DE2235098A1 - GREASE - Google Patents

Description

Grease

The invention "relates to a grease composition used for mostly calculated from "a lubricating oil and about 2 Ms 3o wt% on the total mass, consists of a thickening system ", the essentially lithium soap of a hydroxy fatty acid with 12 contains up to 24 carbon atoms and a monolithium salt of boric acid, according to patent 2,157,2o7.

This is an improved lithium soap grease Of special quality with excellent properties such as a high dropping point, excellent resistance to oxidation, a long lubrication period and water resistance.

Lithium fatala such are known and have been used for many years used extensively. The lithium soaps that

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like fats used as thickeners are usually made by reacting lithium hydroxide or another suitable lithium base with a common high molecular acid or several acids. The main advantages of lithium greases are their high water resistance and the Ease of dispersing these soaps in all types of oil-based lubricants. Particularly useful are fats, which are made from Lythium hydroxystearate, as soaps from Hydroxystearic acid and related hydroxy fatty acids are found to be have proven to be mechanically more stable than the corresponding soaps of ordinary fatty acids.

There are numerous uses for fetal compositions that require a high drop point, such as in the lubrication of traction engine bearings. The bearings of such tractors should work for a period of more than three years without maintenance, where temperatures of up to 121 ⁰ O can occur within the bearings.

According to the invention, there is provided a lithium-based grease excellent in oxidation resistance as well as mechanical Resilience and desirably high dropping points 9-hydroxy, 1ο-hydroxy or 12-hydroxy fatty acid with 12 to 24, preferably 16 to 2o, carbon atoms, and boric acid. In addition, to further improve the trouf .mnktes a second hydroxycarboxylic acid with 3 bio 14 carbon atoms be used in the molecule at which diy hydroxy flu sits on a carbon atom, then no more abs 6 Kohl ons. Loff-

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atoms away from the carboxyl group.

In the American patent 2 94-0 93o is already stated that fats with a high dropping point (26o ° C or higher) are made from mixtures of 'monocarboxylic and dicarboxylic acids can be. In the production of the fats described in the said patent, however, it was also necessary Use glycol. However, the presence of glycol is undesirable, because it makes the fat sensitive to oxidation and the water resistance of the fat is lowered to an undesirable extent in various fields of application. The invention now enables the production of fats with high dropping points from hydroxy fatty acids, without the need to add glycol.

The American patents. 3 223 633 and 3 223 624 describe the production of fats with a high dropping point from a 3-component mixture of acids. The, presence of fatty acids -balzen with 2 to 4 carbon atoms in the molecule, the represent an essential component of such fats, however often undesirable, since such greases have a tendency to harden the surface on standing.

The hydroxyl fatty acid used for the production of the fats according to the invention has about 12 to 24 or more, but preferably about 16 bi; j 20 carbon atoms and is preferably a hydroxystcarinic acid, for example 9-hydroxy-, 1o-hydroxy- or 12-Hydroxystcari nsjjure, and preferably the latter »

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Also Ri zin oil acid ', which is an unsaturated form of 12-hydroxystearic acid represents and a double bond in the 9-10 position can be used. Other hydroxy fatty acids that can be used are 12-hydroxy behenic acid and lo-hydroxypalmitic acid.

If a second hydrocarboxylic acid. along with boric acid and the hydroxy fatty acid is used, it is one in which an OH group sits on a carbon atom that doesn't is more than 6 carbon atoms from the carboxyl group. This acid has 3 to 14 carbon atoms in the molecule and can either an aliphatic acid such as lactic acid, 6-hydroxy decanolic acid, J-hydroxybutanolic acid, 1-hydroxycaproic acid, 4-hydroxybutanolic acid, 6-hydroxy-alpha-hydroxystearic acid and the like, or an aromatic acid such as parahydroxybenzoic acid, salicylic acid, 2-hydroxy-4-hexylbenzoic acid, metahydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentisic acid), 2,6-dihydroxybenzoic acid (Gamma-resorcinic acid), 4-hydroxy-4-methoxybenzoic acid and the

same, or a hydroxyaromatic, aliphatic acid, such as Orthohydroxyphenyl, metahydroxyphenyl or parahydroxyphenyl acid. It can also contain a cycloaliphatic hydroxy acid, such as hydroxycyclopentylcarboxylic acid or hydroxynaphthalic acid, be used. Particularly suitable hydroxy acids are lactic acid, salicylic acid and parahydroxybenzoic acid.

