DEST007830MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: February 25, 1954 Published on June 21, 1956

GERMAN PATENT OFFICE

Synthetic lubricants exhibit in lubrication normal motor vehicle engines have good viscosity-temperature behavior and leave very little residue in the combustion chamber, especially if it is used for a long time. this has a more efficient fuel utilization, a smaller increase in the octane requirement of the engine, a reduced The result is a tendency to pre-ignition and, in general, better functioning of the engine. This Lubricants can also be used to clean up combustion chamber debris that is already in an engine to decrease or remove.

In an attempt to obtain better specialty lubricants, completely new synthetic lubricating oils were developed which, compared with mineral oils, have particularly good viscosities at low and high temperatures. This makes them particularly suitable for the lubrication of machines that have to work within a large temperature range, such as jet engines or turbines for aircraft, piston internal combustion engines for aircraft.
The present invention relates to the use of sulfuric acid esters of organic compounds which have at least one alcoholic hydroxyl group

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and no esterifiable carboxylic or sulfonic acid groups contained as synthetic lubricating oils. It has been found that these esters are extraordinary ; have favorable high and low temperature properties and are therefore particularly good for lubrication of the above motors are suitable. The new

■ bonds have the following general structural formula:

A — 0 — S — Ο — Β

Here A and B are the residues of compounds with at least one alcoholic hydroxyl group, as far as they contain non-esterifiable carboxylic or sulfonic acid groups. ■, - - .-, .., -.,. ... ......

When used ... in piston engines, especially in the lubrication of motor vehicle engines, a lubricating oil must meet various requirements. In order to be able to form an effective lubricating film and to maintain it at low and high temperatures, it must have certain viscosity properties. At low temperatures, the lubricating oil must be sufficiently unstable to be able to circulate in the system's lubrication system and to allow the lubricated surfaces to move without excessive force. In general, a lubricating oil should have an ASTM pour point below about 1.7 degrees so that it has sufficient low temperature instability. At high temperatures, the lubricating oil must be sufficiently consistent to form and maintain a sufficient lubricating film. It has been found that a lubricating oil which is satisfactory in this regard must have a viscosity of about 2 to 60 cSt at 98.9 °. In order to avoid excessive losses of lubricating oil through volatilization and disintegration or even explosions, a lubricating oil mixture should have a flash point of more than approximately 150 ^° . These requirements are included in the term "lubricating oil" and the invention is directed to such synthetic lubricating oils made from sulfite esters of the general formula

A —O— "S —Ο —Β

that have these properties. The esters used preferably have an ASTM pour point below about - 26 °, a flash point above about 190 ⁰ and a viscosity in the range of 2.6 to 13 cSt at 98.9 °.

The above properties are functions of molecular structure and molecular weight. Therefore it is possible within certain limits Manufacture lubricating oils with similar low and high temperature properties in different ways and to make them "made to measure", so to speak, to meet the respective requirements, because the large number of organic substances that contain alcoholic hydroxyl groups allows the produce a wide variety of composite lubricating oils according to the invention.

These organic oxy compounds can contain up to about 60 carbon atoms. It is, however, essential that the sulfurous acid ester molecule in the average contains about 20 to "" 120, "preferably 25" to "6 * 5 carbon atoms. Esters with fewer than approximately carbon atoms do not have the desired ones high temperature viscosity char acteristics, and those containing more than 130 carbon atoms are usually viscous at lower temperatures. ^v '.

The ones that can be used for the production of these esters Connections can be found in the following list. It can of course also other compounds can be used.

I. Unsubstituted alcohols

A. monovalent

1. aliphatic: '·.

'a) "methyl alcohol

b) ethyl alcohol

c) propyl alcohol

- d) isopropyl alcohol

e) n-butyl alcohol

f) isobutyl alcohol

g) see. Butyl alcohol h) tert. Butyl alcohol

i) n-amyl alcohol j) isoamyl alcohol k) n-hexyl alcohol 1) isohexyl alcohol m) 2-ethyl-i-butanol n) 2-ethyl-i-hexanoI o) octyl alcohol

p) iso-octyl alcohol, '■

q) 2-octanol r) isononyl alcohol s) decyl alcohol t) lauryl alcohol u) tetradecyl alcohol V) pentadecyl alcohol w) octadecyl alcohol x) allyl alcohol y) crotyl alcohol z) oleyl alcohol aa) the terpineols

bb) alcohols or mixtures thereof obtained by known synthesis processes

2. aromatic:

a) Benzyl alcohol

b) phenethyl alcohol

c) 3-phenyl-i-propanol

d) a-naphthyl-carbinol

e) cinnamon alcohol

f) Diphenyl-carbinol

g) furfuryl alcohol h) cumic alcohol

i) Vanilly alcohol j.) Piperonyl alcohol

■ i. Glycols:

B. polyvalent

a) ethylene glycol

b) i, 2-propanediol

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c) I, 3-propanediol γ. ::. ■

; d) i, 3-butanediol. . · '■■ "' ^: '

e) i, 4-butanediol. . '.

f) i, 5-pentanediol ■

. g) polyalkylene glycols. .

