DE2312623A1 - GREASES AND METHOD OF MANUFACTURING IT - Google Patents

Description

m. Pi- *. =.-'- ■ · - "i'Tf *. WALTER Bell

DR-S- ^ r: 'I H, -J. wolff March 13, 1973

DR. JUR. " H.ν.w -. V ::. ^ Ti

623 FRAHXr JKT AM MAIN-HOCHJ! OO 1 OCOO

AOa.ONSlÄASä £ l> e * · ** '* - ^W ^ - V

Our No. 18 56Ο

Chevron Research Company San Francisco, CaI., V.St.A.

Lubricating greases and processes for their manufacture

Modern technology is constantly striving to provide the general public and the processing industry with machine tools
that can work within a wider temperature range and at higher loads than the previously usual ones. In addition, many of the newer machines work at extremely high loads

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Speeds ». Many of these machines require very specific ones Properties of the lubricants that are not available with the common ones. Hence the modern development for systems that work at high speed and at high temperature, the pet chemical industry for the development of a second one Generation of lubricants stimulated that meet the requirements of the new machines. Recently, for example, was created an increasing demand for lubricants that are used at temperatures above I50 C in high-speed bearings and gears good operating behavior over a period of over 500 hours demonstrate. It should also be used for further development the high-speed hidden bearings can withstand the lubricant for the life of the bearing «

Numerous lubricating greases have been developed which have the Most of the new, stricter requirements meet «many of these But greases are too expensive to be used on an industrial scale or they only meet certain requirements and fail but in other ways. Common lubricating greases are the lithium greases that can be found everywhere. It is these Simply grease a mixture of a base oil and a hydrocarbon basis with lithium hydroxystearate and small amounts of others Additives. ¥ enn. these greases also have good lubricating properties and show good behavior at medium temperatures, so is their application at. high temperatures and in high-revving Maschidoch not entirely satisfactory. The lithium greases age

high temperatures, especially at temperatures above 175 ° C · The Aging leads to a rapid loss of lubricating effect and ultimately as a "failure of the system"

Another type of τοη lubricating grease with excellent lubricating properties at higher temperatures consists of a lubricating oil (of natural or synthetic origin) that contains a polyurea as an additive. Greases of this type are described in U.S. Patents 3,242,210 , 3 2 ^ 3 372, 3 3h6 497, 3, 376 223 and 3 401 027, all of which are owned by the Chevron Research Company. The polyurea component gives the grease significant high temperature resistance and actually causes slight antithixotropic properties, i.e. an increase in viscosity with increasing shear stress on the lubricant. This property of the grease is advantageous because it prevents the detachment and loss of grease on the moving parts the machine. If most of the problems of the earlier lubricants were solved with this grease, the handicap remained that relatively large amounts of polyurea (between 8 and 20 percent by weight) were required, which caused quite high costs Lubricants have no extreme pressure properties, and EP additives must therefore also be added when high contact pressures occur.There is therefore an urgent need for greases for high temperatures and high speeds, which have good stability over long periods of time, high pressure and anti-wear properties show and which are relatively cheap to manufacture.

The aim of the invention is therefore a new lubricating grease.

The aim of the invention is further a lubricating grease that can be used for long periods of time

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Use at high temperatures shows good performance.

The aim of the invention is also a relatively inexpensive one Lubricating grease which shows good operating behavior at high temperatures in high-performance machines and which has good EP properties owned.

dear invention is finally a method of manufacture this grease,

These goals and the advantages associated with them can be realized through a Ztosammiensosition, which as a main part Lubricating oil that contains (l) 0.5 to 10 percent by weight of a polyurea with 1 to 8 grain groups and a molecular weight between about 375 and 2500 and (2) 3 to 30% by weight of the alkaline earth salt of a carboxylic acid having 1 to 3 carbon atoms contains,

It has been found that by adding an alkaline earth salt of a carboxylic acid to the grease; a reduction in the polyurea content of xxa 50 percent compared to the previously required amount becomes possible without the dropping point and other physical properties being changed. In addition, the presence of the carboxylic acid salt gives the lubricant good high-pressure properties and therefore makes the addition of other EP additives unnecessary in many cases.

The exact mechanism behind this action of the polyureas and the carboxylic acid salt is used in improving the properties of the grease is not known. If the Theory cannot be binding either, it is to be assumed

Λ ·

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that the calcium acetate in some way with the polyurea forms a complex compound and thus has a thickening effect. Even if the mechanism is unknown, so we know that there is a synergistic effect between the two components, so that the lubricating properties of the Fats can be improved to a much greater extent than by the polyurea or the carboxylic acid salt alone · For example The combination causes a remarkable increase in the wear protection properties and also increases the continuous output of fat in bearings.