It can also be used instead of a free hydroxy acid of the latter Type in the production of the fat an ester of a lower alcohol, for example methyl, ethyl, propyl, isopropyl or secondary butyl ester of the acid, such as Methyl salicylate to achieve better dispersion

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enough if the salt is insoluble. The amount of lithium salt the hydroxy acid ranges between about 0.1 to about 1o Grew .- / & of the finished jet and preferably between about 0.2 Ms about 5% by weight. Both the monolithium salt or the dilithium salt of the second hydroxy acid can be used, but the dilithium salt is preferred.

The total soap and salt content of the fat ranges from about 2 to 30% by weight, and preferably from about 5 to 20% by weight. The ratio of the hydroxy fatty acid with 12 to 24 carbon atoms in the molecule to the boric acid is in a range of the weight ratio of about 3 "to 100 parts or more, normally about 5 to 80 parts of the hydroxy fatty acid per part by weight of boric acid . It results in a weight ratio of about o, 1 to 1o or more normal proof _e; o about 5 to about 5 '-Peilen said second hydroxycarboxylic acid per wt .- eil boric acid,!' for the case that the fats can be made from three acid components.

The lubricating oil base used in the manufacture of the fat compositions is used according to the invention, any common mineral oil, a synthetic hydrocarbon oil or a be synthetic ester oil and generally has a viscosity in the range of about 35 to 2oo SUS at 99 ° Ο · Among the usable Lubricating oils include esters of dibasic acids, such as di-2-ethylttexyl sebapate, Esters of glycol, such as a diester of an oxo acid with 13 carbon atoms of letraethylene glycol, or complex esters, such as those obtained by reacting 1 mole of sebacic acid with 2 moles Ethylene glycol or 2 moles of 2-ethylhexanol acid were formed are. Other synthetic oils can be synthetic

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Hydrocarbons, such as alkylbenzenes, for example the alkylated residues from the alkylation of benzene with Tebrapropylene, or copolymers of ethylene and propylene are used, as well as silicone oils, such as Ä'thylphenylpolysiloxane, Mebhylpolysiloxane and the like, also polyglycol oils, such as those obtained by condensation of butyl alcohol can be obtained with propylene oxide, also carbonates, such as the product of a reaction of an oxo alcohol, which contains 8 carbon atoms, with ethyl carbonate to form a half-ester, followed by the reaction of the livelier with tetraethylene glycol, and the like. Other synthetic synthetic oils are polyphenyl acids, such as those that have 3 to 7 ether bonds and about 4 to 8 phenyl groups. (See also U.S. Patent 3,424,678, column 3)

The -Febbe can be produced using all three types of acids can be neutralized together or by adding boric acid and the hydroxy fatty acid is neutralized together, whereupon then the Lithiumaalζ of the two hydroxycarboxylic acid is formed.

The following examples, the preferred embodiments illustrate the production and the various properties of the fats produced according to the invention. It will also comparative examples were used, which show that worse Results are obtained when the boric acid is omitted or when the boric acid is noubralized beyond the monolibhium salt stage will.

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Example 1 (including comparative fat). *.

