JPH0694557B2 - Grease composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel family of compositions. More specifically, it relates to a grease comprising an oil, a hydroxy-containing soap thickener, and a hydroxy-containing borated ester containing a phosphorus component and a sulfur component.

Alcohols are well known for their lubricity when blended with lubricating oils and their ability to remove water when blended with fuels. Phosphorus hydroxy-containing alkyl carboxylates such as glycerol monooleate have also found use as lubricating additives. U.S. Pat. No. 2,788,326 discloses some esters suitable for the present invention such as glycerol monooleate as a minor component of lubricating oil compositions. U.S. Pat. No. 3,235,498 discloses similar esters as additives to other oils. U.S. Pat.No. 2,448,
No. 578, for example, teaches esters with a free hydroxyl group at the acid site, such as tartaric acid. U.S. Pat.No. 2,798,083
No. 2, No. 2,820,014, No. 3,115,519, No. 3,282,91
No. 7, No. 3,309,318 and August 1975, Lubrication Engineering, pp. 454-457, by RR Barnes, entitled "Synthetic Ester Lubricants," describes polyhydric alcohols and hydroxyl groups that are not related to acid function. It teaches lubricants made with acids that do not contain.

According to the invention, a major proportion of grease and the formula: R (COOR ¹ ) n (wherein R and R ¹ are hydrocarbyl or hydroxyhydrocarbyl groups containing 1 to 40, preferably 8 to 20 carbon atoms) Wherein at least one of R and R ¹ is a hydroxyhydrocarbyl group, and n is 1 to 5), and the hydrocarbyl ester is represented by the metaborate or similar boric acid source, boric acid, boron oxide or the formula: R ² O) _X B (OH) _Y , where X is 1 to 3, Y is 0 to 2, their sum is 3, and R ² is 1 to 6 carbon atoms. An improved grease composition comprising a minor amount of a compound prepared by reacting with an alkyl borate having an alkyl group of Characterized in that to produce a grease with a thickener, and dropping point provides grease composition characterized in that at least 240 ° C.. The presence of phosphorus and sulfur components gives higher drop points. Hydrocarbyl and hydroxyhydrocarbyl include alkyl, aryl, aralkyl, alkaryl, and cycloalkyl groups. Preferably the ester is perborated, which means that a stoichiometric or higher amount of boron is present in the product. The ester can contain 1 to 5 hydroxy groups in the molecule. The hydroxy group may be added to R or R ¹ or may be added to R and R ¹ in various ratios. Furthermore, the hydroxy group may be anywhere on the R or R ¹ chain. It will be appreciated that the ester contains at least one free hydroxy group prior to reaction with the boron compound.

The disclosed esters can be made by methods well known in the art. The ester is made by reacting the desired acid or acyl halide with an alcohol at a temperature and for a time that can be easily selected by one skilled in the art. As will be appreciated by those skilled in the art, the proportion of reactants is chosen to provide R or R ¹ with an ester bearing a free hydroxy group. Suitable hydroxy-containing esters before boration are trimethylolpropane monooleate, trimethylolpropane dioleate, trimethylolpropane monostearate, trimethylolpropane distearate, trimethylolpropane monopelargonate, trimethylolpropane monooleate. Ate monopelargonate, pentaerythritol monooleate, pentaerythritol dioleate, pentaerythritol trioleate, pentaerythritol monoisostearate, pentaerythritol monooleate monopelargonate,
Pentaerythritol monoisostearate, monopelargonate or monohexanoate, pentaerythritol pelargonate, glycerol monooleate,
Glycerol dioleate, glycerol monostearate, glycerol monoricinoleate, glycerol monoisostearate, glycerol monopelargonate, glycerol monohexadecanoate, sorbitan monooleate, sorbitan dioleate, sorbitan monostearate, sorbitan Distearate, sorbitan monopelargonate, dipentaerythritol monooleate, dipentaerythritol monooleate,
Dipentaerythritol dioleate, dipentaerythritol trioleate, ethylene glycol monooleate, ethylene glycol monostearate, ethylene glycol monoisostearate, diethylene glycol monooleate, diethylene glycol monopelargonate, diethylene glycol monoisostearate and triethylene glycol Includes monooleate, methyl hydroxystearate and ethyl hydroxy stearate, or mixtures thereof.