(1) polyethylene glycols, '

(a) Diethylene glycol ......

(b) triethylene glycol ·· -.

(c) tetraethylene glycol

(2) polypropylene glycols

(a) dipropylene glycol. . ;

(b) tripropylene glycol h) i, 2-cyclohexanediol. i) Decanediol-i, 10. '· ...'

2. other multivalued:

a) glycerin

b) 2-oxymethyl-2-methyl-propanediol-i,

c) pentaerythritol
d). Sorbitol

e) dipentaerythritol,

f) Dulcit

:: g) Trimethylol-propane h) Tetramethylol-cyclohexanol i) benzotrimethylol

II. Substituted alcohols

A. monovalent ι. aliphatic:

a) halogenated alcohols

(1) ethylene chlorohydrin:

(2) trifluoroethanol

(3) propylene chlorohydrin

(4) the various chlorine-substituted monoethers of polyalkylene glycols

b) ethanolamine, ethanol morpholine

c) 2-aminopropanol

d) 2-nitroethanol

e) 2-nitropropanol

f) 2-nitrobutanol

2. aromatic:

a) p-methoxy-benzyl alcohol

b) the various chlorobenzyl alcohols

c) the various nitrobenzyl alcohols

d) 2-aniline ethanol

i. Glycols:

B. polyvalent

a) halogenated glycols, e.g. B.

(1) 3-chloro-i, 2-propanediol

(2) 2-chloro-i, 3-propanediol

b) nitroglycols, e.g. B.

(1) 2-nitro-i, 3-propanediol

(2) 2-nitro-2-methyl-propanediol-i,

(3) trimethylol nitromethane

c) aminoglycols

. (1) 2-amino-1,3-propanediol

(2) 2-Amino-2-methyl-1,3-propanediol

(3) diethanol amine

(4) trimethylol aminomethane

2. Glycol monoester: .. ■ ■; ■■ ·. .; v, - γ. ■. ■ · '. ":. ^; .", - ■'

, a) Ethylene glycol monoacetate = ^: · ^: ■ '■■■' ■ - \. · ^? .: b) Propylene glycol monobutyrate ■.: ..

c) butylene glycol monolaurate ^■:

d) Polyethylene glycol monoester, ■■

e) Polypropylene glycol monoester:.:. ■:

f) polybutylene glycol monoester

3. Glycol monoether:

a) Ethylene glycol monomethyl ether

b) propylene glycol mono-butyl ether

c) butylene glycol mono-acidic ether. . . '

d) polyethylene glycol monoether,

e) polypropylene glycol monoether

f) polybutylene glycol monoether

g) Polytrimethylene glycol monoether

4. Glycol Mono Formal:

the mixed formals of glycols and alcohols

G. other oxy compounds

1. Esters of oxy acids:,. , ■

a) lactic acid ester

b) glycolic acid ester

c) oxystearic acid ester. -

2. carbonyl-substituted alcohols:

a) oxyketones, e.g. B.

(ι) Oxyacetone γ

b) Öxyaldehyde, ζ. B. ■ ^;

(1) α-Oxy-adipaldehyde

(2) α-oxy-propionaldehyde

3. Oxy-alkyl cyanides:,.

a) ethylene cyanohydrin

b) a-oxy-isobutyronitrile

Organic hydroxyl compounds which are particularly useful for the process according to the invention · "·: ■ are the highly branched aliphatic alcohols that are obtained through the »oxo« synthesis.

Alcohols which are particularly useful for preparing the esters according to the invention can be prepared by applying the oxo synthesis to polymers and copolymers of C ₃ and C ₄ monoolefins, as are readily available in petroleum refinery streams.

In general, the best results are obtained by choosing from the large number of organic hydroxyl- ''. Compounds that can be used as a component of the synthetic lubricant from sulfuric acid esters according to the invention, the branched-chain alcohols, such as the oxo alcohols, initially with a suitable amount of alkylene oxide, such as propylene ■ '. ■' oxide or ethylene oxide, condensed to the ether To form polyalkylene glycols. The viscosity of the end products increases with the amount of alkylene oxide that is condensed with the alcohol. In this way the viscosity of the end product can be adjusted to any desired value. The alcohols used can, if desired, also contain sulfur or other elements. ■

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For the production process of the esters used as synthetic lubricants according to the invention No protection is claimed in the context of the present patent.