The polyurea component

The polyurea component according to the invention is an organic compound which is insoluble in water and oil and has a molecular weight between about 375 and 2,500 and has at least one ureide group and preferably not more than eight ureide groups, in the most favorable case between about 2 and 6 ureide groups. The term "polyurea" is used here in such a way that it also creeps in monoureas, that is to say a ureid group. An ureid group should be defined here as follows [NC-NHy- (l)

The polyureas should not have any terminal primary amine groups, i.e. compounds with a terminal (NH) group and no free carboxyl groups. A particularly preferred polyurea has an average of between 3 and k ureid groups and a molecular weight between about 600 and 1200.

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A particularly preferred group of polyurea compounds has a structure that is represented by the following general formulas can reproduce:

/ 0 0 \ 0 0

(U Ii \ | i Ii

R-NH-Uc-NH-R ₁ -NH-C-NH-R ₂ -NH - / - C-NH-R ₁ -NH-C-NH-R (2)

η 0/0 0 \ 0

f {. R-NH-C-NH-R-NH-IC-NH-R ₁ -NH-C-NH-R-NH-IC-Nh-R - - - (3)

. ■ η

/ 0 0 Λ Ο

/ I » it) H

R-NH-I-C-NH-R -NH-C-NH-R -NHJ -C-NH-R _ _ _ (4)

where: m is an integer from 0 to 3 »

R same or different monovalent

Hydrocarbon radicals with 1 to 30 »preferably 10 to 2h carbon atoms; R- same or different bivalent

Hydrocarbon radicals with 2 to 30, preferably. wise 6 to 15 carbon atoms and R_ identical or different bivalent

Hydrocarbon radicals with 1 to 30 tons are preferred 2 to 10 carbon atoms.

The monovalent organic radical R consists of the above compounds of hydrogen and carbon and can be aliphatic, aromatic or alicyclic and also combined, e.g. Aralkyl, alkyl, aryl, cycloalkyl, alkylcycloalkyl, etc., and he can be saturated or olefinically unsaturated (one or more double bonded carbon atoms, conjugated or non-conjugated) its «Dk · divalent hydrocarbon radical, above with

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R_ and R ₀ denotes, can be aliphatic, alicyclic, aromatic or combined, for example. Alkylaryl, aralkyl, alkyl, Gyclaalkylaryl etc · _r with the two free valences are on ver resigned en carbon atoms "

The polyureas having the structure represented by Formula 2 above are prepared by reacting (n + 1) moles of diisocyanate with two moles of a monoamine and (n) moles of a diamine. (When η in Formula 2 is zero, the diamine is omitted.) Polyureas having the structure represented by Formula 3 above are prepared by reacting ττοη (η) moles of a diisocyanate with (n + 1) moles of a diamine and two moles of a monoisocyanate. (If η in formula 3 is zero, the diisocyanate is omitted ·) Polyureas having the structure represented by formula k above are prepared by reacting (n) moles of a diisocyanate with (n) moles of a diamine and one mole of a monoisocyanate and one mole of a Monoamines manufactured. (If η in formula 4 is zero, diocyanate and diamin are omitted.)

In the preparation of the above polyureas, the relevant Reaction participants (diisocyanate, monoisocyanate, diamine and monoamine) in a suitable reaction vessel and in the corresponding proportions mixed together. The reaction proceeds and is in the absence of a catalyst initiated by simply combining the components under suitable conditions. The reaction temperatures are in Range from 20 ° C to 100 ° C and it is worked at atmospheric pressure. The reaction itself is exothermic and demented

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Speaking of which, higher temperatures are reached when the reaction is initiated at room temperature. But it can also be heated or cooled from the outside.

The monoamine used in the manufacture of the polyurea or monoisocyanate forms the terminal groups. As already Said these terminal groups have 1 to 30 "preferably 5 to 28 and in the most favorable case 6 to 25 carbon atoms »

Examples of the various monoamines are pentylamine, Hexylamine, heptylamine, octylamine, decylamine, dodecylamine, Tetaradecylamine, hexadecylamine, octadecylamine, eicosylamine, dodecenylamine, Hexadecenylamine, octadecenylamine, oatadecadienylamine, Abietylamine, aniline, toluidine, naphthylamine, cumylamine, Bornylamine, penchylamine, t-butylaniline, benzylamine, ß-phenethylamine latsw. Particularly preferred amines are made by amidation obtained natural fats and oils with ammonia, whereby initially amides are formed, which are reduced to the amines. After this Process can be made stearylamine, laurylamine, Palmitylamine, olaylamine, petroselinylamine »linoleylamine, linolenylamine, Eleostearyiamine, etc. Particularly suitable are unsaturated Amines.

