DE1044328B - Lubricant and process for its manufacture - Google Patents

Description

The invention relates to the composition of lubricants based on lubricating oil with a content of a complex metal soap.

Complex metal soaps made from soaps of high molecular weight carboxylic acids (hereinafter referred to as "soaps") and Low molecular weight carboxylic acids (hereinafter referred to as “salts”) are known per se. These complexes that previously used almost exclusively as a thickener for high-temperature lubricating greases, consist of compounds of metal salts of low molecular weight carboxylic acids with metal soaps of high molecular weight fatty acids, and normally in an approximately equimolecular ratio. The molar ratio of low molecular weight acid to High molecular weight fatty acid is used in these common lubricating greases because of the low thickening effect of the low molecular content kept quite low. Even at molar ratios of 3 moles lower molecular weight Acid per mole of high molecular weight fatty acid or even less is needed to produce lubricating greases sufficient penetration, a good deal of the soap-salt compound serving as a thickener. That's why experts say that the molar ratio of 3: 1 is exceeded for these customary soap-salt compounds decidedly refused.

The present invention is based on the surprising finding that you can by strong increase the content of these soap-salt complexes in low molecular weight monocarboxylic acid and thus in metal compounds with completely new properties that are of much greater value than fat thickeners. In particular it has been found that mixed soaps of this type, which are 7 to 40 moles, preferably about 8 to 25 moles, have a lower molecular weight Contain monocarboxylic acid per mole of high molecular weight fatty acid, except for one of the usual ones mentioned above Complex similar thickening effect exceptionally favorable properties for absorbing high loads as well as dispersants, sludge inhibitors, and in various other respects.

The constitution and chemical structure of the mixed compounds of soaps and salts has not yet been clarified. In any case, the X-ray grating spectra of various of these complexes according to the invention, which contain more than 7 and up to 40 mol of a low molecular weight monocarboxylic acid per mole of high molecular weight monocarboxylic acid, show that they are not physical mixtures of salts of the low molecular weight acids with soaps of the high molecular weight acids. In particular, none of the spectra obtained with these compounds shows a structure which agrees with the known structures of the X-ray diffraction spectra of the salts of low molecular acids. Further, the structures of the X-ray diffraction spectia of mixed compounds show the same low molecular acid salt as the metal content and the lubricants and processes
for its manufacture

Applicant:

Esso Research and Engineering Company, Elizabeth, N.J. (V. St. A.)

Representative: E. Maemecke, Berlin-Lichterfelde West,
and Dr. W. Kühl, Hamburg 36, Esplanade 36 a,
Patent attorneys

Claimed priority:
¹ S V. St. v. America October 21, 1953

contain the same soap of high molecular acid, but differ in terms of the molar ratio of low molecular weight to high molecular acid differed, certain differences, which tend to indicate the presence of different chemical compounds than physical mixtures of the same chemical compounds close in different proportions.

These metal-rich complex soaps can be mixed with mineral and / or synthetic lubricating oils excellent lubricating greases with good heat resistance and greatly improved extreme pressure properties that are about 5 to 30 percent by weight mixed

soap included. Similar mixed soaps can be used in relatively small quantities, i.e. H. about 2 to 4 percent by weight, as sludge inhibitors for mineral or synthetic engine lubricating oils, as high-pressure and adding metal binders to metalworking and machine lubricating oils.

The high molecular weight acids used according to the invention are monocarboxylic acids with 12 to 30, preferably with 18 to 22 carbon atoms in the molecule. These acids can differ from saturated or unsaturated, derived from naturally occurring or synthetic fats. Preference is usually given to those customarily used in production Fatty acids used in lubricating greases, especially the more saturated acids. Examples of this are stearic acid, oxystearic acid such as 12-oxystearic acid, Polyoxystearic acids with the exception of dioxystearic acid, and other saturated oxy fatty acids, peanut oil acids, hydrogenated fish oil and tallow acids etc. However, unsaturated acids such as oleic acid, Castoroleic acid and the like can be used.

819 6TS3AS

3 4

In certain cases, see ζ. B. in the production of acid generators, such as nitriles, are used as starting materials.

High-pressure greases and sludge-inhibited oils, preferred substances of this type are naturally occurring

it may be appropriate to add a substantial part, e.g. B. animal and vegetable fats and oils. Even the low-

about 25 to 80 percent by weight, of the high molecular weight molecular carboxylic acids can be in the form of more suitable Fatty acid in the mixed compound by an oil-soluble ester such as the ester of glycerin, ethanol, etc., or

To replace sulfonate, e.g. B. by sulfonates of oil-soluble other acid generators, such as nitriles, can be used. Man

Sulphonic acids with molecular weights of about 350 to can be among those customary for the saponification of these esters

525, preferably from about 420 to 450. Conditions with subsequent drainage and drainage

The low molecular weight acids are saturated and work without alcohol. Esters of this type can

saturated aliphatic monocarboxylic acids with 1 to 6 C- io both for the case of common neutralization as

Atoms suitable, such as formic acid, acetic acid, Pro- also for the separate formation of

pionic acid, furancarboxylic acid, acrylic acid and like soap and salt can be used.

Acids including their oxy derivatives, such as lactic acid. The metal-rich complex soaps according to the invention

etc. Formic acid is preferred and, in particular, can also be prepared in such a way that

Acetic acid. 15 at least part of the soap's high molecular weight

The choice of the metallic constituent depends on an acid and / or the salt of the low molecular weight to a certain degree from the intended use of the soap carboxylic acid, which is initially produced separately, both of which are then intimately complex. Mixes and heated if necessary are useful for many purposes of the present invention. This process is the alkaline earth metals, especially calcium, barium and is especially valuable when magnesium is used for the soap and the salt. These metals offer the greatest advantage, 20 different metals are used
If thickeners are used in the production of other reasons, the use of previously lubricating greases can also be used, since they are advantageous to the lubricating greases of non-manufactured metal salts. The production of the usual load-bearing capacity and good structural stability of the metal complex soaps according to the invention for the production of lubricating grease etc. at high temperatures and under mechanical stress requires large amounts of stress, even in the absence of the usual high-pressure, low-molecular-weight carboxylic acids such as glacial acetic acid. As these and stabilizing additives give. In this regard, when acids are available in large quantities, the alkaline earth metals can differ from the alkaline metals - they can be bought in a wagon or tank truck. Giving complex soaps with high alkali content, in which case the factory must have a tank system and pipes, even if they are added to the dispersing oil in proportionate lines to the kettles with special precautions for moderately large quantities, lubricating greases of 30 to prevent freezing. Even with poorer structural stability. You have to deal with the acid because of its corrosive nature

Other metals advantageous within the scope of the invention, of course, certain precautionary measures must be taken. are the heavy metals of group I, II and IV of the It has been found that by replacing part of the periodic table, in particular copper, zinc and the free acid, with previously prepared metal salts such as lead, manganese, nickel, cobalt and chromium. You 35 calcium acetate, a large number of the disadvantages mentioned can be avoided either on their own or together with earth. In addition, the finished salts, alkali metals used in the production of the mixed soaps, especially calcium acetate, are of a suitable degree of purity. Lead increases resilience. Any of the metals mentioned or also base salts formed in situ with free acid can be considerably cheaper than the conversion of a metal. These pre-several of them as metallic elements of both the 40 parts result when one serves about 30 to 80 weight salts as well as the soaps, ie the metal of the percent, preferably at least 50 percent by weight, of the salt can be the same as the metal of the Soap or the free acid in the composition of the mixed smoke is a different one. Most often contain salt and soap binding for the production of lubricating greases and for however the same metal or the same combination other purposes are replaced by finished metal salt,
of metals. 45 If the metal-rich metal

The complex soaps with a high metal content can be dispersed by soap complexes in a liquid or

Jointly neutralizing a mixture of the high-solvent can be formed so they can be removed from the

and the low molecular weight acids with suitable bases, dispersion or solution by extraction of the dispersant

in particular with the hydroxides and / or isolate the means with a solvent in which the

Carbonates of the metals in question are produced. 50 mixed compound is insoluble. Suitable solvents

This joint neutralization can be in situ in which are n-heptane, isopropyl alcohol, acetone, water etc.,

the same liquid medium in which the complex is made - with the correct choice of the solubility properties

soap should be applied. The acidity of the liquid medium depends on that used to disperse

mix can e.g. B. in part of the lubricating oil or in which the mixed compound was used,

all lubricating oil can be neutralized, which the disperser 55 To produce lubricating grease, lubricating oils can be mineral

greases for which the complex soap is used to thicken the oil and synthetic origin, including

Forms grease. The well-known diesters, mixed esters, hydrocarbon

Joint neutralization is particularly beneficial for polymerizates, silicone oils, polyglycol derivatives, etc.

