification 623 333, N-alkylsuccinimides in particular are mentioned with long chain substituents proposed as lubricants. Such N-alkyl succinimides with however, an alkyl radical of 8 to 12 carbon atoms are solid at room temperature. In contrast represent N-alkylimides which can be used according to the invention. especially those whose alkyl radical R 8 to Has 12 carbon atoms, are liquids that melt at least 40 C lower in the pure state oil mixture

Applicant:

JR Geigy AG, Basel (Switzerland)
. Representative:

Dr. F. Zumstein, Dr. E. Assmann,
Dr. R. Koenigsberger

and Dipl.-Phys. R. Holzbauer, patent attorneys,
8000 Munich 2, Bräujiausstr. 4th

Named as inventor:

Dr. Joachim Dazzi, Riehen (Switzerland)

Claimed priority:

Switzerland of May 12, 1964 (6143)

than the N-alkyl succinimides with the same N-substituent. Mixtures according to the invention usable N-alkyl imides as they arise during the production of technically available primary amines, often solidify only at - 6O ⁰ C. Therefore, in contrast to the previously known N-alkyl succinimides inventive N-alkyl imides even under Arctic or stratospheric conditions used will. Furthermore, the N-alkylimides according to the invention show a significantly better resistance to oxidation than the previously known N-alkylsuccinimides. Thanks to this property, they can also be used as lubricants at higher temperatures. where the previously known succinimides are no longer sufficient. Another advantage of N-alkylimides which can be used according to the invention in comparison with previously known N-alkylsuccinimides is their significantly lower volatility with the same N-substitution.

The imides which can be used according to the invention are colorless to pale yellowish at room temperature. drip liquid oils. Compared to previously known, z. B. products used as turbine lubricating oils N-alkylimides which can be used according to the invention are distinguished by good low-temperature properties characterized by particularly good heat resistance. So they only decompose above 380 ° C, while the most heat-resistant organic esters to date, for example the triesters of fatty acids with trimethylolpropane, are unusable from 360'C.

809 599/500

Another advantage of the N-alkylimides according to the invention over lubricants based on organic and inorganic esters is that, in contrast to the esters, they practically do not form any acidic decomposition products during thermal decomposition. This small inclination of the imides acid to form decomposition products, which are responsible for the corrosion effect, demonstrated by the fact that, for example, those obtained by 6stündiges distributing N-decyl or N-dodecyl-cyclohexane-1,2-dicarboximide at 400 ⁰ C under a nitrogen atmosphere The resulting volatile compounds and the residue are neutral, while the substances which are formed from the triester of trimethylolpropane and pelargonic acid at 360 ^° C. under a nitrogen atmosphere have a combined acid number of about 78 mg KOH / g for volatile components and residue. Another advantage of the imides according to the invention over lubricants based on the alkyl esters of organic. Acids, phosphoric acid esters, alkyl silicones and silicates consist in the fact that they are more resistant to the influence of γ-rays. Furthermore, the alkylimides according to the invention outperform the lubricants based on organic esters with regard to their lower swelling effect on certain plastics which are used for the production of seals. Compared with the silicone oils and polyphenyl ethers, some of which are very thermally stable, the imides according to the invention are distinguished by a better lubricating effect and, compared with the polyphenyl ethers, also by a lower pour point, a more favorable temperature behavior of the viscosity and a lower density.

The imides according to the invention are suitable for lubricating a wide variety of surfaces; so diminish the friction of metal on metal but also that of metal on silicate, such as glass, significant.

The imides according to the invention are with other common oils, eg. B. with those based on of organic esters, polyaryl ethers, polyalkyl melamines, high-boiling phosphoric acid esters, high-boiling mineral oils, certain silicone oils or orthosilicates, easily miscible. This cheap Miscibility allows the manufacture of special lubricants, adding those for a specific use properties that are required but cannot be achieved through manufacture due to the individual components suitable mixtures can be obtained. Another advantage that can be used according to the invention Imide consists in their relatively high dielectric constant, which is why they are used as dielectrics can be. Furthermore, they are practically non-toxic (oral DL50 in the mouse> 5000 mg / kg). The lower the number of carbon atoms in R, the deeper the imides melt. Imide with short N-alkyl chain are therefore in terms of low-temperature properties preferred. On the other hand, the volatility decreases with increasing carbon number of R, so that imides with a long N-alkyl chain are preferred in this regard.

Preference is given to imides in which R is a Ce to C12 alkyl radical is.

Other common additives, such as antioxidants, extreme pressure additives, corrosion protection agents, agents that lower the pour point, can also be added to the imides. Thickener.

Oil mixtures should contain at least 25 percent by weight of imides.

example 1

N-n-dodecyl-cis-cyclohexane-l ^ -dicarboximide

A mixture consisting of 308 g (2 mol) of cis-cyclohexane-1,2-dicarboxylic anhydride, 390 g (2.1 mol) of technical dodecylamine and 200 g of xylene is heated ^{to 150 ° C. for 4 hours.} The water of reaction formed is continuously removed from the reaction mixture as a water-xylene azeotrope by means of a water separator. Vacuum distillation gives 699 g of a product consisting mainly of Nn-dodecyl-cis-cyclohexane-1,2-dicarboximide. Bp 161-166 ° C at 0.05 torr; nf: 1.4802, melting point -3 ° C. The technical dodecylamine used contains 99.0 percent by weight dodecylamine, 0.3 percent by weight! Decylamine and 0.7 weight percent tetradecylamine.