Examples of monoisocyanates are hexyl isocyanate, decyl isocyanate, Dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, phenyl isocyanate, cyclohexyl isocyanate, xylene isocyanate, cumolisocyanate, Abietyl isocyanate, Gylooctyl isocyanate, etc.

The diamines and diisocyanates, which form the internal hydrocarbon bridges between the ureide groups, have, vrle said,

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2 to : y & _t preferably 2 to 26 and in the most favorable case 2 to 18 carbon atoms. Examples are ethylenediamine, propanediamine, btrfcandiamine, hexanediarain, dodecanediamine, octanediamine, hexadecandiamine, cyclohexanediamine, cyclooctanediamine, phenylenediamine, toluenediamine, xylenediamine, dianilinemethane, ditoluidinemetholu, bis (aniline), etc.

Examples of diisocyanates are hexane diisocyanate, deodorant diisocyanate, Octadecane diisocyanate, phenylene diisocyanate, toluene diisocyanate, Bis (diphenyl! Sοcyanat), methylene-feis (phenyl isocyanate) etc.

Another group of polyureas used for the purpose of Invention can be used corresponds to the following general formula:

XA -R ₁ -NH-C-NH-JY

n.

(5)

where: η _{χ is} an integer - * on 1 to 3j

R ₁ as defined above} X and Y monovalent radicals in Table 1 below.

TABLE I.

X Y 0
H
R-- C-NH-
0
Ii
R _k N -
it
0 0
Il
RC-NH-R ₂ -
Q
Ii
Ii
0

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In Table I, R is defined above ;, R_ is equal to R and also defined above "R ^. belongs to a group consisting of arylene radicals with 6 to 16 carbon atoms and alkenyl groups with up to 30 carbon atoms and R ₁ . with a group consisting of alkyl radicals with 10 rock 30 carbon atoms and aryl radicals with

Consists of 6 to 16 carbon atoms

Polyureas of the above formula (.3) can be described as amides and imides iron mono-, di- and triureas. These substances are produced by reacting suitable carboxylic acids or internal carboxylic acid anhydrides with a diisocyanate and an amine or diamine. The various components are then put together in a suitable reaction vessel and heated to a temperature in the range of 20 ° C to 200 ° C for a sufficient period of time. to form the Poljtoarnetoff atu, which generally takes 5 minutes to 1 hour.

Suitable carboxylic acids are aliphatic carboxylic acids with about 11 bli 31 carbon atoms and aromatic carboxylic acids with

7 to 17 carbon atoms. Examples are aliphatic acids such as Laurineäure, myristic acid, palmitic acid, \ margaric acid, stearic acid, arachidic acid, Hehensäure, lignoceric acid, etc. ·, and aromatic · acids such as benzoic acid, 1-naphthionic acid, 2-naphthionic acid _t phenylacetic acid, hydrocinnamic acid, cinnamic acid, mandelic acid, etc. · Suitable anhydrides are derived from dibasic acids that form a cyclic anhydride, such as succinic anhydride, maleic anhydride, phthalic anhydride, etc. * Substituted anhydrides such as alkenylsuccinic anhydrides with up to 30 carbon atoms in the alkenyl radical are also suitable materials.

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Suitable diisocyanates, monoisocyanates, monoamines and diamines have been described above.

The polyureas are generally mixtures of compounds

U,
genes in which n_ is between 0 to / or 1 to 3 »which are simultaneously present in the lubricating grease 2, a certain amount of the monoamine can react with both sides of the diisocyanate and form a diurea. Particularly good results were achieved when the polyurea had an average of four ureid groups.

The amount of polyureas in the fat blend is chosen eo; that a thickening of the base oil to the desired fat consistency occurs when combined with the alkaline earth salt the carboxylic acid takes place. Generally the amount of polyurea is 1 to 15 weight percent, advantageously 1 to 10 percent by weight and preferably 2 to 7 percent by weight the finished fat mixture "

If you want to work with an oil concentrate, you can the concentration of the polyureas in the Ctrundöl or one, oily organic liquid between about 10 and 30 percent by weight of the finished concentrate. The usage of Concentrates are a convenient method of handling and transporting the polyureas, which are then suitable before use Way to be diluted.