Adhesive if the soap and the salt are the same metallic. In general, these oils should have viscosities of about

see own component. Usually one heats the 60 1.6 to 43 cSt at 98.9 ⁰ C and flash points of about

have mutually neutralized material at 177 to 315 ° C before use. The viscosity index can be 100

to high temperatures of about 230 to 260 ° C or or even more; Oils with a lower viscosity

higher to dehydrate the product and the education efficiency index, such as below 60, but give better

to promote the mixed connection. Will heating in yields. It was also found that metal

running a liquid dispersant, this should be 6g complex containing more than 30 moles, e.g. B. 30 to 40 moles,

one low molecular acid located above the heating temperature per mole of high molecular acid

Boiling point, or the heating should contain under pressure, is particularly good for the conversion of synthetic

take place. ester oils are suitable in excellent lubricating greases.

Instead of the high molecular weight fatty acids themselves, the complex-

also their esters, especially the glycerides, or other soap in amounts of about 5 to 30, preferably 10 to

5 6

20 percent by weight, based on the total lubricating solidification point 52 ° C

bold to apply. Acid number 196

The anti-sludge property and high pressure iodine number · maximum 6

Lubricating effect of the complex soaps according to the invention. Saponification number 194

can be used in conjunction with common 5th grade lubricating oils

can be used in a wide variety of ways. In this way it can be seen that the complex soaps containing 7.5 to 20 mol of active metal acetic acid per mole of high molecular weight fatty acid can be introduced into the oil without reducing the solubility (Nos. 5 to 8), fats of excellent quality becomes a problem. In general, the oil should have a consistency, a good dropping point and an excellent load viscosity in the range from 9.3 to 535 cSt at 37.8 ° C and should be available. The fats with 5 or less moles of vinegar-1.6 to 32 cSt at 98.9 ° C, a pour point of about acid per mole of high molecular weight fatty acid (No. 1 to 4) -6.7 to -34.5 ° C and The first-mentioned fats had a flash point of about -177 to 343 ° C. They can be used - both in terms of their own high-pressure mineral oils and synthetic hydrocarbons, which are far inferior to the conditions. The fats with 30 or more moles of hydrocarbon polymers, esters, mixed esters, formals, 15 acetic acid per mole of high molecular weight fatty acid (No. 9 and mercaptals, polyalkylene oxides, silicones or similar oils 10) had excellent extreme pressure properties, including special oils such as di-2-ethylhexyl -sebacate, however, with regard to their consistency, they behaved di-C ₈ -oxoazelate, etc. High-metal-containing metal soaps and their structural stability are less favorable, complexes of the alkaline earth metals, especially magnesium, calcium and barium, have an excellent sludge-protecting effect and considerable resilience, if they are used in amounts of about 0.5 to 10 percent by weight, preferably about 1 to 5 percent by weight, of the following constituents, a lubricating grease was prepared essentially according to Example 1: zent, added to the oil. High metal-containing complexes can lead soap to 20 weight percent, ₂₅ parts, preferably from 2 to 10 weight percent, for -p- ■ 10 0 in amounts of about 0.5

Improvement of the high pressure properties of the lubricating _TT,. ° '' - ^ '.' V .. \ '.'. _ ' _n

.., ^b , ^b Hydrogenated Fischolic Acids 5.0

oils are used. Kalkh drat 7 3

The metal soap complexes can be lubricants for -. _T , J ₁ .- / 'W; i »ij" V-iV + "· +" · '"'

metalworking, such as cutting oils, auxiliaries 30 Naphthiiemsches MmeraloldestiUat with emer

". , _c,. 5. . jj viscosity of 7.8 cSt at 98.9 C 77.7

for drawing, forging, are added, namely

to mineral oils as well as to emulsions, in order to obtain their This lubricating grease had a fairly coarse structure, To improve high pressure properties. In this case, however, the homogenization was carried out after the equalization The metal-rich complex soaps the usual, Gaulin machine smooth and took an excellent one Components used to increase the load-bearing capacity, 35 Appearance. such as sulfur, chlorine, sulfur chlorides and phosphorus Replace or add additions. Favorable properties Results are usually achieved by adding a molar ratio of acetic acid to hydrogenated

about 2 to 20 percent by weight, preferably about 5 to 9.3: 1 fisholic acids

10 percent by weight of the complex soaps, based on the 40 free acid content (as oleic acid

Amount by weight of the total lubricant. Magne- calculated) 0.14

Complex soaps containing sium can be used to prevent penetration at 25 ° C, mm / 10

Corrosion can be used in gear lubricating oils. Resting penetration 210

Walk penetration after 60 impacts 215

Example 1 ⁴⁵ dropping point, ° C> 260

Water solubility insoluble

A number of mineral oil based greases made with calcium complex soaps from hydrogenated fish - Example 3 Oleic acids, which correspond to commercially available stearic acid in terms of their degree of saturation, from hydrogenated egg 50 The following ingredients were used to make a lubricating grease Nut oil obtained oxystearic acid and acetic acid produced according to Example 1 with the exception that the thick, were produced as follows: temperature was only increased to 232 ° C, since the

The hydrogenated castor oil, the hydrogenated fish oil grease already began to become thick at 204 ° C,

and hydrated lime as well as the entire mineral oil were

a directly heated fat with a stirrer - 55 percentages

Kettle and heated to about 55 ° C. Then glacial acetic acid ¹ 7 50

the acetic acid was added. The heating became Hydrogenated Fish Oil Acids''.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'. 7 ^ 0

continued and the temperature increased to 260.degree. Kalkhvdrat 612

Then the heating was turned off and the grease under naphthenic mineral oil from one of them

Stir cooled to 93 ° C. Thereupon the fat in 60 viscosity of 7.8 cSt at 98.9 ° C was 78.88

emer homogenizing machine according to Gaulm with high

Walk speed equalized. The properties thus obtained

Lubricating greases were hydrogenated by milling to their structure-molar ratio of acetic acid

Resistance, according to the Almen test for their resilient ichthyic acids 5: 1

and also examined for their dropping point. 65 Appearance before leveling .. Good, smooth The composition of the fats and their consistency of uniform pro is listed in Table I. dukt with some

The small bits in this example and in the other examples

The hydrogenated fischolic acids mentioned above had the following non-dispersed ones

Key figures: 70 soap

Table I.
Lubricating greases based on calcium complex soaps

No.

I ² 3 4th 5 6th 7th 8th 3.20 5.30 7.90 7.90 10.50 12.60 9.50 2.50 2.50 3.75 2.50 2.50 2.00 1.00 12.50 7.50 3.75 2.50 2.50 2.00 1.00 4.35 5.00 6.42 6.10 7.50 9.20 6.60 0.50 0.50 0.50 0.50 0.50 0.50 0.50 76.05 79.20 77.68 80.50 76.50 73.70 81.40 0.71 0.50 0.55 0.67 0.36 0.42 0.28 1: 1 2.5: 1 5.0: 1 7.5: 1 10: 1 15: 1 22.5: 1 18.2 15.3 15.4 12.9 15.5 16.6 15.6 234 153 103 165 168 180 290 258 165 144 210 206 198 310 > 260 > 260 > 260 > 260 > 260 260 > 260 10 10 9 15th 15th 15th 15th

10

Composition, percent by weight

acetic acid

Hydrogenated castor oil

Hydrogenated fish oleic acids

Hydrated lime

Phenylnaphthylamine

Naphthenic mineral oil distillate, viscosity 7.8 cSt at 98.9 ⁰ C .....