The borated ester of the present invention can be prepared by reacting the above ester with a boron compound such as boron oxide, metaborate, boric acid, alkyl borate or a mixture thereof. The products obtained are predominantly boric acid esters, but other possible products contained are products which form the corresponding boronic esters in the reaction between ester dimers or higher oligomers and boron compounds. Is.

As mentioned above, the boron compound used is boric acid, boron oxide,
Alternatively, it is an alkyl borate, preferably boric acid.
Alkyl borates are mono, di, and trialkyl borates, such as mono, di, and trimethyl borates, mono,
Includes di and triethyl borate, mono, di and tripropyl borate mono, di and tributyl borate, mono, di and tripentyl borate, and mono, di and trihexyl borate.

The reaction to form the borate ester can be carried out at 80 ° C to 260 ° C, preferably 110 ° C to 180 ° C. The temperature selected will often depend on the particular reactants and whether or not a solvent is used. The reaction pressure can be vacuum, atmospheric pressure or positive pressure. In carrying out this reaction, it is preferred to select the amount of reactants so that the molar ratio of ester to boron compound is 1 to 4, preferably 1 to 2, or more preferably about 1. The ester may be reacted with excess borate species to form 0.1% to 10% by weight or more of boron to form the borate ester.

Although atmospheric pressure is generally preferred, the reaction can be advantageously carried out at 1 to 5 atmospheres. Furthermore, a solvent can be used as a condition for guaranteeing this reaction. Generally, relatively non-polar, non-reactive solvents can be used and include benzene, toluene, xylene and 1,4-dioxane. Other carbon hydrogen solvents and alcohol solvents such as propanol, butanol, hexamethylene glycol can also be used. Mixtures of alcoholic solvents and hydrocarbon solvents can also be used.

The reaction time is not critical. Thus various aspects of the process can be carried out in 1 to 20 hours.

A narrow group of thickeners are used to make the greases of this invention. Thickeners include at least a portion of hydroxy-containing fatty acids having 12 to 30 carbon atoms per molecule, fatty glycerides and fatty esters of alkali metals, alkaline earth metals or amine soaps. Typical metals are sodium, lithium, calcium and barium. Lithium is preferred. Preferred among these acids and fatty substances are 12-hydroxystearic acid; and 12-hydroxystearate, 14-hydroxystearic acid, 1
It is a glyceride containing 6-hydroxystearic acid and 6-hydroxystearic acid.

It is not necessary that the total amount of thickener be derived from the ingredients. Significant benefits are obtained with only 15 parts by weight of total thickener. A wide variety of thickeners with replenishing amounts, for example up to 85% by weight, can be used in the greases of the present invention. Other useful thickeners are methyl 12-hydroxystearate of alkali and alkaline earth metal soaps, to C ₄ not containing C ₁₂ diesters of dicarboxylic acids and tall oil fatty acid. 12 carbon atoms
Other alkali or alcal earth metal soaps from 30 to 30 containing no free hydroxy groups may be used. These include stearic and oleic soaps.

The thickener can be produced in various grease producing devices such as an open kettle operated at reduced pressure, normal pressure or positive pressure; a high pressure reaction chamber operating at 180 psig and high pressure; or a continuous production device.

Other thickeners are salts and complex salts and soaps such as calcium stearate-acetate (US Pat. No. 2,197,26).
3), barium stearate acetate (US Pat. No. 2,564,561), calcium stearate-caprylate-acetate complex (US Pat. No. 2,999,065),
Calcium caprylate-acetate (US Patent 2,999,06
No. 6), and calcium salts and calcium soaps of low, medium and high molecular weight acids and nut oils. Another group of thickeners includes substituted ureas, phthalocyanines, induslenes, pigments such as perylimide, pyromellitodiimide and amelin, and certain hydrophobic clays. These thickeners can initially be made from hydrophobic clay,
These clays are converted to a hydrophobic state by introducing long-chain hydrocarbon groups onto the clay surface by pretreatment with an organic cationic surface active agent such as an onium compound before being used as a component of a grease composition. . A typical onium compound is a tetraalkylammonium chloride, such as diethyldioctadecyl ammonium chloride,
Dimethyldibenzylammonium chloride, and mixtures thereof. This conversion method is well known in the art.

