HU192197B - Heavy duty grease compositions resistant to high temperature - Google Patents

Abstract

The invention relates to aluminium complex lubricating grease compositions which are resistant to high temperatures and high stresses and are prepared from known base materials. Relative to the total quantity, the composition contains 1 to 15 % by mass of an antioxidant, an organic or inorganic additive which increases the lubricity, and a corrosion-inhibiting additive as well as, if appropriate, an additive which improves the rheological properties, an additive which reduces the syneresis or increases the colloid stability, and an additive which enhances the hydrophobic character.

Description

or a C 15 -C 19 carboxylic acid copolymer having a molecular weight of 800 to 1500; and optionally containing from 0.03 to 0.06% by weight of silicone oil having a molecular weight of 5000 to 100,000 as a water repellent.

It is known that grease lubrication requirements for roller bearings and other heavy duty lubrication points have increased significantly as RPM, load and operating temperature increase. Today, lithium-based and alkali-metal complex-based machine greases are used primarily for such lubrication points. Of these, lithium and lithium-calcium mixed-base fats, due to their relatively high drop point, become unstable due to their phase transition point of 125-135 ° C, and therefore cannot be recommended for lubrication above 120 ° C.

German Patent Nos. 232,201; and U.S. Patent 3,402,615).

Calcium complex, barium complex, and benzene-based complex machine greases have an unsatisfactory life span, are lengthy, complex, and costly (Hungarian Patent Nos. 163,675, 3,656,944 and Hungarian Patent 175,353).

To overcome these difficulties, more recently, fats, called aluminum-based complexes, have been used which have a higher thermal stability than lithium fats, rheological properties and a longer life than calcium complex fats (2,654,710, 2,719,826, 3,511,781, 3,574,111,

591,505; U.S. Pat. No. 4,132,658.

Despite their many advantages, the aluminum complex greases known to date do not fully meet the modern lubrication needs. For modern greases, in addition to consistency and thermal stability, it is necessary to ensure a very long, preferably thermooxidative stability over the entire lifetime of the particular machine element, high load-bearing capacity (preferably high pressure lubricity) and corrosion resistance.

Aluminum complex machine greases known to date do not meet these three conditions together and generally meet at most one or two of the above requirements. Thus, U.S. Patent No. 2,719,826 only meets the requirement of lubricity, U.S. Patent No. 3,725,275 only corrosion protection, U.S. Patent No. 3,591,505 only meets the requirement of thermooxidative stability. U.S. Patent Nos. 3,663,726, 3,620,975 fulfill only the requirement of thermooxidative stability in their entirety and do not meet the state of the art requirements for lubricity (hereafter EP property = Extreme Pressure). The anti-corrosion properties of any fat are not satisfactory.

The lubricating grease 2 described in Polish specification No. 78,424 contains only lubricant and antioxidant additives and has no corrosion protection effect. Polish Patent No. 101,989 also refers to aluminum complex corrosion-resistant grease which does not have sufficient thermal oxidation stability.

It is apparent from the list that no known lubricating grease is present at the same time in the known patent literature.

The present invention relates to a machine grease composition which simultaneously fulfills the most important requirements and which has:

- thermal stability,

- thermo-oxidation stability,

- lubricity and EP properties,

and corrosion inhibiting effect.

It has now been found that by addition of an aluminum complex grease made from the raw materials corresponding to the above patents in any known manner by a suitable combination of the additives listed below, a high temperature, long life corrosion inhibiting lubricating grease is obtained.

The base oil required for the preparation of the machine grease composition is a fine mineral oil having a viscosity of 10-30 mm '/ sec at 100 ° C.

The raw materials for soap and gel formation according to known methods include aluminum isopropylate (ALIP), cyclic aluminum isopropoxide of formula (III), cyclic aluminum trioxide tri (C 15-19) acylate.

The reagents used to make the complex so-called mixed salt soaps may be C15-C19 fatty acids, the cyclic acid benzoic acid. The reagent used to form the basic double salt is water as needed.

The functional additive package of the composition comprises at least three, but preferably 3-5, of the substances listed below and grouped by mode of action.

These groups of substances are:

Antioxidant additives, compounds of the formula I and / or II, wherein R is C 5 -C 15 alkyl or C 6 -C 15 aryl,

Me denotes zinc, antimony, lead or tin or methyl or phenyl-β-naphthylamine

1-5% by weight.

2. Anti-corrosion additives, namely barium (C 6-14 alkyl) sulfonate, barium or calcium (C 6-14 alkyl) (C 9-11 aryl) sulfonate, dicyclohexylamine (C 15-19) fatty acid ester, triethanolamine (C15-C19 fatty acid) ester or sodium nitrite in an amount of 0.25-10% by weight.

3. Inorganic or organic lubricants, namely molybdenum disulphide, soft graphite or calcium acetate or barium or lead dinonylnaphthalene sulphonate, (C15-C19-fatty acid) lead salt, dibenzyl disulphide, sulfur -C 19 fatty acid or tricresyl phosphate in an amount of 0.5 to 10% by weight.