% Free Alkali as NaOH

Molar ratio
Acetic acid to high molecular acid total acid content

Acetic acid + high molecular acid

properties

Penetration at 25 ° C, mm / 10

Resting penetration

Walk penetration (60 strokes) ....

Drop point, ⁰ C

Almen test

(Loading with weights)

0.80 2.50 12.50 2.75 0.50

80.95 0.22

1: 2.5 15.8

too soft ;

goes seperate ways

in oil and

soap

11 12.60 1.00 1.00 8.70 0.50

76.20

30: 1 14.6

353

Poor structural stability, becomes semi-liquid

14.20 O 0.85 > ^ 0.85 ■ co
00 9.70 0.50 73.90 0.42 40: 1 15.9

Semi-liquid fat; some separation of soap in granular form

15 Bad condition of the pen

Appearance after leveling in the Gaulin homogenizing machine. Excellent

Penetration at 25 ° C, mm / 10

Rest penetration 176

Walk penetration after 60 thrusts 180

Walk penetration after 70,000 thrusts ... 190

Drop point, ° C> 260

Water solubility insoluble

Although, according to the invention, greases with an excellent structure of saturated or unsaturated high molecular weight fatty acids, it has been found that some of these lubricating greases after begin to harden in a short time, initially on the surface of the grease exposed to air forms a crust and then gradually excessive hardening progresses through the whole mass. It has now been found that the hardening and crust formation is prevented if the whole high molecular weight fatty acid or at least half of it from oxy acids, e.g. B. monostearic acids. This is illustrated by the following example:

Example 4

Three greases a, b and c were prepared by mixing the ingredients listed below in the cold the specified amounts and heating to about 260 ° C with stirring. The fats were then on 93 ° C cooled, leveled and packaged. The phenyla-naphthylamine was added while cooling at about 120 ° C.

Example 5

Two greases A and B were manufactured on an industrial scale from the following ingredients:

Hydrogenated fish oleic acids

Hydrogenated castor oil

Glacial acetic acid

Hydrated lime

Phenyl naphthylamine

Naphthenic mineral oil distillate, viscosity 7.8 cSt at 98.9 ° C

A I B percent by weight

2.0 2.0 8.0 6.0 0.5

81.5

1.6 1.6 6.4 4.8 0.4

85.2

Weight percent fat a I fat b I fat c

Components

Oxystearic acid

Hydrogenated castor oil

Hydrogenated fish oleic acids.

Glacial acetic acid

Hydrated lime

Phenyl-a-naphthylamine ...

Naphthenic mineral oil distillate, viscosity
7.8 cSt at 98.9 ° C

properties

Look immediately after
Manufacturing

Appearance after 1 month ..

Appearance after 6 months

Penetration at 25 ° C, mm / 10
Walk penetration after

60 pushing
after 6 months

5.0

10.0 7.5 0.5

77.0

2.0 2.0 8.0 6.0 0.5

81.5

35

5.0 10.0 7.5 0.5

45

77.0

excellent even

excellent

excellent

a little harder than originally

245 238

262 252

Crust on the very fat

hard

250 202

60

65

The greases a and b having an oxy fatty acid residue contained, were therefore decidedly superior to the grease c in terms of hardening.

The hydrogenated fish oleic acids, the hydrogenated castor oil, the hydrated lime and the mineral oil were heated together to 57 ° C in a directly heated kettle. Then the glacial acetic acid was added and the mixture heated to 26O ⁰ C. This temperature was reached within 4 ¹ Z ₂ hours. The heating was switched off, the kettle was closed, flushed with CO ₂ and then placed under 2 atmospheric pressure. The grease formed was forced into a cooling vessel provided with a cooling jacket by the air pressure.

During the over-pumping, the temperature of the grease fell to 227 ° C and then fell within one Continue to 121 ° C for about 1 hour while the grease was stirred and cooling water was passed through the jacket The agitation and water cooling were turned off overnight and the grease cooled during this period further down to 79 ° C. Then some of the grease in a Morehouse mill became very low Gap width and an outlet temperature of 116 ° C. The remainder of the grease left in the boiler was diluted to a softer consistency with mineral oil and with the same grinder setting homogenized. The milling speed was considerably faster and the exit temperature was 82 ° C.

properties

Fat A fat B

Appearance

Penetration at 25 ° C, mm / 10
Resting penetration

Walk penetration after 60 impacts

Walk penetration after

75,000 thrusts

Water wash sample,% loss ..

Immersion in boiling water for 3 hours

Drop point, ⁰ C

Wheel bearing test, 6 hours at
104 ° C

Evaporation,% (50 hours at 98.9 ° C)

Deposition, ° / ₀ (50 hours at 98.9 ° C)

Corrosion of copper (24 hours at 98.9 ° C

Excellent

195 238

308 0

244 291

369 0

insoluble

> 260

Well

5.0

> 260

Well

4.0

1.6

»09 679043

Properties ': Fat A Fat B Norma Hoffmann oxidation test, kg / cm ² drop in O ₂ pressure after 100 hours 0.07 0.14 AFBMA-NLG / spindle sample, hours (121 ° C, 10000 rev./min.) .... > 1800 > 1800 (149 ° C, 10000 rev./min.) .... - 334 4-ball sample, kg load Running load - 252 Sweat load - 282 Ancestral sample, number of weights 15th 15th Timken sample (33 O.K. exposure) - Limit line Wear test, 7.5 kg, 30 Mi utes at 75 ⁰ C, scuffs diameter, mm 0.26 0.23

properties

The greases therefore had excellent properties in terms of wear, resilience, behavior at high temperatures, water resistance, consistency and stability.

Example 6

A Stauffer grease of the usual type was produced as described from the following components:

Components

Weight percent

9.50

1.35

0.95

Animal fat

Hydrated lime

Water ,

Naphthenic mineral oil distillate

(Viscosity 12 cSt at 98.9 ⁰ C) 87.70

Polybutylene (to increase adhesion) 0.50

A steam-heated boiler was charged with equal parts of this fat and the fat B according to Example 5, and the mixture was heated to 149 ° C with stirring. The temperature was held at this level for 2 hours, until all the water had escaped from the Stauffer fat. On cooling, it became an excellent, smooth Get fat.

Example 7

In a different approach, the Stauffer fat according to Example 6 was prepared by adding the kettle with the fat and half of the mineral oil was charged and the mass was heated to 54 ° C, whereupon the lime was added. The heating was continued up to 149 ° C and this temperature was maintained until all of the fat was saponified. Then the complex soap fat according to Example 6 was added without prior cooling, and the two Fats were boiled together for 2 hours until a solid structure had formed. Then that became Heating interrupted and the rest of the oil added. Then the fat was quickly passed through cold water cooled by the cooling jacket of the boiler. The fat was then stripped, nitrided and packed up. The appearance of the fat was improved by homogenizing.

■ Appearance: Excellent smooth and even fat

Drop point, ⁰ C> 260

Penetration at 25 ^° C., mm / 10

Rest penetration 285

Walk penetration after 60 impacts 300

Walk penetration after 65,000 hits .. 320

Wheel bearing test (6 hours at 104 ^° C.) good

Loss due to coasting 0

Water solubility ... insoluble in boiling water. Lubricity, service life

10,000 rev./min., 121 ⁰ C, hours .. 1134
Norma Hoffmann oxidation test,
kg / cm ² drop in O ₂ pressure

100 hours 0.21

In the previous two examples, the grease thickened with the simple calcium soap contained the Calcium soap of an animal fat. The invention also encompasses Stauffer fats, i. H. with simple calcium soaps Thickened fats in which unsaturated and / or saturated fatty acids are used.

Valuable lubricating greases thickened by means of alkaline earth mixed soaps can be produced in which the Complex soap a low molecular acid, e.g. B. acetic acid, and a high molecular weight, oil-soluble sulfonate together with a high molecular weight fatty acid. The complex soap can be neutralized by common the free acids with an alkaline earth metal hydroxide in the presence of the alkaline earth metal sulfonate. The alkaline earth metal of the complex soap can be a single metal or a mixture of metals. In any case The salt of the low molecular acid forms the main component of the complex soap. This embodiment the invention is illustrated by the following example.