The set labeled A was prepared by using a combination of lithium 12-hydroxystearate and monolithic borate as a thickening agent. The base oil used in the manufacture of this grease was a refined solvent. "Mid-Oontiiient-Lubricating Oil Distillate ¹ , ¹ which is known under the name" Solvent 4-5o Neutral "and has a viscosity of about 45o SUS at 38 0 Half of the total oil that is used in the finished fat), whereupon the mixture was heated until the 12-hydroxystearic acid melted, this temperature being approximately 82 ⁰ G to 88 G. The boric acid and the lithium hydroxide monohydrate were then an aqueous solution whereupon the resulting mixture was stirred and heated to a final temperature of about 193 ° C. to 199 ° O. The remaining portion of the base oil was then added and the mixture was cooled to ambient temperature and ground in a conventional fat mill a comparison fat produced which corresponds to fat A, but with way-Ia.ο solution of boric acid.

Two additional fats were made, with the same ratio of 12-hydroxystearic acid and boric acid in each case to the base oil as in case A, but while the amount of lithium hydroxide monohydrate was increased by a dilithium borate and to form 'urilithium borate in place of moaiolithium borate ".

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Each of the fats produced in this way has been its drop point and its ASTM penetration at 25 ° G were tested. The composition of fats and theirs Test results are summarized in Table I below.

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Table I.

Zus ar-inens ec G-ra.irrm

Li0H.H ₂ 0

12-nydrosys-uaari2is aur e

Boric acid

Gruiidol

Check ere e'Dnl s s e

Invention sg emäfie s
fat No boron
acid Comparative fet; te E'r il i tii um—
borate Honolithium borate . 1 borate 3 A. 7, o
5o
O
'4-33.1 2 23.8
5o
8.3
4-53.1 12.6
5o
4-33.1 17.2
4-33.1

ASiEM peaerration at

25 C nacii 60 claim.uii—

2o8

239

2o6 I2o

O (O OO

ro C. co C. cn C. ο C. co C. co

22350

The advertising in l'aballe I soap i'otg

A comparison of the fat λ with the fat 1 seig'b that iaü Hono-11 bhiuniborat a FebU with a high drip puakb an era'tL-sben .. advertise consistency results.

The values for BVbbe 2 and 3 show that if the ratio from lithium to boric acid via that for the formation of mouoli. r ^ iii-i :: - borat required ratio is increased, the desired improvement the drip point is not reachable.

Example 2

Two b'abbe were produced, with -: -! a combination of Dilibhiumsalicylat, Libhium-IS-Hydroxyütäarat uru Monolithiumborab was used, whereby the Yarhältriissa fd: Thickening mib beibes tied with Le in the two i? etban very cd orb vmx'den. The base oil that was used to produce this B'abbe vecwen lot, wax * a solution medium for refined "Mil-Oonbinerio- -j-Minior: - öldesbillab", which is known as "Üolvanb 600 Neubr &L" bskannb is-c ^ n ^ \ i.ini Viskosibäb bei ^z ) i ^ G von ebwa 6oo u \ i'6 bealbzb, Htichylsuii ^ j .l.at and Ί2-Hyd-roxys beacic acid became sLnem {DsLl des Grandöli; added b, v; orauC the mixture was heated b. Wao-hdem baobachbeb v / urde that the 12-hydroxysbearic acid geaohmolzen v / ar, the I'eniperabur bebi-ug ebwa B2 ° U to 88 ⁰ G, the total was ι '... :;: Ü. um · hydroicyd, which is responsible for the formation of the various. Li.bhLuiihuiLzt; / ewfcüdeb was, Ln B ¹ OrIIi of a lo / iLgen vnissrlgon solution hLnauje-i'-i.-.-. ,, wöbeL this solution auIUirdeui dLe zv.v He) L ¹ SbUlLuHg; the i''a.;ij; .- ■ or before the boric acid had been delivered. OLa himself urg.ibvu.iu ^ LL s ο hung was stirred; and am on jLne 'L'oinoeratiUt' from dbv / a

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BAD LOCAL

193 ° G "heated to 199 O. Then the remaining part of the base oil was added and the mixture was ^{cooled to ettfa 121 0} G.» Before an antioxidant and other fat ingredients, such as rust prevention agent, were added, the fat was then ground in a conventional fat grinder *

Comparative example

Using the same method as in Example 2 were made Comparative fats produced, in one case the methyl salicylate and in the second case the boric acid was omitted, while in the third case neither boric acid nor methyl salicylate were used became. In each case, the appropriate amount of lithium hydroxide, that was required to form the soap or salt of the omitted ingredient is also omitted.