The third component that can be included in the present grease composition is a phosphorus component and a sulfur component. Both of these are of the same molecule, for example a metal or non-metal phosphorodithioate of the formula: Where R ³ is a hydrocarbyl group having 3 to 18 carbon atoms, M is preferably a metal but may be a non-metal, for example one of those mentioned below, n is M
And Z is oxygen or sulfur, and at least one Z is sulfur).

In this compound, R ³ is preferably an alkyl group which may be a propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl or octadicyl group, isopropanol, propanol, butanol, isobutanol, sec-butanol, 4 -Methyl-2-
Includes those derived from pentanol, 2-ethylhexanol, oleyl alcohol, and mixtures thereof.
Further included are alkaryl groups, later butylpentyl, octylphenyl, nonylphenyl and dodecylphenyl groups.

The metals included in M include those included in Group IA, Group IIA, Group IIB and Group VIII of the Periodic Table. Examples include lithium, sodium, calcium, zinc, cadmium, silver, gold and molybdenum. Non-metal ions include vinyl esters such as vinyl acetate, vinyl ethers such as butyl vinyl ether, and organic groups derived from epoxides such as propylene oxide and 1,2-epoxide dodecane. Phosphorus and sulfur may be supplied from a combination of two separate compounds, such as (1) dihydrocarbyl phosphite or a mixture of phosphites having 2 to 10 carbon atoms in each hydrocarbyl group, and (2) sulfurization. A combination of sulfurized isobutylene, dibenzyl disulphide, terpene sulphide, phosphorodithionyl disulphide and diodijoba sulphide. Phosphites include dibutyl, dihexyl, dioctyl, didecyl and similar phosphites. Phosphate esters containing from 4 to 20 carbon atoms in each hydrocarbyl group can also be used, for example tributyl phosphate, toldecyl phosphate, tricresyl phosphate and mixtures of such phosphates.

In summary, in practicing the invention resulting in a grease with improved dropping point, it is essential to incorporate at least the first two of the above components into the composition. Thus, with regard to grease preparation, the thickener should be at least
It contains 15% by weight of metal- or non-metal hydroxy-containing soap, the total amount of thickener being 3 to 20% by weight of the grease composition.
Is. Second, 0.01 to 10% by weight, preferably 0.2
To 2% by weight of borated ester is added to the grease, where such ester, preferably at least equimolar, is reacted with the boron compound. Thirdly, the composition is 0.01 to 10% by weight, preferably 0.2 to 2% by weight.
Of phosphorus and sulfur-containing compounds or mixtures of two or more compounds which supply phosphorus components separately. If separate compounds are used, the desired amounts of phosphorus and sulfur are provided in an amount equal to the above concentration level of the mixture.

When a hydroxy-containing thickener is used with a borated ester, the grease dripping point is a grease from a similar grease pigment and a similar borated ester but with a different thickening agent such as a non-hydroxy-containing thickener. I found it to be unexpectedly higher than. Thus, a broad range of the present invention is a grease composition comprising the above two components.

In general, the reaction products of the present invention provide the desired degree of friction reduction,
It can be used in an amount effective to impart antiwear activity, antioxidant activity, high temperature stability and antirust activity. However, in many applications, borated esters and phosphorus and / or sulfur containing compounds and 0.02 to 20% by total weight of the composition are used.
Effectively used in combination amounts of weight percent, preferably 0.2 to 4 weight percent.

The grease of the present invention can be made from mineral oils or synthetic oils. In general, mineral oils containing paraffins, naphthenes, and both, have 45 SSU at a suitable viscosity range such as 37.8 ° C.
Can be 6000 SSU at 37.8 ° C. These oils have a clay index in the 100 or higher range. 70
A viscosity index of from 95 to 95 is preferred. The average molecular weight of these oils may range from 250 to 800. In making the grease, after weighing the desired amount of thickener, and other additives to include in the grease formulation, the lubricating oil that produces the grease is generally added in an amount sufficient to balance the total grease composition. Uses.