Example 8

A sulfonate grease is made from the following ingredients:

τ-,, ,,., weight-

_{Constituent percent}

Calcium sulfonate (molecular weight about 1000;
30 ° / ₀ sodium concentration of soap in micro

mineral oil) 7.0

Hydrogenated fish oleic acids 2.0

Glacial acetic acid 8.0

Hydrated lime 5.7

Naphthenic mineral oil distillate, viscose

did 7.8 cSt at 98.9 ° C 77.3

The calcium sulfonate, the hydrogenated fish oil acids and two-thirds of the mineral oil were placed in a grease kettle and heated to 66 ⁰ C. Then it was first

the acetic acid and then a slurry of the hydrated lime in the remainder of the mineral oil. Heating was continued to drive off the water and the fat was then heated ^{to 238 ° C.} The heating was then interrupted. The fat that was initially completely liquid, froze when reheated to about 23O ⁰ C to a solid product.

properties

Appearance Smooth, even fat

Molar ratio of acetic acid to hydrogenated

Fish oleic acids 20: 1

Penetration at 25 ^° C., mm / 10

Resting penetration 220

Walk penetration after 60 thrusts 310

Walk penetration semi-liquid after 1000 strokes

After solidifying 10 minutes after

Walking with 1000 strokes 275

Drop point, ⁰ C '260

Gearbox smear test ... The part of the grease that comes with

was in direct contact with the gearbox, became fluid and caused excellent lubrication. The rest of the fat stayed solid

High pressure behavior

Almen-Probe Withstood a load

15 weights off - resulted in slight scratches

Water solubility Insoluble, but goes in

emulsion

The above example shows a thixotropic grease that contains equal molar amounts of high molecular weight fatty acid and sulfonic acids. The thixotropic property of the lubricating grease can be regulated. If the sulphonate content is increased, the lubricating grease becomes more fluid under operational stress. If the concentration by weight of the fatty acid salt is increased beyond that of the sulfonate, the structural resistance to mechanical stress increases. Even small amounts of sulfonate change the structure of the grease. A mixture of 5 ° / ₀ of the fat defined above in a high-performance lubricating base oil was prepared.

Weight percent

Mineral oil concentrate of the complex soap 5

High-performance lubricating oil base

(Viscosity 101.5 cSt at 37.8 ° C; 10 cSt at

98.9 ° C; Viscosity index = 102.6) 95

The lubricating oil thus produced was homogenized, checked for viscosity and an oil additive filter sample subject with the following results:

Nature of the additive and the finished oil mixture Properties of the additive

Drop point, ° C> 260

Penetration at 25 ° C, mm / 10

Resting penetration 220

Walk penetration after 60 thrusts 300

Properties of the finished oil

Viscosity at 37.8 ⁰ C, cSt 125.3

Viscosity at 98.9 ⁰ C, cSt 13.3

Viscosity index 116.6

Ancestral test, load capacity 15 weights

The following examples describe greases made in accordance with the invention containing metals other than calcium contained in the complex soap.

For many purposes, thickened lubricating greases can be used with the complex soaps according to the invention mixed metal content to give the grease the properties of a certain, with mixed soap a single metal thickened grease while eliminating the shortcomings of using a mixed soap a single metal thickened grease. For example, soaps are thickened with calcium complex soaps Lubricating greases in which the molar ratio of low-molecular to high-molecular acid is low, relatively hard and often almost brittle. On the other hand, greases thickened with sodium complex soaps tend to be both at a relatively low and at a relatively high molar ratio of the low molecular weight to the high molecular acid, a liquid or

40

45

50 semi-liquid consistency. If these two greases are now combined with one another in such a way that a complex soap grease on a mixed metal base is produced, in which the ratio of high molecular to low molecular acid corresponds to the present invention, an excellent, stable lubricating grease of soft consistency, excellent water resistance and sufficient absorption capacity for water is obtained, to prevent corrosion. A grease of this type is illustrated by the following example:

Example 9

A lubricating grease B thickened with a baking soda mixed soap was produced from the following components:

Weight components of the lubricating grease B percent

Acetic acid 12.6

Hydrogenated fish oleic acids 4.0

Sodium hydroxide 9.2

Naphthenic mineral oil distillate, viscosity 7.8 cSt at 98.8 ° C 74.2

The hydrogenated fish oil acids, the mineral oil and the sodium hydroxide solution (40% aqueous solution) were charged in a kettle and heated to 40 ⁰ C. Then the acetic acid was added and completed the fat by dewatering and then heating to 26O ⁰ C. The grease was cooled to 93 ° C. with stirring and then leveled in a Gaulin homogenizer.

properties

Free alkalinity as NaOH,% 0.17

Semi-liquid consistency

Example 10

A grease thickened with sodium-calcium soap was prepared by mixing 50% of Grease 4 (Example 1) Made with 50% of the grease from Example 9. This grease was composed as follows :

Components by weight percent

Acetic acid 10.250

Hydrogenated fish oleic acids 3.875

Hydrogenated Castor Oil 1,875

Hydrated lime 3.220

Sodium hydroxide 4,600

Naphthenic mineral oil distillate, viscosity 7.8 cSt at 98.9 ° C 75.940

Phenyl-a-naphthylamine 0.250

The cold greases A and B were mixed together in a grease mixer of conventional design. Included an excellent, smooth, uniform grease was obtained.

properties

Molar ratio of acetic acid to high molecular weight acid about 10: 1

Penetration at 25 ° C, mm / 10

Resting penetration 265

Walk penetration after 60 thrusts 235

Walk penetration after 100,000 hits 250

Water resistance water wash test

(Water temperature 66 ⁰ C) no loss'

Norma Hoffmann oxidation test

O ₂ pressure drop by 0.35 kg / cm ² in
Hours 247

properties

Molar ratio of acetic acid to high molecular weight acids

10: 1

215

245

290

> 260

Lubricating greases with improved corrosion protection, which are suitable for use in the heat in the presence of acidic reacting waters can be a Contain calcium-zinc complex soap according to the invention. The mixed organic acids, e.g. hydrogenated fish oleic acids, oxystearic acid and acetic acid, can be neutralized in situ in the mineral oil with a mixture of zinc oxide and calcium hydroxide will.

The previously known lubricating greases thickened with calcium soaps are excellently suited for use in the presence of moisture. However, they easily cause corrosion of the metal parts, since they have no or only absorb little water. They also have no resistance to high temperatures, which results from their low dropping point. Water insolubility and static corrosion prevention are of particular importance Importance in canning. In this industry one uses to close the Bushes a pre-ao working with a steam stream "

direction. This machine required a number of £ _{m of} softer grease which was diluted by thinning

Lubricants, including a lubricating grease, with 39.0% of the same mineral oil, intimate mixing that both lubricates the seam roller bearings and prevents their subsequent equalization in the Gaulinian corrosion. These bearings are made of an ambient homogenizing machine,
of water vapor (of about 93 ° C) and food as

steam exposed, which in the case of citrus and to- ■ weight

machine industry react angrily. They also come with you from time to time when washing and sterilizing cold water and steam in contact.

A lubricating grease that meets these high requirements can be produced from zinc-calcium complex soaps in the organic part of which acetic acid is the predominant component. They also own these Excellent extreme pressure properties. Typical greases of this type are in the following examples described.

Penetration at 25 ° C, mm / 10

Resting penetration

Walk penetration after 60 thrusts

Walk penetration after 100,000 hits.