Each of the greases produced in Example 2 and in the experimental example were tested for their drop point and ASTM penetration at 2Jp ^{0 G.} The composition of these fats and their test results are listed in Table II below. . ■. - ■

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Table II

fat according to the invention Σ comparative fats M. H T Z

ammensetion in wt .-%

LiOH.HpO 12-hydroxystearic acid Boric acid methyl s alicyl at base oil phenyl-alpha-naphthylamine NaSuI-BSN

Test results drop point, ASTM penetration at 25 ° 0

over 26ο

unprocessed

after 6o stresses

after I0.000

B e ansp.

gene

1.9 2.5 2.9 1.8 1o, 4 12.9 11.5 12.9 o, 5 , 1.1 - - o, 5 - 2.5 - 84.7 82.5 81.1 85.3 1, o 1, o 1.0 -

over 26o

275

28o

299

262

255

291

213

217

24o

243

2o7

261

250

7th NJ NJ CO cn I. CO ιέ

That. Phenyl-alpha-Jffa $ Hylamine mentioned in the table was used as Antioxidants used. The term Na-SuI-B8N is a brand name for a product that acts as a fiost prevention agent serves. It is a 5o wt% concentrate of one neutral barium salt of that of tripropylene alkylated Naphthalene derived dinonylnaphthalene sulfonic acid in a light mineral oil. ·;

Looking at the values in Table II, a comparison of fat Z with fats Z and M shows that when monolithium borate is added to the lithium hydroxystearate fat, the dropping point increases somewhat, but the increase in the dropping point is considerably greater when lithium salicylate is also used will. A comparison of the fats Ί Z shows that if lithium salicylate is added without monolithium borate, the dropping point is not significantly improved.

Various other conventional additives can be added to the present invention Composition are added, as the skilled person knows. Such additives are, for example, antioxidants, agents to prevent rust formation, means to improve the Adhesion, odor-modifying agents, colors, extreme pressure agents and the same.

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Claims (1)

Patent claims A lubricating grease composition consisting largely of a lubricating oil and about 2 to 3o% by weight, calculated on the total mass, consists of a thickening system, which is essentially a Libhiumseife Hydroxy fatty acid having 12 to 24 carbon atoms and contains a monolithium salt of boric acid, according to patent 2 157 2o7, characterized in that the weight ratio of hydroxy fatty acid to boric acid is 3: 100 amounts to. I bed composition according to claim 1, characterized in that that the thickening sysbem is also called third component is a lithium salt of a second Contains hydroxycarboxylic acid with 3 to 14 carbon atoms in the molecule, v / o with the hydroxyl group on one Carbon atom that sits no further than 6 carbon atoms removed from the carboxyl group is, where the weight ratio of the second Hydroicy carboxylic acid to boric acid is about 0.1 to about. 3rd bed composition according to claim 1, characterized in that that it is the hydroxy fatty acid; to 12-Hydroxys tearic acid hando L b. 4. Fat composition according to. , Claim 2, characterized characterized in that the second ■ hydroxycarboxylic acid is salicylic acid. 5. I fat composition according to claim 2, characterized characterized in that the two-tone hydroxycarboxylic acid is lactic acid. .. 6. Fat composition according to claim 2, characterized in that characterized in that the second hydroxycarboxylic acid is parahydroxybenzoic acid acts. * 3098 2 0/0896