4. Synthesis-reducing and Colloidal Stability Additives, namely 3000-6000 Molecular Weight Polyacetyl Methacrylate, 1,000,000-3,000,000 Molecular-21

192 192.

0.5 to 1.0% by weight of a polyisobutylene or copolymer of 15 to 19 carbon atoms of a weight of from 800 to 1500.

5. Water repellent additives, namely silicone oils having a molecular weight of 5,000 to 100,000, such as polyalkylsiloxanes.

To achieve the desired effect of the listed additive groups, at least one compound must be present in the composition as an antioxidant additive, an anticorrosive additive, an lubricant, and an EP effect additive. However, it is possible to add one or more additives (polymers, silicones) from each of the groups, that is, in addition to the three groups, if the purpose of use requires it.

The base fat of the above-listed composition is prepared in a known manner and then the additives are blended in the cooling phase of the fat production, the resulting composition is completely cooled, homogenized, peeled off and packaged.

The maximum admixture temperature is the decomposition temperature of any of the additives.

The following examples of the preparation of the lubricant composition described above are provided without limiting our scope to the substances and concentrations listed in the examples.

Example 1

The composition of the base fat

4.6% C 15-19 fatty acids

2.0% benzoic acid

3.3% Al isopropylate (ALIP)

0.3% water

89.8% 1: 1 blend of refined and paraffinic heavy and residual oils with a viscosity of at least 10 mm ² / sec at 100 ° C

100.0%

The oil was dissolved in ² parts of finely crushed Al isopropoxide at 70-80 ° C. Stearic acid is then added and the material is gradually heated to 120 ° C. The material is maintained at this temperature for about one hour with stirring. The rest of the oil is dissolved in benzoic acid at 100-110 ° C and added to the reaction mixture obtained above. The resulting reaction mixture was again heated to 120-125 ° C for one hour. The system is then cooled to 80-90 ° C and water is added slowly with vigorous stirring. After the addition of water, the temperature was raised continuously to 210 ° C, maintained at this temperature for about 20 minutes and then cooled to 70-80 ° C. To the cooled fat are added the additives listed in the examples below, then the fat is homogenized, homogenized and de-aerated.

To 95 kg of base fat above add the following additives:

Zn-di (C 5 -C 15 alkyl) dithiophosphate 2.5 kg

Pb-Sb-di (C 5 -C 15 alkyl) dithiocarbamate 1.5 kg

Badinonyl naphthalene sulfonate 0.5 kg

Polyisobutylene (PiB) 0.5 kg (Ms = 1,000,000-3,000,000)

Example 2

The following additives are added to 94 kg of base fat of Example 1:

Zn-di (C 5 -C 15 alkyl) dithiophosphate 2.0 kg

Di-benzyl disulfide 2.0 kg

Dicyclohexylamine oleate 1.0 kg

Polyacetyl methacrylate (Ms = 3000-6000) 1.0 kg

Example 3

To 95 kg of base fat of Example 1, the following additives are added:

Sb-di (C 5 -C 15 alkyl) dithiocarbamate 2.2 kg

Sulfuric oleic acid 1 kg

Tris-cresyl phosphate 0.25 kg

MoS ₂ i, 0 kg

Triethanolanine (C15-C19 fatty acid) ester 0.5 kg

Phenyl-β-naphthylamine 0.05 kg

Example 4

To 96 kg of base fat of Example 1, the following additives are added:

: 1 mixture of Zn-di (C 5 -C 15 alkyl) dithiophosphate and Zn-di (C 6 -C 15 aryl) dithiophosphate

2.4 kg

Chlorparaffin 0.5 kg

Calcium acetate 0.80 kg

Sodium nitrite 0.25 kg

Silicone oil 0.05 kg

Example 5

The composition of the base fat:

4.9% of C15-19 fatty acids

1.7% benzoic acid

3.6% cyclic Al isopropoxide

89.8% SAE 40 Base Oil, Viscosity 100 'Con 13-15 mm ^J / sec.

Part of the base oil of 70-80% ° C and the dissolved amount of stearin acid of the formula, the temperature was 100 ° C is increased, and by addition of the residual oil dissolved in ^l aluminum isopropoxide. Under vigorous stirring and circulation, the temperature was raised to 205 ° C, then the reaction mixture was cooled to 70-80 ° C at a constant rate. The following additives are added to the cooled base fat, then homogenized and vented.

To 96.0 kg of the above base fat add the following additives:

Pb-di (C 5 -C 15 alkyl) dithiocarbamate 2.0 kg Pb stearate 0.5 kg Cadinonil-naphthalenesulfonate 0.5 kg (C15-C19 carboxylic acid) - ester copolymer 1.0 kg (Ms = 800-1500) 3

192 197

Example 6

The following additives are added to 98 kg of base fat of Example 5:

Zinc di (C 5 -C 15 alkyl) dithiophosphate 1.0 kg

Barium sulfonate (Ms = 800-1200) 1.0 kg

Example 7

The composition of the base fat is 2.43% C 15-19 fatty acids 0.84% benzoic acid

1.81% cyclic Al isopropoxide

47.50% SAE 50 base oil, viscosity 100 ° C

17-20 mm ² / sec.