Drop point, ° C

Water solubility at 100 ° C

Moisture chamber: steel sheets smeared with grease for 7 days at 100% Humidity and 49 ° C (1 day at room temperature) None

corrosion

Ancestral test, load capacity 15 weights

Components

Example 11

A lubricating grease is made from the following components:

percent

Fat, according to the information in this example

made '61.0

Mineral oil 39.0

properties

Appearance Excellent smooth fat

Penetration at 25 ^° C., mm / 10

Resting penetration 345

Walk penetration after 60 impacts 354

Drop point, ⁰ C> 260

Almen test, load capacity 15 weights

Components by weight percent

Oxystearic acid 2.0

Hydrogenated fish oleic acids 2.0

Acetic acid 8.0

Hydrated lime 6.0

Zinc oxide 2.0

Naphthenic mineral oil distillate, viscosity 7.8 cSt at 98.9 ° C 80.0

All components except acetic acid were placed in a directly heated fat kettle and heated to 54 ° C. with stirring. At this temperature, the acetic acid was added and then the whole is heated to 232 ⁰ C. During the dehydration process, further heating was carried out carefully. Heavy smoke begins to develop at 232 ° C and the grease takes on a solid structure. The heating was then interrupted and the mixture was cooled to 93 ° C. with further stirring. At this temperature, antioxidants such as phenyl-a-naphthylamine or other corrosion-preventing agents such as titanium oxide or magnesium hydroxide can be added. Then you equalize the grease and get an excellent, even product. Titanium oxide can also be used in place of zinc oxide; however, it is not certain whether the titanium is MLdet with the acids complex soaps. Magnesium hydroxide in combination with calcium hydroxide enters the soap complex and forms an excellent anti-corrosion agent to prevent static corrosion.

The following example explains the use of a ready-made metal salt of a low molecular weight carboxylic acid in the preparation of the inventive, greases thickened with complex soaps.

Example 12

By mixing the ingredients indicated below in the proportions shown in a fat mixer of the conventional type, and heating the mixture to about 260 ⁰ C were prepared three lubricants 1, 2 and 3. FIG. In the case of greases i and 3, the free acetic acid was added after the mixture of the remaining ingredients had reached a temperature of about 57 ° C, and heating was then continued to 260 ° C. The lubricating greases were then cooled ^{to about 120 ° C. while stirring.} The phenyl-a-naphthylamine was then added and the mixture was cooled further to 93 ° C., leveled and packaged.

1 Grease I 3 2.00 2.0 2.0 I 2 Weight percent 2.00 2.0 2.0 8.00 4.0 Components 6.00 0.6 3.3 Hydrogenated fish oleic acids 10.7 5.3 Hydrogenated castor oil ... 0.50 0.5 0.5 Glacial acetic acid Hydrated lime Calcium acetate 81.50 84.2 82.9 Phenylnaphthylamine .. Naphthenic mineral out bad out oil distillate; viscosity draws draws 7.8cSt at 98.9 ° C ... > 260 > 260 properties Appearance and structure. 220 210 Drop point, ⁰ C Penetration at 25 ⁰ C, 238 230 mm / 10 Resting penetration ... Walk penetration 308 315 after 60 thrusts. insoluble insoluble Walk penetration after 75000 15th 15th Bump Weights Weights Water solubility Alpine pasture test, resilient speed 224 224 252 252 4-ball test according to Shell Running load, kg Welding load, kg ..

It should be noted that the grease 3, to which a significant amount of finished calcium acetate has been added, has an excellent appearance, good consistency, water insolubility and extreme pressure properties and that Lubricating grease 1, whose caleium acetate was formed entirely in situ, is completely on par. The grease 2 however, which only contains ready-added calcium acetate, behaves noticeably less favorably.

According to the invention, finished metal salts can also be used for such lubricating greases whose salt and soap fractions contain various alkaline earth metals.

Calcium complex soaps according to the invention give greases of excellent thermal and mechanical properties Resistance, long-term lubricity and good resilience. To manufacture the In complex soaps, alkaline earth metals other than calcium can also be used. Calcium soaps will, however preferred because of their good structure and ease of manufacture.

It has been found that greases of excellent structure and good resistance are mixed Alkaline earth bases can be produced when the alkali metal is of higher molecular weight than finished Salt of the low molecular acid is used. By using the dry salt in place Its formation in situ from the hydroxide are the large quantities of water of hydration which are generally found in alkaline earth hydroxides are included, turned off. This enables a more economical and faster manufacturing process. To the soap formation of the high molecular weight Acids and the necessary part of the not as a finished salt of the heavier alkaline earth metal To complete the introduced low molecular weight acid, one can use dry calcium hydroxide. the Soap and the salt of calcium are formed simultaneously in the presence of the finished salt of the heavier alkaline earth metal.

Example 13

A lubricating grease is made from the following components:

Components by weight percent

Glacial acetic acid 4.00

Hydrogenated fish oleic acids 2.00

Hydrogenated castor oil 2.00

Strontium acetate 7.00

Hydrated lime 3.20

Phenyl-a-naphthylamine 0.50

Naphthenic mineral oil distillate; Viscosity 7.8 cSt at 98.9 ° C 81.30

All ingredients except the acetic acid and the phenyla-naphthylamine were placed in a direct-fired fat kettle and heated to 57 ° C. with mixing. At this temperature, the acetic acid was added and then heated to 260 ⁰ C. At 104 to 120 ^° C., some foaming occurred. The mixture was then cooled to 120 ° C. with stirring. The phenyla-naphthylamine was then added and the fat was further cooled to 93 ° C., then leveled in the Gaulin homogenizer, filtered and packaged.

properties

Molar ratio of acetic acid to high molecular weight acid: .. 10: 1

% free alkalinity as NaOH 0.25

Drop point, ⁰ C> 260

Penetration at 25 ^° C., mm / 10

Resting penetration 220

Walk penetration after 60 thrusts 282

Walk penetration after 100,000 hits. 325

Solubility in boiling water 0

Water wash test, ° / "Loss 0

Wheel bearing test, 6 hours at 104 ^° C. good

As mentioned, other lower carboxylic acids can also be used instead of or together with acetic acid will. Attempts to produce lubricating greases with good structure using calcium complex soaps from formic acid and high molecular acids (especially oxy acids) as thickeners, the calcium formate being the predominant component, however, did not lead to full success. These Complex soap can be dispersed at higher temperatures, but tends to precipitate on cooling. The precipitated soap can be redispersed by homogenizing with high shear stress However, the product obtained is no longer solid.

Lubricating greases with excellent structural stability and excellent consistency for pressing out of hand-operated Syringes or mechanical centralized lubrication systems are available from Use of mixtures of formic acid and

aa9 67S043

Acetic acid in the complex soap. This embodiment of the invention is illustrated by the following examples.

Example 14

A grease was made up of the following ingredients manufactured:

^. ,., Weight

_{Constituent percent} .

Formic acid (98 to 100%) 10.0

Oxystearic acid 5.0

Hydrated lime 9.4

Naphthenic mineral oil distillate;

Viscosity 7.8 cSt at 98.9 ° C 75.60

The fat kettle was charged with the oxystearic acid and two thirds of the mineral oil and the charge heated to 54 ° C. Then the formic acid and immediately afterwards a slurry of the lime in added to the rest of the mineral oil. The mixture was heated further to 260 ° C. with stirring and the mixture was then cooled calmly. As it cooled, the soap appeared to be failing. After homogenizing the non-uniform A uniform, but liquid product was obtained.

Example 15

A lubricating grease is made from the following components:

_ Weight

_{Constituents percent}

Acetic acid 5.00

Formic acid 5.00

Hydrogenated fish oleic acids 2.50

Oxystearic acid 2.50

Hydrated lime 8.25

Naphthenic mineral oil distillate;

Viscosity 7.8 cSt at 98.9 ° C 76.75

Manufacturing

Similar to example 14
properties

Molar ratio of low to high molecular weight acid .. 10: 1

Appearance Excellent, smooth

homogeneous product penetration at 25 ° C, mm / 10

Resting penetration,. 238

Walk penetration after

60 thrust 280

Walk penetration after

100,000 thrusts 365

Water solubility insoluble

Drop point, ⁰ C> 260

Bearing tests at

27 ° C, 104 ° C, 121 ° C .. excellent lubrication of the bearing 204, no tendency to fiber or leak out of the bearing, no leakage through the Bearing seals

Almen test, load capacity 15 weights (good.

Condition of the pen)

Certain additional ones. Advantages result from the use of oxyacids as a low molecular weight component the metal-rich thickeners of the invention. Lactic acid cutting fats have less of a tendency to harden in storage as lubricating greases in which the low molecular weight acid is not an oxy acid. Also owns the lactic acid grease has a more cohesive, fibrous structure, which is often an advantage. A This type of grease is illustrated in the following example.