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Alkaline earth salts of carboxylic acids

The second component of the fat blend is the alkaline earth metal salt of a carboxylic acid having 1 to 3 carbon atoms, all earth metals should be used Wearden ₉ for example, magnesium, calcium, strontium, barium, etc. However, calcium is best suited. The carboxylic acid group preferably has 1 to 3 carbon atoms and in the best case 2 carbon atoms. Compounds that can be used with success are calcium formate, barium formate, magnesium formate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, calcium propionate, barium propionate, magnesium propionate, etc.

The amount of the alkaline earth salt used in the grease depends on the desired lubricating properties of the grease, the selected polyurea component, the type of alkaline earth salt, etc. In general, the carboxylic acid salt is present in an amount ■ 3-30 weight percent of the finished grease and preferably from about 4 to 15 weight percent _o The ratio of carboxylic acid alkaline earth metal salt zn polyurea also depends on the above conditions, but will generally be on a weight basis at 1 up to 15 parts of carboxylic acid salt per part of polyurea and preferably 3 to 7 parts per part of polyurea.

A concentrate formulated with polyurea and alkaline earth salt can also be used. The concentration of the carboxylic acid salt is then from 20 to 50 weight percent and preferably 25 to 40 weight percent of the concentrate, as a liquid medium of the concentrate, the base oil is used at the best, since it can be easily diluted to the desired Fettmisehung ₀

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Base oil

The third component, which is necessarily in the inventive Mixture must be present is a liquid base oil. A wide variety of lubricating oils could be used as base oils naphthene-based, paraffin-based and mixed-based will. Other hydrocarbon oils include lubricating oils made from coal products and synthetic oils such as alkylene polymers (e.g. polymers of propylene, butylene, etc. and their mixtures), alkylene oxide polymers (e.g. alkylene oxide polymers produced by polymerization an alkylene oxide in the presence of water or alcohols such as ethyl alcohol, for example Propylene oxide polymers), carboxylic acid esters (e.g. esters made by Esterification of a carboxylic acid such as adipic acid, azelaic acid, seboric acid, sebacic acid, alkenyl succinic acid, fumaric acid, Maleic acid etc. can be obtained with alcohols such as butyl alcohol, hexyl alcohol, 2-Ä * thy lhyxjtl aiko hol, pentaerythritol, etc.), liquid Esters of phosphoric acids, alkylbenzenes, polyphenol (e.g. Biphenols and terphenols), alkyl biphenol ethers, silicon polymers such as tetraethyl silicate, tetraisopropyl silicate, tetra (4-methyl-2-tetraethyl) silicate, Hexyl (4-methyl-2-pentoxy) disilane, poly (methyl) siloxane and poly (methylphenol) siloxane, etc. The Base oils could be used individually or in combinations provided that they are mixable or by mutual Solvents can be made miscible «

Making the fat blend

The greases that have the superior properties according to the Invention can be prepared by first j the production of the polyureas takes place in situ, whereupon

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the formation of the alkaline earth salt of the carboxylic acid is also carried out in the base oil. In this embodiment, the base oil is introduced into the boiler together with the precursors for polyurea and carbonic acid salt, that is to say the reaction components for the formation of these compounds. If a polyurea is to be produced that corresponds to formula 2, the required amounts of diisocyanate, diamine and monoamine are added together with the base oil. In the production of polyureas that correspond to Formula 3! the Garundöl with the desired amounts of diisocyanate, diamine and monoisocyanate is mixed * If the polyurea of the formula k .entsprechen, so the Qrundöl be admixed with the requisite amounts DiLLsοcyanat, diamine, monoisocyanate and monoamine * If, finally, the polyurea of the formula 5 correspond, so is the base oil is added to the boiler together with the desired amounts of carboxylic acid or anhydride, diisocyanate and mono- or diamine. The contents of the kettle are stirred and the temperature is raised. 20 ° C to 160 ° C and maintain this temperature for a long time until the formation of the polyurea has taken place, which generally requires about 0.5 to 3 hours.

When the polyureas are formed, alkaline earth hydroxide or oxide and carboxylic acid are added to the kettle. The ratio of alkaline earth hydroxide to carboxylic acid is on an equivalent basis between 1 and 4: 1 and preferably between 1 and 2 * 1 · The Κ; · * · «1 is kept at a temperature between 21 ° G and 5 ° 0 during the process, to bring about the neutralization of the alkaline earth hydroxide or oxide by the carboxylic acid *

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During the reaction, water is released and is best removed from the system by applying a weak vacuum tone to the fat cooker for 50 h ± 72 cm Hg at a temperature of about 100 C and above. _E

The fat blend can then be further treated by is subjected to shear hardening. This is done by rolling the fat in a roller under increased pressure. Through this the dispersion of the polyurea and the carboxylic acid salts in the base oil is improved, resulting in a "fat" of significantly improved Consistency leads. In the American patent application 11 517 describes a suitable method for shear hardening which is also applied to the mixtures according to the invention can be.

