DE1152496B - Process for the production of lubricating greases - Google Patents

Description

The invention relates to a process for the production of lubricating greases consisting of mineral, vegetable, animal or synthetic oils containing an oil-soluble sulfonate and a basic metal compound from the group of hydroxides and carbonates. These greases have the properties required for multipurpose use, as well as the additional ones Advantage of lower manufacturing costs than the previously known lubricating greases.

It is useful to have a multi-purpose grease available that can be used to lubricate Wheel bearings, water pumps, chassis bearings, universal joints, electric motors, quick-release bearings and Sleeve bearings are suitable. The use of a general purpose grease provides the following two essentials Advantages: Firstly, the need to store lubricating greases is reduced and, secondly, they are excluded the risk of bearings being greased with an unsuitable lubricant.

Lithium-based ones have found widespread use as multipurpose lubricating greases. These Fats have numerous possible uses. Characteristic features of lubricating greases Lithium is based on the following:

(1) Soft or buttery texture,

(2) high melting points (usually 177 ° C),

(3) good pumpability at low temperatures,

(4) high water resistance,

(5) excellent shear strength,

(6) good metal wetting properties.

One disadvantage associated with lithium-based greases is their high price.

Another type of grease can be made according to a known method by introducing larger Produce quantities of higher molecular weight aliphatic sulfonates in a lubricating oil, with additional Thickener, ζ. B. alkali salts of carboxylic acids, must be used to achieve the fat consistency. This method has the disadvantage that very high sulfonate concentrations are required as well the further disadvantage that the salts used as thickeners are carboxylic acids such as sodium acetate cause a certain instability of the grease compared to water. From this circumstance results a limited range of applications for such products, which therefore turn out to be multi-purpose grease.

It has now been found that lubricating greases can be made using sulfonic acids such as those used as dispersants are known, can be prepared by the carrier oil in the presence of an oil-soluble

Process for the production of lubricating greases

Applicant:

Continental Oil Company,
Ponca City, Okia. (V. St. A.)

Representative: Dr. W. Germershausen, patent attorney,
Frankfurt / M., Neue Mainzer Str. 49-51

Claimed priority:
V. St. v. America of October 20, 1958 (No. 768 089)

Magnesium or aluminum sulfonates with a compound from the group of aluminum alcoholates and the magnesium alkoxy carbonate complexes, the cation of which is different from the cation of the sulfonate is, mixed, then mixed with water and heated, the aluminum alcoholate or the Magnesium alkoxy carbonate complex decomposes and any solvents present, as well as excess water be removed; the total amount of these compounds acting as thickening additives is in the finished grease at least 6 percent by weight of the grease. It is essential that that magnesium and aluminum are used in combination.

Usually, the combination of a lubricating oil with a metal sulfonate also works when used excess metal to form liquid dispersions. Crucial to converting a Lubricating oil in the lubricating grease according to the invention is therefore the combined use of magnesium and aluminum in the form of suitable chemical compounds. It is essential that the achievement the fat consistency is not based on an increase in the amount of sulfonate in the end product, but on the aforementioned combination of magnesium and aluminum. The eligible amounts of suI-fonat can even be considerably lower than is customary for the production of liquid ones Oil-based dispersions.

According to the invention, it is a relatively simple and inexpensive method of manufacture of lubricating grease compositions, which in turn are also suitable as thickeners. Farther

309 650/236

Drawing "Petroleum sulfonic acid" is intended to include all sulfonic acids derived from petroleum products.

A sulfonic acid preferred for the present invention is that obtained by sulfonating postdodecylbenzene represented postdodecylbenzenesulfonic acid. Postdodecylbenzene is a by-product of manufacturing of dodecylbenzene, which as a distillation residue after distilling off Dodecylio benzene and postdodecylbenzene occurs in general. This material is also known as "stripped" postdodecyl

the lubricating greases of the invention have a higher melting point than those based on lithium. In other properties, the present grease compositions are those at least equivalent based on lithium. They have the properties to a great extent a multi-purpose grease.