Pure NnD.odecyl-cis-cyclohexane-l ^ -dicarboximide boils at 241 to 242.5 ° C / 12 Torr and has an n% of 1.4812.

Example 2 N-n-decyl-cis-cyclohexane-1,2-dicarboximide

1,290 g (8.4 mol) of cis-cyclohexane-1,2-dicarboxylic anhydride be provided in a two inlet funnels, a thermometer, and a combined water separator and reflux condenser, heated 4.51 four-necked flask to 120 ⁰ C. To this mixture technical decylamine (commercial product) was added dropwise in 1383 g (8.8 mol) over 90 minutes, keeping the temperature of the reaction mixture between 120 and 150 ⁰ C is maintained. At the same time, toluene is added dropwise in order to remove the water of reaction that forms from the reaction mixture as it forms as a toluene-water azeotrope. Imide formation has ended after 5 hours and the theoretical amount of 151 g of water has been separated off. The reaction mixture is distilled in vacuo. The lead, 66 parts, consists mainly of technical decylamine. The main fraction weighs 2460 g and is a mixture consisting mainly of Nn-decyl-cis-cyclohexane-l ^ -dicarboximide. Boiling point 155 to 158 ° C at 0.01 to 0.02 torr; Density at 20 ⁰ C: 0.984; nl °: 1.4823. Yield 94.3%, based on cis - cyclohexane -1,2 - dicarboxylic acid anhydride. This product solidifies below -55 ⁰ C. The fatty amine used 10 D consists of 1.0 percent by weight dodecylamine, 76.4 weight percent n-decylamine, 21.8 weight percent n-octylamine, 0.3 weight percent n-hexylamine and 0.5 weight percent lower boiling impurities.

Example 3 N-n-Octyl-cis-cyclohexane-1,2-dicarboximide

616 g (4MoI) cis-cyclohexane-l ^ -dicarboxylic anhydride as described heated at 2 to 120 ⁰ C and at this temperature the mixture was added dropwise 547 parts of technical octylamine. The water of reaction formed is continuously removed as a toluene-water azeotrope and then fractionated. 1009 g of a mixture consisting mainly of N-η-octyl-cis-cyclohexane-1,2-dicarboximide are obtained. Bp. 134 to 140 ^° C

at 0.005 to 0.01 torr; nf: 1.4842. Density at 20 ⁰ C: 0.960. Yield 95.0% based on the cis-cyclohexane-1,2-dicarboxylic acid anhydride. The technical octylamine used for this synthesis boils between 159 and 179 ° C and consists of 4.5 percent by weight of n-hexylamine, traces of n-heptylamine, 95.5 percent by weight of n-octylamine and traces of decylamine.

Example 4

N-n-Hexadecyl-cis-1-4 -cyclohexane-1,2-dicarboximide

This is made from 100 g (0.65 mol) of cis-cyclohexane-1,2-dicarboxylic acid anhydride and 168.5 g (0.7 mol) of technical-grade n-hexadecylamine. 192 to 202 ^° C at 0.1 torr.

Example 5

N-n-decyl-cis ^ o-endomethylene cyclohexane-1,2-dicarboximide

This is made from 328 g (2 mol) of anhydride of the cis - bicyclo [2.2, l] heptene - (2) - 5,6 - dicarboxylic acid and 333 g (2.1 moles) of fatty amine were prepared. Bp 191 to 194 ° C at 0.1 torr.

IO

15th

Example 6

N-n-Dodecyl-cis ^ o -endomethylene cyclohexane-1,2-dicarboximide

Substance used diameter
the wear
dome in mm
(Mean of three
Measurements) Imid No. 1 0.645
0.817
0.850
0.915
0.898
1.154
1.953
(after
2V2 minutes
represents
welding
of the balls
a) Di-3,5,5-trimethyl-hexyl-sebacate
Di-2-ethylhexyl sebacate
Di-2-ethylhexyl adipate
Mineral oil (viscosity at
37.8 ⁰ C = 65.7 cSt)
Pentaphenyl ether (viscosity at
37.8 ° C = 369 cSt)
Methylphenyl silicone (viscosity at
37.8 ° C = '78.3cSt)

25 The imides of Examples 2 to 6 show similar results in this smear.

This is made from 205.5 g (1.25 mol) of cis-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride and 243 g of technical n-dodecylamine produced. Bp 191 to 194 ° C at 0.1 torr.

The imide from Example 1 is suitable for the lubrication of metal surfaces. For a quantitative comparison of its lubricating effect against five commercially available lubricants, the diameter of the wear cap was measured in a precision 4-ball apparatus. These measurements were made in accordance with US Federal Specifications Lubricants and Related Products WL 791 e. Method 6503 Load Carrying Capacity (means Hertz Load) «carried out. This apparatus ran for 30 minutes at a speed of 1480 revolutions per minute kg at a load of 40 and using ^ -inch steel balls SKF A-quality and at an initial temperature of about 40 ⁰ C. The results are in the following table compiled.

Claims (1)

Claim: oil, optionally in a mixture with known lubricating oils or lubricating oil additives from imides of the formula NO in which R 'and R "are each hydrogen or together an alkylene radical having 1 to 2 carbon atoms and R is a straight-chain Cs- to Cis-alkyl radical means. ! 09 599/500 8.68 θ Bundesdruckerei Berlin