47.42% Bright Stock, Viscosity at 100 ° C 26-30 mm ² / sec.

The manufacturing technology is the same as described in Example 5. To 96 kg of the resulting base fat add the following additives:

Sb-di (C 5 -C 15 alkyl) dithiocarbamate 2.5 kg

Pb stearate 1.0 kg

Ba- (C 6 -C 14 alkyl) sulfonate, 0.5 kg

Example 8

The composition of the base fat:

0.3% C 15-19 fatty acid 1.7% benzoic acid

10.9% Al-tristearate

85.50% base oil (see Example 1 base fat base oil).

The manufacturing technology is the same as described in Example 5. To the 96.5 kg of base fat obtained, the following additives are added:

Methyl di (C 5 -C 15 alkyl) dithiocarbamate 2.0 kg

C15-C19 fatty acid Pb salt 0.5 kg

Ba- (C 6-14 alkyl) sulfonate 1.0 kg

Example 9

The following additives are added to 87 kg of base fat of Example 8:

Fluff graphite 10.0 kg

Sn-di (C 5 -C 15 alkyl) dithiocarbamate 2.45 kg

Pb-dinonylnaphthalenesulfonate 0.5 kg

Silicone oil 0.05 kg

The example

The following additives are added to 96 kg of base fat of Example 1:

Sulfuric oleic acid 2.0 kg

Pb-di (C 5 -C 15 alkyl) dithiocarbamate 2.0 kg

Example B

The following additives are added to 96.6 kg of the base fat of Example 5:

: 1 mixture of Zn-dialkyl dithiophosphate and Zn-diaryl dithiophosphate 2.4 kg

TEA-04-19 fatty acid ester (Triethanolamine (C 14-19 fatty acid) ester)

Example 10

The following additives are added to 95.5 kg of the base fat of Example 1:

Zn-dialkyl dithiocarbamate 0.75 kg

Methylene di (C 4 -C 6 alkyl) dithiocarbamate 2.25 kg

Badinonyl naphthalene sulfonate 0.1 kg

Polyisobutylene (Ms = 1,000,000-3,000,000) 0.5 kg

1-10. Comparing the fat test results of Examples 1 to 4 with those of Examples A and B, it is shown that if any of the three most important additives are missing, the fat does not meet the corrosion resistance or the corresponding EP requirement.

Characteristics of the lubricating greases according to the examples

The number of the example penetration province At 25 ° C, 0.1mm MSz KGST 755 Oxidation stability. Pressure drop after 400 h N / m ² at 100 ° C MS 11705 Corrosion- resistance degree DIN 51,802 ill. BS 18091/15. Timken OK load, N ASTM D 2782 1 265-295 41 0-0 220 2 265-295 55 0-1 200 3 265-295 48 0-1 200 4 265-295 69 0-1 180 5 265-295 48 0-0 210 6 265-295 69 0-0 110 7 355-385 69 0-0 220 8 265-295 48 0-0 200 9 265-295 69 1-2 220 10 265-295 48 0-1 180 THE 265-295 83 4-5 220 B 265-295 62 2-3 65

A patent claim

Claims (3)

A patent claim Aluminum complex double salt based grease composition, where the grease is 100-30 ° C in a petroleum refinery with a viscosity range of 10-30 mm ² / s 4-141.51% of a salt of a complex of C15-19 fatty acids, benzoic acid and aluminum, dispersed in an amount of from 1 to 51% by weight of the fat of the formula I and / or II as an antioxidant additive. compound - in the formula R is C 5 -C 15 alkyl or C 6 -C 15 aryl; Me is zinc, antimony, 192 197 lead or tin or methyl or ferric β-naphthylamine; as an anti-corrosive additive in an amount of from 0.25 to 1.0% by weight of barium (C 6-14 alkyl) sulfate or barium or calcium (C 6-14 alkyl) (C 9-11 aryl) sulfonate having a molecular weight of 600-1200 or dicyclohexylamine (C 15 -C 19 fatty acid) ester or triethanolamine (C 15 -C 19 fatty acid) ester or sodium nitrite; 0.5 to 101% molybdenum disulfide or soft graphite or calcium acetate, barium or lead dinonylnaphthalene sulfonate or a (C 15 -C 19) fatty acid lead salt or dibenzyl as an inorganic or organic lubricant additive -disulfide or sulfurized C 15 -C 19 fatty acid or tricresyl phosphate; and optionally a syneresis-reducing and 5 as colloidal stability-enhancing additives in an amount of 0.5-1.0% by weight of polycellylmethacrylate having a molecular weight of 3000-6000, or a polyisobutylene having a molecular weight of 1,000,000-3,000,000 or a carboxylic acid ester copolymer of C15-19-19; 10 and optionally 0.03 to 0.06% by weight of silicone oil having a molecular weight of 5000 to 100,000 as water repellent. 1 page drawing Published by the National Office of Inventions Responsible for publishing: Zoltán Himer, Head of Department Taken by the Printing Photocopier Factory (878398/09) 89-0010 - Dabasi Nyomda, Budapest - Dabas Chief Executive Officer: Csaba Bálint Director