According to the invention, the production of the new lubricating grease compositions can be carried out in the following process steps can be made:

a metallic compound, which on the part of _wifd ^ ^ _{and also}

referred neither em aluminum alcoholate or em ma- _d description as PDB,

gnesmmalkoxykarbonatkomplex can be, _ ° ,, " _Λ , f ,. ,. "",

/ ι-Λ % ■ t. · Τ ·· ο if * i. j · Postdodecylbenzene consists of monoalkylbenzenes

(b) adding a solution, 2 consisting of a metal-containing _d y ^^ _{in the} approximate molar ratio of compound which are transactions either a> * em aluminum alkoxide or alkoxymagnesium such fotet

can be carbonate complex, but which is not ₂₀ ^s '

contains the metal contained in solution 1, specific gravity at 38 ° C 0.8649

(c) Adding water to the combined solutions. Average molecular weight 385

genes 1 and 2, percent sulfonable 88

(d) Removal of solvents and excess

pouring water, ₂₅ ASTM D-158 Engler

(e) Cooling and homogenizing the obtained initial boiling point 341 ° C

Grease. 5% transition 361 ° C

Optionally, the metal compound can be from 50% 380 ⁰ C.

Step (a) and that of step (b) against each other - 90% 405 ° C

To deceive. 3 ° 950 / ,, 413 ° C

For the manufacture of the products according to the invention, the final boiling point is 415 ° C

Raw materials of the following properties are suitable: _,,. , - ^ _n λ < . _nnn

^{b 6} Refractive index at 23 ° C 1.4900

Sulfonic acids viscosity

These include alkylsulphonic acids, alkarylsulphone-35 at -10 ° C 2800 cP

acids, the so-called mahogany or petroleum sulfonic at 20 ° C 280 cP

acids. The mahogany sulfonic acids include 78 cP at 40 ° C

especially the oil-soluble aromas from crude oil at 80 ° C 18 cP

matic sulfonic acids. Lots of the aromatic suI aniline point 69 ° C

in the 40 ^p " _17Or ,

Side chains of cycloalkyl (that is, naphthene) groups. HieüpunJct u, i ^

The mahogany sulfonic acids cannot be aromatic oil-based Contain sulphonic acids, which are used in conventional sulfuric acid preparations of lubricating oil distillates or The oily liquid carriers can be mineral lubricants the industrial use of fuming oils from common processing methods. Other Sulfuric acid is produced in the processing of crude oil. oily materials are e.g. B. vegetable oils such as corn-Im in general, alkyl sulfonic acids require such as oil, cottonseed oil, castor oil, etc., as well as tie-24 Carbon atoms to be oil soluble. The rische oils, such as lard oil, whale oil. For some purposes Alkarylsulfonic acids are, however, only about the various synthetic oils with special properties Carbon atoms required in the alkyl radical. Use for their advantage, for example poly-achievement the required oil solubility requires alkylene glycols, ester oils e.g. dicarboxylic acid diesters hence the hydrocarbon radical of the sulfonic acid is a di- (2-ethylhexyl) ester like azelaic acid, polymeric Molecular weight between 350 and 1000. Preferred silicone oil.

its molecular weight is wisely between 400 metal-containing compounds and 700. Particularly suitable sulfonic acids are 55

Diwaxbenzenesulfonic acids, Diwachstoluolsulfonsäu- In the process according to the invention can be acids and postdodecylbenzenesulfonic acids. probably aluminum alcoholates as well as magnesium others use appropriate sulfonic acid alkoxyd carbonate complexes in accordance with the procedure, are z. B. mono- and poly wax-substituted naphtha- The alulin sulfonic acids used in the present invention, Diphenyläthersulfonsäuren, Dicetyl- 60 miniumalkoholate are converted by a thianthrenulfonic acids, dilauryl - ^ - naphtholsulfon- alcohol with aluminum metal. The aluminum acids, Dicarpryl-nitronaphthalenesulphonic acids, ungeminium can be in the form of bars, rods, saturates Paraffin sulfonic acids, hydroxyparaffinsulfon chips or beads can be used. There are acids, tetraamylenesulphonic acids, mono- and poly- all alcohols suitable that easily with aluminum Chlorine-substituted paraffin sulfonic acids, nitrosoparaf- 65 react and are volatile. These include aliphafin sulfonic acids as well as cycloaliphatic sulfonic acids table alcohols having 1 to 8 carbon atoms, where Like lauryl-cyclohexyl-sulfonic acids, mono- and poly- it was found that the primary alcohols are lighter wax-substituted cyclohexylsulfonic acids. The bees react with aluminum as the secondary or

5 6

tertiary alcohols. With the normal chips or powder examined very quickly, under certain circumstances

straight-chain alcohols, the regularity is almost explosive,

found that their responsiveness with at times it is useful from different

increasing boiling point. Unfortunately, reasons such as profitability

the solubility of the normal, primary Aiko- 5 based, first to produce magnesium methylate and

bring the aluminum alkoxides produced in this way to transesterify this to isobutoxide.