In addition to the polyurea and the alkaline earth salt, other additives can also be used in the lubricating grease according to the invention find without the high stability and the good operational behavior be affected within a wide temperature range. An oxidation stabilizer, for example, is added. This additive prevents the formation of varnish and sludge deposits on the metal parts and grain corrosion of alloy bearings. Can be used as antioxidants organic compounds containing sulfur, phosphorus or nitrogen such as organic amines, sulfides, hydroxysulfides, Phenols, etc., used alone or in combination with metals such as zinc, tin or barium. Particularly suitable stabilizers for fats are phenyl-06-naphthylamine, i ± Ls (alkyl phenyl) amine, N, N-diphenyl-p-phenylenediamine, 2,2,4-

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Trimethyldihydroquinoline Oligoraere, Bis (4-isopropylaminophenyl} -ether, Ή-ΆογΙ — ρ— aminophenols Η— Acylphenthiazine ₉ N-Hydrocarbylamides of the ethylenediaminetetraacetic acid _} Alkylphenpl-Formalde-

hyd-ainine polycondensates etc,

Another additive, "which were the findings he ACCORDING TO SEN greases added can _see is a Kosnpo sions inhibit or _o This is to prevent ₉ crushed fe-so that the formation of acid -Substances .im- • oxidation, and films on the metal! form surfaces which mildersia the action of corrosive substances on the free metal parts as corrosion inhibitors organic compounds are used ,, the active sulfur enthaltenj ₉ phosphorus or nitrogen such as, _e B ₉ organic sulfides ^ phosphides, metal salts of thiophosphoric acids and sulfonated waxes "particularly effective corrosion inhibitors are ammonium dinonylnaphthalene sulfonate and sodium nitrite _e

Other additives that are used are additives to metals active! eruhge You are used to the catalytic influence of metals to counteract the oxidation or to prevent this, which'by formation of catalytically inactive Complexes with soluble or insoluble metal ions happen. Metal deactivation agents are complex organic compounds containing nitrogen and sulfur, e.g. certain complexes Amines and sulfides. A well-known metal deactivator is mercaptobenzothiazole.

Except to the additives mentioned - 'ho oh- various other ■ applied ■ · additives in Hahmen the Ifrfihdung as stability' capacitors ■, Pilmf it tigkei tsver better, Tropfpunlctsverbesserer

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Lubricants, color additives, odor enhancers, etc.

The following examples serve to illustrate the embodiments of the invention, not to restrict it »

EXAMPLE 1

In this example, a diurea suitable as a thickener is prepared and its properties are examined. 3.75O g of neutral oil 126 and 305 g of alkylamine from tall oil are introduced into a stainless 48 1 mixer equipped with a stirrer. The contents are stirred for 30 minutes at 55 ° C., and then a further 3.75O g of neutral oil 126 with 95 % of toluene diisocyanate are added to the mixer given. The contents are stirred for 10 minutes and passed through a roller at 525 kgf / cm for a further 20 minutes. ·

The milled fat is then heated to 92 ° C. and 6 g of ethylenediamine are added to the mixer in order to neutralize unreacted Taxlaol diisocyanate. After rolling at 525 kp / cm, the fat is cooled to 65 ⁰ C and treated with 2.500 g of neutral oil 126 and I-.7O8 gr hydrated lime (Ca (OH)). 3,9OO & neutral oil will be sent to you. 126 and 1.8 ^ 5 S acetic acid in the mixture, which is then stirred for about 80 minutes at about 65 ° G *

The mixture is then mixed with 200 g of commercially available host inhibitor and sent through the roller again at 525 kp / cm for dispersion. According to ASISi, the lubricating grease has a resting penetration (P) of 207 and, after treatment with 60 double cycles, a worked penetration (P ^ ₀ ) of

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■. - 18 - ,. ■

EXAMPLE 2

This example is intended to illustrate the manufacture of a door, the invention's characteristic features, made of tetrahydrofuran and calcium acetate. 7 · 5ΟΟ g of a naphthene-paraffin oil mixture with a viscosity of 15 cSt, which is referred to here as "base oil ¹¹ , and 880 g of an alkylamine from tall oil and £ 2 g of ethylenediamine are introduced into a stainless 48 1 mixer equipped with a stirrer. The contents of the mixer is stirred for 20 minutes at 55 ° C and then mixed with 6000 g of base oil and 54.8 g of toluene. the mixture is stirred and the temperature maintained for 30 minutes at 65 ⁰ C.