If synthetic oils are desired over mineral oils, various compounds of this type can be conveniently utilized. Representative synthetic vehicles are polyisobutylene, polybutene, hydrogenated polydecene, polypropylene glycol, polyethylene glycol, trimethylolpropane ester, esters of neopentyl and pentaerythritol, di (2-ethylhexyl) sebacate, di (2-ethylhexyl) adipate,
Dibutyl phthalate, fluorocarbon silicate ester, silane, ester of phosphorus-containing acid, liquid urea, ferrocene derivative, hydrogenated synthetic oil, chain polyphenyl, siloxane and silicone (polysiloxane), butyl-substituted bis (p-phenoxyphenyl) ether Include alkyl-substituted diphenyl ethers represented by and phenoxyphenyl ethers.

Metal soap soap compositions containing one or more borated hydroxy-containing esters, one or more combinations of sulfur and phosphorus described herein, have increased drop points, improved grease consistency properties, anti-rust properties. It offers properties and potential anti-fatigue benefits as well as anti-wear and anti-oxidant benefits not available with conventional greases. The grease composition of the present invention is unique in that it can be suitably prepared by mixing an added amount of alcohol borate with a soap grease which has been sufficiently formed after the completion of saponification.

The following example illustrates the invention.

Production Example 1. Glycerol monooleate (115 g) consisting of a mixture of about 60% glycerol monooleate and about 40% glycerol dioleate, xylene (38 g) and butanol (122 g) was heated with a stirrer and The reactor was equipped with a condenser. The contents of the reactor were heated to 50 ° C. and boric acid (100 g) was added to the ester and solvent. The reaction mixture was heated to 204 ° C and held for about 3 hours until the evolution of water ceased. The contents of the reactor were cooled to 155 ° C. and a vacuum (2 mm Hg or less) was applied to remove the solvent. 1 more crude product
Cooled to 05 ° C. then filtered through diatomaceous earth to give a viscous amber liquid.

Preparation Example 2. Same as Preparation Example 1, except that the excess boron was provided using the following weight ratio: Glycerol monooleate 7.55
Pound / pound, butanol borate 1.13 lb / lb, borate xylene 0.17 lb / lb, nitric acid Comparative Example 1. 12-Sudroxystearic acid (8%) and its glyceride (9%) in a mineral oil vehicle in a sealed contactor. A lithium hydroxystearate grease thickener was prepared by saponifying the mixture containing ## STR1 ## with lithium hydroxide at 177.degree. After depressurizing in an open kettle to dehydrate the thickener, a sufficient amount of mineral oil was added to reduce the thickener content to 9.0%. After cooling to 99 ° C, a typical grease additive package consisting of an amine antioxidant, a phenol antioxidant, a metal dithiophosphate, a sulfur-containing metal deactivator and a nitrogen-containing antirust agent was added. This provided a base grease for evaluating the effect of borated hydroxy-containing esters on grease dropping point and other properties.

Example 1. 2% by weight of borated glycerol monooleate of Preparation Example 1 was added to the grease of Comparative Example 1. This addition is 110 ℃
To 116 ° C. in a laboratory grease mixer.

Example 2. Example 1 was repeated except that 2% by weight of borated glycerol monooleate of Preparation Example 2 was used.

Comparative Example 2. A grease similar to Comparative Example 1 was prepared except that the mineral oil was thickened with lithium soap of a 50/50 (by weight) mixture of stearic acid and palmitic acid.

The results obtained using the ASTM D-2265-78 test are summarized in Table 1.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10M 137: 04 135: 02 159: 12) (C10M 159/12 139: 00 129: 68) C10N 10:02 10 : 04 10:16 30:00 Z 8217-4H 30:06 30:10 30:12 50:10 (72) Inventor Jyon Anton Keller Junier United States New Jersey 08071, Pittman, Thompson Avenyu 10 (56) References JP-A-53-115706 (JP, A) JP-A-57-172997 (JP, A) US Pat. No. 2943054 (US, A)

Claims (19)