borrowed hydrocarbon solvents extremely low. The production of alcoholates and the alkoxy

It was also found that the reactive carbonate complexes are not the subject matter of the present

ability of primary, branched alcohols of the pri- invention,

normal alcohols with the same boiling point as solvents

compare was; in addition, however, the solubility was ° "

Far better in common solvents. In general, the volume of solvent, the alcohols used and their boiling points, which results from the solutions of the individual reactants in the order of increasing reactivity, are sufficient for the process. O-compiled. If necessary, additional solvents _T 1 it · ι, 1 co co r · can be used. To do this, the following solutions are

isopropylalkorioi 82, i L · ^^ _suitable . p _etr oleumnaphtha, other aliphatic

tert-butyl alcohol 82.9 C _tables hydrocarbon solvents, aromatics, aluminum

sec-butyl alcohol 99.5 ° C alcohols. In general, any volatile organ-

Methyl alcohol 64.7 ° C _ao African solvents, if there is insufficient

n-propyl alcohol 98 ° C active hydrogen atom or ion for a decomposition

Contains n-butyl alcohol at 117 ° C.

Isobutyyl alcohol 107 ° C. The amount of the

n-amyl alcohol 138 ° C made thickeners or greases used

n-Hexyl alcohol 157 ° C ² 5 Gelling agent can contain between 6 and 50% of the lubricant

7-ethyl-butylalkohoi 149 ° C ^{rich Betra} g ^s> J ^{e of the} desired consistency

I ¹ ... ,,,, ",, _1O . _o "and the type of sulsonate used. In general

2-Ethyl-hexyl alcohol 184 ° C _mdnen ^^ _{preferred amount in the range of v} ^s _on

The magnesium alkoxy carbonate complex is 8 to 15%. forms by: 30 The sulphonate content of the thickener can be between

a) reaction of magnesium with the excess ^{4 (L and 9W} <> ^concerning ^ ^s 'is preferably 60 to 80' / .. an alcohol having less than 6 carbon _Q f ^ie f ™™ composition of the atoms in these, with a alcohol-insoluble Ma- lubricating grease systems dispersed inorganic substances forms magnesium alkoxide; f ™ Μ ™ α & · ^{It is} assumed that the above

.. "". ., ",. , 35 different magnesium in several or more of the

b) Production of an alkanolless magnesium present in the following forms: Magnesium hydroxide, alkoxy-carbon dioxide complex by introducing Mg (OH) ₂ ; Magnesium carbonate, MgCO ,; basic of carbon dioxide in the magnesium * koxyd- magnesium carbonates, 4MgCO ₃ · Mg (OH) ₂ · 4H ₂ O alkanol mixture until em soluble complex corresponds _oc j _er 3 m ° CO "· Mg (OH) ₀ -3HO

is standing. ₄₀ Similarly, it is assumed that the existing AIu-

The minium used in the process according to the invention in one or more of the following forms Magnesium can be in the form of bars, rods, lathes: aluminum hydroxide Al (OH) ₃ ; Aluminum chips or powder are present. For the oxide Al ₂ O ₃ ; and hydrated alumina, suitable alcohols include all those AlO (OH). Obviously these are only hypotheses; which react easily with magnesium and are volatile 45 no restriction is intended. Ways are. These include saturated aliphatic the complex nature of the dispersed inorganic alcohols with up to 5 carbon atoms. Since metha- see phase and for the sake of clarity, in the nol and ethanol are very easily reacted with magnesium, the concentrations of the dispersed yaws and are readily available, phase as magnesium hydroxide or aluminum these are preferred. Isopropanol is also suitable, its 5 ° hydroxyd expressed. However, implementation with magnesium is difficult one. ^ ₁₁

and runs very slowly. The primary example 1

Alcohols down to normal hexyl alcohol are quite a representation of aluminum isobutylate

satisfactory in terms of their reactivity - starting materials -

compared to magnesium, and they are volatile. The 55: .. "., '.,. . . ", _No. "", _A1 _ _N

secondary and tertiary alcohols up to the hexyl ¹⁵ ' ^{5 Teüe} Ammimummetall (99.9V. Al bars)

Alcohols can be used, but 294.5 parts of a solvent mixture (40% xylene -

their reactions with magnesium take a very long time - 60% isobutanol)

sam. Magnesium powder, magnesium with pure upper.