Example 16

A grease was made up of the following ingredients manufactured:

Weight components. percent

Hydrogenated fish oleic acids 4.0

Lactic acid, 100% (used as

85% acid) 8.0

Hydrated lime 4.2

Naphthenic mineral oil distillate;

Viscosity 7.8 cSt at 98.9 ° C 83.8

The hydrogenated fish oleic acids and two thirds of the Mineral oil was placed in a fat kettle with direct firing and heated to 66 ° C. then the lactic acid was added followed immediately by a slurry of the lime in the remainder of the mineral oil. The mixture was then heated to 260 ° C. and the grease was cooled to 93 ° C. with thorough mixing. Thereon it was leveled, nitrided and packed.

properties

Molar ratio of lactic acid to

hydrogenated fish oleic acids .. 7: 1

Free alkalinity as NaOH,% 0.32

Appearance Excellent, smooth

even fat, slightly fibrous and coherent penetration at 25 ° C; mm / 10

Resting penetration 245

Walk penetration after

60 Push 261

Walk penetration after

65,000 thrusting 400

Water solubility insoluble

Ancestral test, load capacity 15 weights (good

Condition of the pen) Norma Hoffmann oxidation test, 0.35 kg / cm ²

O ₂ pressure drop in hours 235

Bearing tests at

27 ° C, 104 ° C, 121 ° C ... excellent lubrication,

no tendency to exit the camp or

to lick through the seal

Wheel bearing test, 6 hours
good at 104 ° C

The high pressure properties of the lubricating greases according to Examples 1 to 5 can be achieved by adding lead or improve significantly with other letterpress sets, as the following examples show.

Example 17

A leaded grease was made from the following

Ingredients manufactured: ". ,,

⁰ weight

Constituents percent

Glacial acetic acid 8.0

Oxystearic acid 4.0

Hydrated lime 6.0

Lead acetate (CH ₃ COO) ₂ Pb · 3H ₂ O 2.0

Naphthenic mineral oil distillate;

Viscosity 7.8 cSt at 98.9 ° C 80.0

A fat boiler with direct firing was charged with the oxystearic acid, the lime and the mineral oil and the agitator turned on. As soon as the lime was completely dispersed, the mass was heated to 54 ° C. then the acetic acid and then the lead acetate was added as a solid salt. It was further heated to 238 ° C. then the grease was cooled to 93 ° C with stirring and in a Gaulin homogenizer at one time Throughput equalized at 340 at.

properties

Molar ratio of acetic acid to

Oxystearic acid 10: 1

Appearance Excellent, smooth

homogeneous fat

Free alkalinity as NaOH,%
Penetration at 25 ° C, mm / 10

Resting penetration

Walk penetration after

60 pushing

Walk penetration after

92,000 thrusts

Drop point, ⁰ C

Ancestral test, resilience

0.26 330

340

380> 232

15 weights (good condition of the pen) Water solubility insoluble

Two greases A and B were made from the following ingredients without the addition of lead:

Components

Glacial acetic acid

Hydrogenated fish oleic acids

Hydrogenated castor oil

Hydrated lime

Naphthenic mineral oil distillate; Viscosity 7.8 cSt at 98.9 ° C ...

Molar ratio of acetic acid to high molecular weight acids

A I B percent by weight

6.4 1.6 1.6 4.8

85.6

8.0 2.0 2.0 6.0

82.0

about 10: 1

The lead-containing grease was tested by high pressure tests in a 4-ball apparatus according to Shell with the Greases A and B compared. The results were as follows:

High pressure tests

Grease

Lead fat

Calcium complex soap fat A
(without lead)

Calcium complex soap fat B
(without lead)

4-ball test

Schram-

men-

by-

knife,

mm ¹ )

285 + 252 - 224 -

252 + 224 -

252 + 224 -

- 2.45 2.06

2.39

2.25

¹ J Mean diameter of the scratches from three spheres.

With the loads marked with - \ - the balls were welded, with the loads marked with - not.

The values show that the lead-containing grease increases in comparison with the lead-free greases at high loads leads to less wear of the friction surfaces.

A product that meets all the requirements placed on a drawing lubricant consists, according to the invention, of a calcium complex soap of a high molecular weight carboxylic acid and a low molecular weight acid, e.g. Acetic acid, in which the low molecular weight acid is up to 90 ° / ₀ of the complex soap. This complex soap can be prepared according to the following example.

Example 18

A grease-like mass was made from the following ingredients:

Components by weight percent

Acetic acid 10.00

Hydrogenated fish oleic acids 5.00

Hydrated lime 7.30

Naphthenic mineral oil distillate;
Viscosity 7.8 cSt at 98.9 ° C 77.70

The acetic acid and hydrogenated fish oleic acids were mixed with two thirds of the mineral oil and heated to 66 ° C warmed up. Then the lime was added as a slurry in the remainder of the mineral oil and the fat up Heated to 230 to 260 ° C, forming a solid, fatty base. This had the following properties :

properties

Molar ratio of acetic acid to hydrogenated

Fish oleic acids 10: 1

Drop point, ° C> 260

Penetration at 25 ° C, mm / 10

Resting penetration 210

Walk penetration after 60 thrusts .. 215

Walk penetration after 75,000 thrusts 190

Ancestral test, load capacity 15 weights

This base mass was then diluted to 75% with mineral oil and put in the Gaulin homogenizer equalized.

The product was of a semi-liquid, somewhat gelatinous consistency and had a dropping point of 260 ° C maintained. An ancestral sample showed that the diluted product had excellent high pressure behavior, by enduring a load of 15 weights.

In the cutting oils and metalworking fluids of the prior art, the extreme pressure properties usually brought about by the addition of sulfur, phosphorus and / or chlorine. These substances can immediately boiled down in the oil or reacted with other substances, such as fats, to form concentrates and then mixed with the oil. These liquids are generally corrosive, the higher the level, the more so their resilience is. According to the invention, non-corrosive cutting oils of excellent resilience are obtained. Mineral oils in which the soap additive according to the invention is dispersed by homogenization are stable and show no tendency to settle during prolonged storage.

Mixtures of various proportions of Grease A of Example 17 were made in the following Concentrations of a naphthenic mineral oil distillate with a viscosity of 3.2 cSt at 98.9 ° C

added. The mixtures were in, a Gaulinschen Homogenizing machine leveled. The one with the 4-ball apparatus The shell pressure values and scar diameters obtained are shown below. Farther examinations carried out on a typical

sulphurized fat (sulphurized sperm oil with 12% sulfur content) to which the same additive is added was, show that the usual extreme pressure additives through Adding this soap not only does not suffer, but greatly improves it.

4-ball high-pressure test according to Shell, carried out on metal treatment oils, consisting of dispersions of

Calcium complex soaps in mineral oil

Lubricating oil I. Soap additive 2.5 load 90 welding Scratch diameter,
mnij mean basis % kg ' 176 (immediate welding) of three balls mineral oil 0 176 (welding after 3 seconds) . mineral oil 20.0 176 (welding after 6 seconds) - mineral oil 10.0 156 good - mineral oil 5.0 176 good - 200 good 2.64 TV IT 'Λ "Λ f 5.0 +] 224 boundary welding 2.05 mineral oil J 5.0% sulphurized I. 156 welding 2.42 Sperm oil 140 good mineral oil

Other alkaline earth soaps, such as barium and strontium soaps, behave similarly to calcium soaps. At Instead of the fatty acids or together with them, other high molecular acids, such as branched-chain oxo acids, be used. Naphthenic acids or sulfonic acids can also be added with advantage, since they result in a more soluble product.

Further special lubricants that can be produced according to the invention are lubricants for twist rings. When twisting cotton or rayon cords, threads or tire cord, they become twisting rings and runners generally lubricated with a grease. Petrolatum has the right one for this special structure and adhesive structure required for easy application and adherence to the ring is. However, petrolatum has a low melting point, and any excessive increase in temperature during twisting, the petrolatum melts and drips off the ring and with it mutual contact of the metal parts and excessive wear and rapid failure of the rotor. The addition of substances that increase the melting point of petrolatum without affecting its consistency and color ■ influencing significantly results in an improved • lubricant and longer range of use. at Such lubricants have hitherto been known as bentones and silica gel as thickeners and melting point improvers applied. However, the former are expensive and the latter causes abrasion.