The contents of the kettle are then sent through the roller at a pressure of 525 kgf / cm and then heated to 92.degree. One; A small fat sample is analyzed and traces of diisocyanate are found. Another 40 g of ethylenediamine are added and mixed with the milled fat for 10 minutes at a temperature of 100 ° C. The kettle is then cooled to 65 ° C and another 5,000 g of base oil with 2,480 g of hydrated lime (Ca (OH) ₂ ) entered. Lime and base oil are mixed with the milled fat for 5 minutes, then a further 5.460 g base oil and 2 * 800 g acetic acid are slowly added to the mixer within 25 minutes. It is stirred for 30 minutes at 65 0 »to ensure that the neutralization between the calcium hydroxide and the acetic acid is complete:« Then 320 g / commercial rust inhibitor are added and the mixture is rolled at 525 kp / om. After adding a further 8,920 g of base oil, it is rolled again at 525 kp / om · The product has a .Rahpenetration

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(Ρ) of 232 and after όθ double cycles a fulling penetxation (P ₆₀ ) of 282 (ASTM-217). The dropping point is 238 ° C (ASTM-D-2265).

The composition of a fat sample is calculated as follows

Gaicxuuiaceirs.t 11 t7 k-ev ^ -t » Polyurea " 3 _} s Qew. ^ More commercially available Corrosion inhibitor 0 Weight ^ Base oil 82

Po Ivharns t ο ff -TO-HH- G-NHJf ^ -NH- C-NH- CH-GH _n -NH- C-NH-IiJrNH- C-NH-TO where TO is a tall oil residue-.

This example is intended to demonstrate the effectiveness of a lubricating grease according to the iSrfindung, the polyurea and an alkaline earth carboxylic acid salt contains, show in a long-term test in comparison with a known lithium stearate grease. The fat according to the invention is prepared according to the method of Example 2, Da.s lithium grease has the following composition:

Lithium hydroxys tearate 9 Gvew $ Lubricating oil 83 wt

Commercially available

EP additive 7.5% by weight <£

More commercially available

Corrosion inhibitor 0.4 wt

According to ASTM, the lithium grease has a worked penetration after 60 Double rate of 320 and an ASTM dropping point of 182 ° C.

The two fats are subjected to a Timken test to determine the

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maximum permanent load and the maximum contact pressure to determine the / continuous load. The test procedure is in ASIM D-2509. The results of this test are in the shown in Table II below.

TABLE II

Timken Test Results Grease Load (kg) Contact Pressure (kp / cm)

Polyurea 22.7 2250

Carboxylic acid salt

Lithium 20.4 844

The Timken test provides information about wear properties of the grease at higher loads and higher contact pressure and proves the better anti-cracking properties of the invention Fat. The table shows that the Fat according to the invention, the lithium grease with regard to the permanent load superior and far superior in terms of contact pressure.

The two fats are subjected to a high temperature thin film test subjected. This test provides information about the ability of the grease to lubricate a bearing over a long period of time and provides information on the service life of the bearing. In the test, the two fats are each in a layer -vron 0.8 mra Thickness applied to two pieces of steel and one in the oven Exposed to temperature of 150C. The fats will last for a while observed, and the point in time when the fat loses its fat-like properties (hardens or when it cools down transformed into a varnish) is known as the thin film lifetime .

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The lithium grease and that made by the procedure of Example 2 Fat were subjected to the thin film test; the results are shown in Table III »

TABLE III Thin Film Life at 150 ° C

Approximate life state of the fat

Grease duration (hours) at room temperature

Lithium Hydroxy- 3OO Isart & Cracked

stearate

Polynurea 1000 fat-like

Carboxylic acid salt

The above table shows that according to the method of the invention manufactured fats in their commercial version the common ones Lithium hydroxystearate fats are far superior. The table shows an expected increase in service life by 33 percent.

EXAMPLE k

This example is intended to improve the functionality of the erfindungsgeraässen Grease at low temperatures and show its superiority over the common lithium greases. The viscosity of the Fefct prepared according to Example 2 is -18 ° C and at -1 ° G according to ASTM D-IO92 · The values are with the viscosity of the lithium grease described in Example 3 compared. The viscosities of the two fats are shown in Table IY.