as well as reaction initiators such as mercury

chloride and carbon tetrachloride are in the reac- The aluminum was in a three-necked

tion with the higher alcohols is useful. The 0.5-1 round bottom flask with thermometer and reflux reaction rate submitted for implementation by Ma Kühler. The solvent mixture was added magnesium with methanol depending on the size of the and then 2 drops of a saturated Surface and on the extent of the mechanical 65 solution of mercury chloride in isobutanol added deformation of the magnesium crystals. Bar joint. The flask was heated and the solution magnesium reacts in a very medium refluxing manner compared to sticks, until all of the aluminum is slowly, while the reaction with magnesium minium was implemented. After cooling it was

a clear product containing 5.05% by weight of aluminum was obtained.

Example 2
Preparation of magnesium isobutyl carbonate

Starting materials:

25 parts magnesium metal (bars)
553 parts of isobutanol
515 parts of methanol

Way of working

The magnesium was placed in a 2-liter three-necked flask with two reflux condensers and a CO _{2 inlet frit.} 515 parts of isobutanol and 515 parts of methanol were added. A catalytic amount (0.2 part) of mercury chloride was then added. The contents of the flask were heated to reflux temperature and the introduction of CO _{2 was} started. After about 20 hours had passed, all of the magnesium had reacted, whereupon the methanol was removed by heating to 96 ° C. During this process, CO _{2 was also} introduced. After cooling, 38 parts of isobutanol were added to the contents of the kofben. The product contained 4.5 percent by weight magnesium.

Example 3

Representation of sulfonate-containing lubricating grease with excess base and mixed cations

Starting materials:

A. 401 parts PDB sulfonic acid (0.572 meq / g total acidity; 0.517 meq / sulfonic acid acidity; Solvent naphtha)

1090 parts cylinder oil 400 SSU at 37.8 ° C

55 parts of aluminum isobutylate solution
(in xylene; 5.6% Al)

B. 264 parts of magnesium isobutoxy carbonate

solution (in isobutanol; 4.7 ° / c Mg)

C. 60 parts of water

Way of working

The starting materials of group A were fed to a mixer. The mixture was heated to 50 ° C heated and mixed with the magnesium solution while stirring. The water was then added. With continued stirring, the contents of the vessel were heated to 200 ° C. in order to remove the volatile solvents and remove the unreacted water. At this temperature the product was fat-like Consistency. After cooling, the grease turned into a light brown, clear, somewhat granular Mass homogenized. An addition of one percent or less of high molecular weight fatty acids eliminated the graininess. This grease had the following theoretical composition:

Aluminum hydroxysulfonate 8.3%

Aluminum hydroxide

Magnesium hydroxide 2.4%

Cylinder oil 400 89.3 ° / o

The physical properties of this grease are shown in the table.

Example 4

Representation of sulfonate-containing lubricating grease
with excess base and mixed cations

Starting materials:

A. 401 parts PDB sulfonic acid (as in Example 3) 1090 parts cylinder oil 400 SSU at 37.8 ° C

264 parts of magnesium isobutoxy carbonate

solution (in isobutanol), 4.7% Mg)

B. 55 parts of aluminum isobutylate solution

(in xylene, 5.6% Al)

C. 60 parts of water

Way of working

The procedure was the same as in Example 3, with the modification that the magnesium and the Aluminum solution were swapped. The fatty gel began to close at about 150 ° C in this reaction form. Under the working conditions at 230 ° C, the product was fat-like. The product was clear, light brown in color and had a buttery consistency. It had the following theoretical composition:

Magnesium sulfonate 10.38%

Magnesium hydroxide 1.86%

Aluminum hydroxide 0.72%

Cylinder oil400 87.18%

The physical properties of this grease are shown in the table.

Example 5

Representation of a grease mixed with
Cations from a natural sulfonic acid

Starting materials:

A. 135 parts petroleum sulfonic acid (1.53 meq / g ge

velvet acidity; 53.8% sulfonic acid;
44.5% thinner oil)

823 parts light oil with a viscosity of 900 SSU at 37.8 ° C

19.5 parts of water

237 parts of magnesium methoxycarbonate
in methanol (5.05% Mg)

B. 137 parts of aluminum isobutylate in xylene

(5.32% Al)

C. 88 parts of water.

35

55 How it works

The raw materials of group A were fed to a mixer. The mixture was heated to 100 ° C to remove the methanol. The aluminum isobutoxide and then 88 parts of water were added with stirring. The volatile solvents were removed by heating to 150 ° C at atmospheric pressure, followed by heating to 210 ° C under a nitrogen atmosphere. The product was liquid at 210 ° C, but assumed a fat consistency on cooling. After homogenizing twice, the fat had a penetration depth of 300 mm · 10 ^-1 . It was dark brown in color and stable in operation.