It has now been shown that the calcium-rich complex soaps according to the invention, which are relatively cheap, are excellent for increasing the melting point of petrolatum without significantly affecting its consistency, structure, structure or color. In order to disperse this complex soap in petrolatum, temperatures of about 230 to 260 ^° C. are required, the petrolatum turning dark. According to a particular embodiment of the invention, the complex soap is first produced and dispersed in a mineral oil at the high temperature required for dispersion. The complex soap concentrate obtained in this way is then mixed with the petrolatum without supplying heat. The mixture can be homogenized to facilitate dispersion. The composition and method of preparation are described in the following example.

Example 19

Manufacturing

of the calcium-rich complex soap concentrate

Components by weight percent

Hydrogenated fish oleic acids 5.00

Glacial acetic acid 10.00

- Hydrated lime .......... 7.30

Naphthenic mineral oil distillate;
Viscosity 7.8 cSt -at 98.9 ° C ......... 77.70

The high molecular acid was introduced together with two Third of the mineral oil in a steam-heated kettle and the mixture heated to 66 ⁰ C. The acetic acid was then added, followed by the lime as a slurry in the remaining mineral oil. It was further heated to 230 to 26O ⁰ C. The mass was then cooled to 93 ° C. with mixing.

Manufacture of the bonding ring lubricant
Components by weight

Calcium complex soap concentrate 20.00

Snow-white petrolatum 80.00

The petrolatum and complex soap were mixed intimately and then in a Gaulin homogenizer leveled to obtain a uniform product. To achieve sufficient lubrication however, leveling is not required.

25 26

Properties of Finished Twist Ring Lubricant The acetic acid, the hydrogenated fish oleic acids and two

The molar ratio of acetic acid to one third of the silicone oil was added to a fat kettle

hydrogenated fish oleic acids. 10-1 introduced direct firing and heated to 66 ° C.

Appearance ..: The lime was excellent at this temperature in the form of a

excessive affixable ^{5 A} ™ ^sch lambing added in the rest of the silicone oil.

Lubricant ^{The mass} was further heated to 260 ° C to complete the formation

To effect penetration at 25 ° C, mm / 10 ^ ^he complex soap. The anhydrous product

Rest penetration. '. 300 had excellent lubricating properties after cooling

Walk penetration fat structure, which is still achieved by leveling in a Gaulinschen

after 60 thrusts 320 ¹⁰ homogenizing machine has been improved.

Effect of varying amounts of complex soap on the properties of petrolatum

mixture Calcium
soap-
concentrate Petro
latum drip
Point colour Vo % ⁰ C Petrola tum - 100 38 White 1 10 90 49 White 2 20th 80 149 Yellow stitch *) 3 50 50 204 Pale yellow 4th 100 - > 260 yellow

*) Acceptable.

So you can by adding suitable amounts of complex soap to the dropping point of the petrolatum Increase about 200 ° C without an excessively discolored product to obtain.

The following examples illustrate the production of lubricating greases according to the invention from synthetic ones Lubricating oils.

Up to now, silicone oils have posed difficulties when thickening them into lubricating greases, as they are compatible with the well-known Are incompatible with soaps. However, new ways have been found to use soaps as thickeners here to be able to, such. B. the solvent transfer. To a certain extent one also had with inorganic ones Thickeners such as copper phthalocyanine, silica gel, benton and carbon black, succeeded. However, none of these was Products completely satisfactory.

It has now been found that silicone oil greases with excellent properties can be obtained with the aid of thickeners can be made according to the invention that take advantage of both inorganic and organic thickeners unite on the type of soaps. In addition, the raw materials are cheap and readily available.

properties

Molar ratio of acetic acid to
hydrogenated fish oleic acids 10: 1

Drop point, ° C> 260

Penetration at 25 ° C, mm / 10

Rest penetration 275

Walk penetration

after 60 hits 285

Walk penetration
after 75000 collisions ... 320

Water solubility In boiling water

insoluble

a ₅ Excellent lubricity (measured

by the A.B.E. C. Exam)

Example 21

Components by weight

Glacial acetic acid 4.00

Hydrogenated fish oleic acids 1.00

Oxystearic acid 1.00

Hydrated lime 3.60

Phenyl-a-naphthylamine 0.50

Di-2-ethyl-hexyl sebacate 39.90

Silicone oil 710 50.00

The hydrogenated fish oleic acids, the oxystearic acid; two thirds of the ester and the silicone oil were abandoned and heated to 66 ° C. At this temperature the acetic acid became and then that in the remainder Ester slurried hydrated lime added. The mass was then heated to 230 to 260 ° C and below Stir cooled. The phenyl-a-naphthylamine was added while cooling at 150 ° C and that The grease is then further cooled to 93 ° C. It owned a

The silicone oil greases have high drop points

and good structural stability. Even at 50, they have an excellent, permanent structure. The boiling point of the water is insoluble and water-repellent. The lack of lubricity of the silicone oil under load is caused by the metal-rich
Complex soaps noticeably improve the grease
give excellent high pressure properties. In the 55th
In contrast, lithium and inorganic soaps impart
Thickeners no increased resilience. These
Lubricating greases, their manufacture and their properties
are described below.

Example 20

A lubricating grease was made from the following components:

τ? x. jx-1 weight

_{Constituents percent}

Glacial acetic acid 10.00

Hydrogenated fish oleic acids 5.00

Hydrated lime 7.30

Silicone oil 710 *) 77.70

*) A methylphenysilicon with a high phenyl content.

properties 10: 1 Molar ratio of acetic acid to > 260 high molecular acids Drop point, ° C 295 Penetration at 25 ° C, mm / 10 Resting penetration 315 Walk penetration after 60 thrusts 355 Walk penetration insoluble in boiling after 75,000 hits water Water solubility 22nd example

A base grease was prepared by essentially following the procedure of Example 21 from the following Components manufactured:

M9 679045

Components by weight percent

Glacial acetic acid 10.00

Hydrogenated fish oleic acids 2.50

Oxystearic acid 2.50

Hydrated lime 7.30

Azelaic acid di-isooctyl ester 77.70

The grease was made with the same without heating Amount of silicone oil 200 (a methyl phenyl silicone with a high methyl content; viscosity 10 cSt at 25 ° C) mixed. The soft and very uneven mixture was added to a Gaulin homogenizer an excellent, smooth grease with good properties.

properties

Molar ratio of acetic acid to

high molecular acids 10: 1

Drop point, ° C> 260

Penetration at 25 ° C, mm / 10

Resting penetration 310

Walk penetration

after 60 thrusts 325

Water solubility insoluble in boiling

water

Example 23

Components by weight percent

Hydrogenated fish oleic acids 5.0

Glacial acetic acid ... 10.0

Hydrated lime 7.4

Phenothiazine 1.0

Polyester lubricating oil (monohydric alcohol
-dibasic acid- polyglycol -dibasic acid - monohydric alcohol;
Bp> 230 ° C at 0.15 mm Hg; Viscosity 17 cSt at 98.9 ° C, 111 cSt at 37.8 ° C) 76.6

A direct fired fat kettle was charged with the high molecular weight acid and two thirds of the polyester. The mass was heated ^{to 66 ° C. with stirring.} The acetic acid was then added, followed immediately by the lime as a slurry in the remaining polyester. The fat was heated to 26O ⁰ C and then cooled with stirring to 93 ° C. During cooling, the phenothiazine was added at 150 ⁰ C. The fat was then leveled, filtered and packaged.

properties

Molar ratio of acetic acid to

hydrogenated fish oleic acids.