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TABLE IV

Scheimzdsko si tat viscosity 200 sec (Poise) 200 sec ^x - -ore 330
400 - at -18 ^U C X2Q0
2300 b-edl ■ ^χ 20 sec " ¹ Grease 20 sec 2800
4800 Polyurea
Carbomic Acid Alz
lithium 900
1000

As can be seen from the table, the grease according to the invention has both teei -IC and at -18 C a lower viscosity than the lithium grease. The proof that l & ei -18 ° C in the test - at 20 seconds "the viscosity of the grease according to the invention is 2000 poise lower than that of the lithium grease is particularly significant.

BED [GAME 5

This example is intended to show the effectiveness of monoureas and galium acetate in the production of an improved lubricating grease. 140 g, Neutra.1-oil 600 and 43.5 g of alkyiamine from tall oil are introduced into a 1 l Waring mill at room temperature. While stirring the contents, 19 % phenyl isocyanate are added. The contents are stirred for about 30 minutes and then left to stand overnight.

Calcium hydroxide (, 11th g) is placed in the mixer and mixed intimately with the urea-oil mixture. Then 12.4 pounds of acetic acid are added and the mixture is stirred until neutralization is complete * The vegetables are dehydrated and mixed with 50 g of oil 60 double cycles (P ^ ₀ ) 31? · Di © Walkpenetration (Pg ₀ ) of the mono- "

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urea fat without added calcium y m n is the 336th

This example clearly shows the improvement in the milled penetration of the lubricating grease through the addition of Calciumaceta.t «

BEESPIH, 6

This example is intended to show in general the production of various lubricating greases according to the invention. A · Fettkooher- iron? | 5 l, equipped with cooling jackets and stirrers, is charged with 1.9 l of a lubricating oil at tree temperature. M ₉ Diisocyanates, monoisocyanates, diamines, carboxylic acids and monoamines are slowly added to the kettle »The amines are added before the isocyanate and dissolved in the oil» The temperature of the mixture is increased to 92 C and this temperature is maintained «After about 30 minutes be added a further 1.9 1 oil, which the corresponding amounts of an alkaline earth! hydroxide containing "the kettle contents at 490 kp / cm rolled to the alkaline earth metal hydroxide in the fat to disperse" Ansehliesaend a carboxylic acid is added and the KesselinhaJtt for two hours at § .25 kp / cm rolled. The temperature is kept at 92 ° C. while the alkaline earth metal hydroxide and carboxylic acid are added.

After the two hours have elapsed, the fat is cooled down to room temperature and rolled twice at 490 kgf / cm. Then there are tests according to ASTM D-2265 (drip purict) and according to the Federal Test Method 33I.I (Navy High Speed Hearing Test) carried out «All greases show, as expected, a relatively good dropping point and a satisfactory service life in the storage test.

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TABLE V Polyharnatoff precursors

O
(O
00

O
00

O
00

composition

Type

■ IA, 4'-diidocyanate ' ¹ ^
ρ-phenylenediamine
Octadecylamine
p-toluidine

Hexyl isocyanate
Di alii 1 in e than
Bis (diphenyl isocyanate)

Amine from sebum
p-toluidine.

Ethylenediamine
Hexanediisocyanate

Stearic acid
Tolylene diisocyanate
p-phenylenediamine

Hydrozinic acid

Phenylene diisocyanate

Naphthylamine

Maleic anhydride
Decane diisocyanate
Amine from tall oil

(1) Diphenylmethane-4,4 * -diisocyanate

(2) Pentaerythritol tetfacaproate.

• Carboxylic acid salt precursors ·; Lubricating oil

Quantity type (wt. ^) Type

Barium hydroxide 9.5 acetic acid 3

Calcium hydroxide 5.5 formic acid 5.5

Magne s ium hydroxide 5, ° Propionic acid 10.4

CaIc iumhydrοxid acetic acid

Barium hydroxide acetic acid

Calcium hydroxide acetic acid

6.2

5.0

PET C

(2)

280 neutral

Mineral *

Mineral * ·· '

7.2 alkyl methyl _; S ₁ O silicone *

5.6 mineral

• 60. / ·

Claims (1)