9 10

This lubricating grease had the following theoretical atmosphere: it was heated to 165 ° C. It occurred to me

composition: dark, clear, liquid product of the following ingredients

Magnesium sulfonate 7.5 «/. composition at:

Magnesium hydroxide 0.6% Magnesium PDB sulfonate 33.2 ^fl / o

Aluminum hydroxide 2.1% ⁵ magnesium hydroxide 2.3%

Axle oil 89.8% azelaic acid di-2-ethyhexyl ester .. 64.5%

15th

Example 6

Representation of a mixed cation grease with a synthetic liquid base

Starting materials:

A. 3080 parts PDB sulfonic acid (0.56 meq / g

Total acidity; 26.5% sulfonic acid acidity; 23.5% oil; solvent Naphtha)

776 parts of azelaic acid di-2-ethylhexyl ester
116 parts of water

B. 2427 parts of magnesium isobutoxycarbonate

in isobutanol (4.03% Mg)

Way of working

The starting materials of Group A above were placed in a suitable reaction flask. The mixture was heated to 55 ° C. with stirring, after which the magnesium isobutylate solution was added. The volatile solvents were removed by heating to 130 ° C, followed by sticking the grease
Starting materials:

A. 867 parts of the intermediate obtained above

product

1442 parts of azelaic acid di-2-ethylhexyl ester

B. 111 parts of aluminum isopropylate (13.17% Al) 440 parts of benzene (as a solvent therefor)

C. 148 parts of water

Way of working

The starting materials of group A were placed in a mixer, heated to 50 ° C and the benzene Aluminum isopropylate solution added. The water was then added. By heating to 200 ° C. and with stirring, the volatile solvents were removed. Still in the heat 11.8 parts of phenothiazine were added as an antioxidant. The physical properties of this grease are shown in the table.

Physical properties of the greases

Commercially available
Lithium grease Example 3 Example 4 Example 186 226 243 199 250 300 260 227 275 340 310 295 290 350 315 355 2.75 5.8 1.4 2.5 2.2 3.0 2.8 , 7.4 4.5 4.8

Dropping point, ⁰ C ¹

Penetration depth; how received

60 strokes 2

10,000 strokes

Water washout ³ %

Weight loss, 1000 operations
(Navy gear wear)

g (5-pound load), mg

g (10-pound load), mg

¹ ASTM method D 566.

² ASTM method D 217.

^s ASTM method D 1264.

Claims (5)

PATENT CLAIMS: 1. A process for the production of lubricating greases consisting of a mineral, vegetable, animal or synthetic oil base, an oil-soluble sulfonate and a basic metal compound from the group of hydroxides and carbonates, characterized in that the carrier oil is in the presence of an oil-soluble magnesium or aluminum sulfonate with a compound from the group of aluminum alcoholates and magnesium alkoxy carbonate complexes, the cation of which is different from the cation of the sulfonate, mixed, then mixed with water and heated and after the aluminum alcoholate or magnesium alkoxy carbonate has been added. complex removes the solvent and excess water present, the starting materials being mixed in such amounts that the total amount of thickening additives in the finished lubricating grease is at least 6 percent by weight of the total grease. 2. The method according to claim 1, characterized in that the oil-soluble magnesium or Aluminum sulfonate in situ by adding a compound from the group of aluminum alcoholates and magnesium alkoxycarbonate complexes to form an oil-soluble sulfonic acid solution in which the carrier oil is produced. 3. The method according to claim 1, characterized in that the sulphonate is postdodecylbenzenesulphonate. 309 650/236 11 12 4. The method according to claim 1, characterized by dicarboxylic acid with aliphatic alcohols or indicates that the cation is the basic compound of a silicone polymer. bond a mixture of magnesium and aluminum minium is. 5. The method according to claim 1 to 4, characterized in 5 publications considered: characterized in that the oil base is known U.S. Patent Nos. 2,540,533, 2,629,692; synthetic lubricating oil in the form of a poly- British Patent No. 789,820; alkylene glycol, a diester, an aliphatic French patent specification No. 1066,631. © 309 650/236 7.63