Appearance

For the lubrication of jet motor bearings, furnace hinges, wagon wheel bearings intended for insertion into furnaces and for other uses at very high temperatures, petroleum based lubricants have become popular proved unsuitable. The liquid portion of these lubricants evaporates and leaves you behind Soap residue that charred, causing failure of the bearing or at least loss of lubrication leads. It is known that complex esters with multiple ester bonds, such as the systems: monobasic Acid - Glycol - Dibasic Acid - Glycol - Monobasic Acid - Monohydric Alcohol - Dibasic Acid Polyglycol - dibasic acid - monohydric alcohol, etc., exceptional lubricity at high temperatures own. Complex esters of this type are z. Described in U.S. Patents 2,575,195, 2,575,196. It has now been found that from such. Complex esters with the help of the complex soaps according to the According to the invention, solid lubricating greases which can be used at high temperatures can be produced as thickeners can, for which the alkaline earth complex soaps such. B. the calcium soaps are suitable in which Calcium acetate forms a major component.

Greases of this kind provide excellent lubrication at moderately high temperatures of about 150 to 200 ⁰ C. In the range of 26O ⁰ C and beyond, where few other substances with success are used, they also act as a lubricant. In this temperature range, even the mixed polyesters or polyesters volatilize. If this occurs with a lubricant according to the invention, a residue of calcium soap remains from the metal-rich complex soap thickener, which adheres firmly to the friction surfaces. This extremely persistent residue acts as a lubricant and has excellent extreme pressure properties. It is believed that the calcium acts as a flux on the metal surfaces, preventing welding and providing lubrication. An example of such a lubricant is given below.

Drop point, ⁰ C

Penetration at 25 ° C, mm / 10

Resting penetration

Walk penetration

after 60 thrusts

Walk penetration

after 100,000 hits ...
Water solubility ...,

Testing in the muffle furnace,
16 hours at 288 ° C

30 minutes at 371 ° C ..
High pressure properties:

Ancestral test, resilience.

Norma Hoffmann Oxy

dation sample:

0.35 kg / cm ² O ₂ -pressure-

fall in hours

10: 1

Excellent, smooth fat

> 260

240
260

335

insoluble in boiling water

Charred surface,
Remainder in good condition, surface charred

15 weights

375

The metal-rich metal complex soaps of the invention can be used in lubricating oils for the production of semi-liquid gear lubricants of excellent quality can be added. When lubricating gears that work at high temperatures, result liquid lubricants provide the best lubrication. If you use a solid grease, it becomes part of pushed away from the surfaces of the intermeshing gear teeth, causing premature channeling of the lubricant and rapid wear of the transmission due to insufficient lubrication. On the other hand, that's supposed to Lubricant have sufficient substance or viscosity to prevent it from leaking out of gear cases, that are not completely tight. If the gearbox is working under high load, it is a lubricant required to withstand this load without tearing the lubricating film.

A lubricant that meets these requirements is obtained according to the invention if one Lubricating oil adds a metal complex soap rich in metal, in which the molar ratio of low to high molecular weight

1 U44

Very high acidity, d. H. at least 30: 1 and preferably is at least 40: 1. As shown above, with a weight ratio of low to high molecular acid of 2: 1 a solid lubricating grease with relatively low concentrations of dipping agent. However, if the weight ratio of low to high molecular weight acid is 9: 1, the result is the same total concentration of thickener is not a solid grease but a semi-liquid product excellent high pressure properties, which is suitable for the lubrication of gears. This is made possible by the the following example illustrates.

Example 24

A lubricant was made from the following ingredients:

Weight constituent _percent

Hydrogenated castor oil 1.00

Acetic acid 9.00

Hydrated lime 6.15

Naphthenic mineral oil distillate; viscosity 7.8 cSt at 98.9 ° C 83.85

The fatty oil was placed in a boiler with direct firing along with two-thirds of the mineral oil and heated to 66 ° C. with stirring. Then the acetic acid and then a slurry of the Hydrated lime was added in the remainder of the mineral oil, followed by further heating up to 260 ° C. Then became the mixture was cooled to 93 ° C. with stirring. Soap seemed to settle on standing. The product was mixed and then homogenized. A consistent, smooth product resulted. After 1 month of storage no separation of the components was noticeable.

properties

Molar ratio of acetic acid to
high molecular acids 45: 1

Consistency semi-liquid

High pressure properties:
Ancestral test, load capacity 15 weights; good condition of the pin heat test, 204 ° C ... grease starts,

getting thin approximates the viscosity of an oil

The consistency and consistency of this lubricant makes it suitable for use in centralized lubrication systems that work with spray valves, which apply the lubricant in measured quantities to sliding surfaces or open gears.

The invention also enables the production of sludge-inhibited motor oils. Because it has pointed out that the metal-rich soap complexes according to the invention as sludge inhibitors for motor oils are usable. This is especially true of the alkaline earth complex soaps, which are produced by common neutralization a high molecular weight fatty acid, a sulfonic acid and a low molecular acid are formed. Soaps with a very high metal content also give the lubricating oil a sludge-inhibiting quality and excellent high pressure properties.

There are already many different substances and especially alkaline earth soaps as sludge inhibitors for modern ones Vehicle engine oils used. It has been found that a high metal content is desirable for this. the

Invention enables the addition of metal-rich additives to engine oils.

Claims (14)

Patent claims: 1. Lubricant based on lubricating oil made from synthetic or mineral oils with a content of a complex metal soap, characterized in that the complex metal soap is at least one metal soap at least one high molecular weight monocarboxylic acid, with the exception of dioxystearic acid, and contains at least one low molecular weight monocarboxylic acid, the molar ratio of the low to high molecular acid is at least 7: 1. 2. Lubricant according to claim 1, characterized in that the molar ratio of the low to high molecular acid 7: 1 to 45: 1, preferably 8: 1 to 25: 1. 3. Lubricant according to claim 1 and 2, characterized in that it is the complex metal soap in in an amount of 5 to 30 percent by weight. 4. Lubricant according to claim 1 to 3, characterized in that the high molecular weight acid 12 to 30, preferably 18 to 22 carbon atoms in the molecule and the low molecular weight acid 1 to 6 carbon atoms contains in the molecule. 5. Lubricant according to claim 1 to 4, characterized in that the metals of the complex soap one or more alkali metals or alkaline earth metals, including magnesium, or copper, zinc, titanium, Manganese, nickel, lead, cobalt, chromium, preferably a mixture of calcium and zinc, calcium and Magnesium or calcium and titanium. 6. Lubricant according to claim 1 to 5, characterized in that the metal content in the complex soap consists of a metal, preferably calcium, or various metals. 7. Lubricant according to claim 1 to 5, characterized in that the complex metal soap a mixture of calcium soaps of high molecular weight monocarboxylic acids and calcium acetate on the one hand and consists of sodium soaps of high molecular weight monocarboxylic acids and sodium acetate on the other hand, wherein the molar ratio of acetate to high molecular weight acids in each complex is at least 7: 1 amounts to. 8. Lubricant according to claim 1 to 7, characterized in that the high molecular weight acid to a substantial part is a monooxy acid, for example monooxystearic acid. 9. Lubricant according to claim 1 to 6, characterized in that the high molecular weight acids to 20 to 75 percent by weight of carboxylic acids and 80 to 25 percent by weight of sulfonic acids. 10. Lubricant according to claim 9, characterized in that the complex metal soap Calcium acetate, a calcium soap of a high molecular weight carboxylic acid and an oil-soluble calcium sulfonate in which the molar ratio of acetate to sulfonate and soap is at least 7: 1 amounts to. 11. Lubricant according to claim 1 to 10, characterized in that the complex metal soap Contains mixture of acetate and formate. 12. Lubricant according to claim 1 to 10, characterized in that the low molecular weight acid is a Is oxyacid, for example lactic acid. 13. A method for the production of lubricants according to claim 1 to 12, characterized in that the complex metal soap by common neutralization of the acid mixture with one or more 31 32 Metal oxides or hydroxides, preferably mixed with one another thereupon and the mixture in the Lubricating oil base, is formed. complex metal soap, if necessary with heating 14. Process for the production of lubricants. according to claim 1 to 13, characterized in that the soaps of the high molecular weight and / or low- 5 ■ Older patents considered: Molecular acids fully or partially preformed, German Patent No. 947 420. ® «09 679043 11.5»