Claim » 1. grease with a lubricating oil al "Bauptanteil and" in · "polyurea Koraponente as Xuaatz, characterized in _t that -es 3 to JO per cent by weight of a Brdalkalisalζes a carboxylic acid having 1 to 3 carbon atoms and that the polyurea component 0.5 to 10 percent by weight and consists of a polyurea or a mixture of polyureas with at least one ureide group and a molecular weight between 375 and 2500 « 2. Lubricating grease according to claim 1, characterized in that the polyurea or the polyurea mixture is chosen so that it does not have more than eight ureide groups. 3. Lubricating grease according to claim 2, characterized in that the polyurea or the polyurea mixture has 2 to 6 ureide groups 4 * lubricating grease according to claim 1, 2 or 3, characterized in that the polyurea or the polyurea mixture has 3 bi · k ureid groups and a molecular weight between 600 and 1200. 5. Lubricating grease according to one of the preceding claims, characterized in that the polyurea component is present in an amount xon 2 to 7 percent by weight of the mixture, 6, lubricating grease according to one of the preceding claims ·, characterized in that the alkaline earth metal salt of the carboxylic acid in 309843/0808 ♦ u an amount of k bi «15 percent by weight of the mixture is present. 7 grease according to one of the preceding claims, characterized in that the ratio of alkaline earth salt of Carboxylic acid from polyurea component on * weight basis 1 to 15 parts of carboxylic acid salt per part of polyurea is. 8 · Lubricating grease according to claim 7 »characterized in that the ratio is 3 to 7 parts of carboxylic acid salt per part of polyurea. 9. Lubricating fat.nach one of the preceding claims, characterized characterized in that the lubricating oil is a hydrocarbon oil. 10 »Lubricating grease according to one of the preceding claims, characterized characterized in that the alkaline earth salt of the carboxylic acid is calcium acetate. 11 «Lubricating grease according to one of the preceding claims, characterized in that the polyfaarnea or the polyurea mixture has a structure which is characterized by one of the following Formulas can be reproduced: R-NH- UC-NH-R ^ -NH-C- ^ ii-R -WK-JC-NH-R ₁ -NH-C-NH-Ri η
0/0 0 \ 0 ». hi a to R-NH-C-NH-R -ΛΗ-lC-NH-R ₁ -I ^ lC-NIi-R -Nil-JC-NH-R j 'TL (fo. o ■ \ ο -C-NH-R ₁ -NH-C-NIi-R-NH-) -C-WH-Rj 309843/0808 where X is one of the following monovalent (croup. ο Ν R - C-NH- and R ·, *** H ο Y a · of the following monovalent groups ο ι R_-C-NH-R -> R. ' ^ AR- and R- is > and where mean: XL · an integer from 0 to 3;
n. an integer from 1 to 3;
R with the same or different hydrocarbon radicals 1 to 3 ° carbon atoms;
R- same or different divalent coal water substance residues with 2 to 30 carbon atoms; R identical or different divalent hydrocarbon radicals with 1 to 30 carbon atoms; R_ with the same or different hydrocarbon radicals 1 to 30 carbon atoms}
Rl arylene radicals with 6 to 16 carbon atoms or alkylene residues with 2 to 30 carbon atoms; R “alkyl radicals with 10 to 30 carbon atoms or aryl radicals with 6 to 16 carbon atoms, 12 · Concentrate of a linseed fat according to one of the preceding Claims, characterized in that the alkaline earth metal salt of the carboxylic acid has a proportion of 20 to 50 percent by weight and the polyurea component has a proportion of IQ to 30 percent by weight matters 309843/0808 13 * Process for the production of "ίηβ3 lubricating grease according to ei η eis The claim" 1 to il _f characterized _f that "s xuh & clitit sin first mixture is produced _{} in} that as the main & atail -adra Schaii" oil and a smaller proportion a diisocyanate * 5.n Di.suaIn and a Monoiaoc-jranat or a monoamine in entepr-echendeE ¥ © rhältnis and in sufficient amount veraii'echt together vsTden _t to a final product to be obtained in which a bi PoXyaamstofT with 1 x 8 Ureidgruppen in an amount of 0 tone, 5 to 10 percent by weight ■ is present that the mixture is stirred sufficiently long and at a suitable temperature to form the polyureas, that a second mixture is prepared by adding an alkali metal hydroxide or oxide and a monocarboxylic acid with 1 to 3 carbon atoms to the first mixture that contains polyurea _? 'is added, wherein alkaline earth hydroxide or oxide and conocarboxylic acid are present in sufficient amounts to form 3 to 30 percent by weight of an alkaline earth metal salt of the carboxylic acid in the second mixture that the second mixture is stirred for a sufficient time and at a suitable temperature »to form the alkaline earth metal salt Carboxylic acid and that the second mixture is then ensured so that it has the consistency of a fat. For: Chevron Researotr Company San Franc i sco, - / jC & l,, " ^r .. St> Ä. Tr.H.J.Woir;) P S-. "^ - ';-; π JJ r> \ J r-_ ~ \ f_ BATH ORIGINAL