The following examples serve to further explain the invention:

example 1

A 5-liter four-necked flask equipped with a stirrer, condenser, thermometer and dropping funnel is charged with 300.2 g (19 mol) of C ₁₀ -oxo alcohol (from tripropylene). It is added in 35 minutes at 25 to 45 ⁰ IOyI g (9 mol) of SOCl ₂ . It is then heated and the temperature is kept at 100 ° for ι hour. The heat source is then switched off and N _{2 is} blown through to remove traces of HCl. The yield of crude sulfuric acid ester is 3380 g.
..; Purify the sulfite by - always at room temperature - first ₂ CO and then washed with 5 ° / _o strength Na ₃ solution three times with water. After drying with Na ₂ SO ₄ , the sulfite is distilled under reduced pressure in a short-path distillation device. The distillate between 122 and 143 ⁰ at 0.1 mm pressure is 84% of the charge; it has the following composition and characteristics:

Sulfur 8.54%

Acid number 0.168 mg K O H / g

Ester number 294.0 mg K O H / g

Kinematic viscosity

at 37.8 ° 6.5 cSt

Kinematic viscosity

at 98.9 °; 1.2 cSt

Viscosity Index .......... 103

Flash point. 182.0 ° C

Pour point below - 59.0 ° C

. Example 2

..-. The production is similar to that of C ₁₀ -oxO-sulfite .. It is also distilled under reduced pressure in a short-path distillation device and the bulk of the distillate is collected at 180 to 185 ° under 0.15 mm pressure. This distillate has the following key figures:

Sulfur. ........... 7.01%

Acid number 0.785 mg K O H / g

7 ester number, '..'. 240.7 mg KOH / g

Kinematic viscosity

- '■■■ "at 37.8 °' 18.5 cSt. '

Kinematic viscosity

Viscosity index 106 '

Flash point 224.0 ° C

■ ' ] ■ Flow point ......... below - 59.0 ° C

'. ,: Example 3,.

C ₁₃ oxo alcohol is condensed with an average of 3.2 mol of ethylene oxide. This alcohol is then converted into a sulfuric acid ester in the following way: ..: ■ ·. . .

With rapid stirring, to 1 mole of the alcohol is reacted ¹ Z ₂ MoI of thionyl chloride added dropwise. During the addition, the temperature is kept at 30 ° and the mixture is then stirred for a further 2 hours at room temperature. The mixture is then heated to 130 ° for ι hour. Nitrogen is bubbled through the reaction mixture throughout the treatment.

When the reaction has ended, the product is placed in a Clais flask and heated below 1 mm Pressure to a metal bath temperature of 250 °. You only gain a few drops of distillate, which are discarded will. The residue that has not passed over consists of a straw-colored, viscous oil ■ of the following Properties: " '

Kinematic viscosity at 37.8 ° 44.9 cSt

- 98.9 ° 6.7 cSt viscosity index ............... 137

Flash point 232.0 ° C

Pour point, -45.0 ° C

Example 4

C ₁₃ -oxo alcohol is condensed with an average of 6.8 moles of ethylene oxide. The polyethylene glycol ether obtained has the following properties:

Kinematic viscosity at 37.8 ° 33.0 cSt - - 98.9 ° 5.0 cSt Viscosity index 136

This ether is then condensed as described in Example ι. with thionyl chloride. The emerging Oil consists of a straw-colored viscous liquid that has the following properties:

Kinematic viscosity at 37.8 ° 53.9 cSt

- 98.9 ° 8.2 cSt

Viscosity index 140

Flash point ..,.;. 235.0 ° C

Pour point. -17.8 ° C

105 Example 5.. -

In a manner similar to that described above, thionyl chloride is condensed with isodecyl lactate. The The resulting product is a straw-colored oil with the following properties:

Kinematic viscosity at 37.8 ° 24.5 cSt

- 98.9 ° 3.3 cSt

Viscosity index 72.5. .115

Flash point. 218.0 ° C

Pour point. ... - 46.0 ° C

The synthetic lubricating oils described above are compatible with a large number of additives, which are commonly used to improve certain properties of lubricants. Man can e.g. B. put these new lubricating oils with sludge inhibitors, pour point depressants, oxidation inhibitors, V.I. improvers. You can also in any mixing ratio with mineral

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Lubricating oils can be mixed to improve their properties.

Claims (4)

Patent claims: i. Use of sulfurous acid esters of the general formula A — 0 — S — Ο — Β whose molecules contain 20 to 120 carbon atoms, with A and B being residues of compounds with at least one alcoholic OH group, provided they contain non-esterifiable carboxylic or sulfonic acid groups, as synthetic lubricating oils with an ASTM pour point below 1.7 °, a flash point above 150 ⁰ and a kinematic viscosity in the range from 2 to 60 cSt at 98.9 ° on its own or in a mixture with other lubricating oils. 2. Use of sulfuric acid esters according to claim 1, in which A and B are different radicals of mono- or polyhydric aliphatic or aromatic alcohols which can be unsubstituted or _{substituted by halogen, NH 2} or NO ₂ groups, oxy ethers, esters of oxy acids, oxyketones or oxyaldehydes. 3. Use of sulfuric acid esters according to claim 1, in which A and B are residues of reaction products of alcohols with an alkylene oxide. 4. Use of sulfurous esters according to claim 1, in which A and B are residues of condensation products of an alkylene oxide with a branched-chain alcohol of the oxo synthesis, ζ. B. an ethylene or propylene oxide with a C ₈ - to C ₁₃ alcohol.