[Claims] 1. A grease having a major proportion; (b) Formula: R (COOR ¹ ) n (where n is 1 to 5, and R and R ¹ contain 1 to 40 carbon atoms). A hydrocarbyl or hydroxyhydrocarbyl group, wherein R and
At least one of R ¹ is a hydroxyhydrocarbyl group) 0.01 to 10% by weight of a reaction product produced by reacting a boron compound with an ester; and (c) hydroxy having 12 to 30 carbon atoms. Fatty acids,
An improved grease composition comprising a thickener containing at least 15% by weight of lithium soap of a fatty glyceride or a fatty ester; and having a dropping point of at least 240 ° C. 2. A compound of phosphorus and sulfur or a mixture of a phosphorus-containing compound and a sulfur-containing compound is further contained in an amount of 0.01 to 10% by weight to give an equal amount of phosphorus and sulfur.
The composition according to the item. 3. A thickener is 12-hydroxystearic acid,
A composition according to claim 1 which is derived from 14-hydroxystearic acid, 16-hydroxystearic acid, or glycerides or esters thereof. 4. A composition according to claim 1 wherein R is alkyl, aryl, aralkyl, alkaryl, cycloalkyl or hydroxy substituents thereof. 5. The ester is trimethylolpropane monooleate, trimethylolpropane dioleate, trimethylolpropane monostearate, trimethylolpropane distearate, trimethylolpropane monopelargonate, trimethylolpropane monooleate monoester. Pelargonate, pentaerythritol monooleate, pentaerythritol dioleate, pentaerythritol trioleate, pentaerythritol monoisostearate, pentaerythritol monooleate monopelargonate, pentaerythritol monoisostearate, monopelargonate or monohexano Ate, pentaerythritol triperargonate, glycerol monooleate, glycerol dioleate, glycero Monostearate, glycerol mono-ricinoleate, glycerol monoisostearate, glycerol mono pelargonate, glycerol mono hexa decanoate, sorbitan monooleate, sorbitan dioleate, sorbitan monostearate,
Sorbitan distearate, sorbitan monopelargonate, dipentaerythritol monooleate, dipentaerythritol monooleate, dipentaerythritol dioleate, dipentaerythritol trioleate, ethylene glycol monooleate, ethylene glycol monostearate, ethylene A glycol monoisostearate, diethylene glycol monooleate, diethylene glycol monopelargonate, diethylene glycol monoisostearate, and triethylene glycol monooleate, methyl hydroxystearate, or ethyl hydroxystearate. The composition according to. 6. Boron compounds are metaborates; boric acid; boron oxides; mono-, di- and trimethylboric acids; mono-, di- and triethylboric acids, mono-, di- and tripropylboric acids; mono-, di- and tributylboric acids. A composition according to claim 1 selected from the group consisting of: mono, di and tripentyl boric acid; and mono, di and trihexyl boric acid. 7. The phosphorus component and the sulfur component are represented by the formula: (Wherein R ³ is a hydrocarbyl group having 3 to 18 carbon atoms, M is a metal or a nonmetal, n is a valence of M, and Z is oxygen or sulfur, at least one of which is A composition according to claim 2 provided by a phosphorothioate of the formula: 8. The composition according to claim 7, wherein R ³ is an alkyl or alkaryl group. 9. R ³ is a propyl, butyl, pentyl, hexyl, octyl, dodecyl, tetradecyl, octadecyl, butylphenyl, octylphenyl, nonylphenyl, dodecylphenyl or oleyl group or mixtures thereof. Item 8. The composition according to item 8. 10. The method of claim 9 wherein R ³ is derived from isopropanol, butanol, isobutanol, sec-butanol, 4-methyl-2-pentanol, 2-ethylhexanol or mixtures thereof. Composition. 11. The composition according to claim 7, wherein M is a metal of Group IA, IIA, IIB or VIII of the Periodic Table. 12. The composition according to claim 11, wherein the metal is lithium, sodium, molybdenum, calcium, zinc, cadmium, silver or gold. 13. A composition according to claim 7, wherein M is derived from vinyl acetate, butyl vinyl ether, propylene oxide, 1,2-epoxydodecane, or nitrogen compounds. 14. A phosphorus component and a sulfur component are (1) a dihydrocarbyl phosphite having 2 to 6 carbon atoms in each hydrocarbyl group, a mixture of such phosphites,
Or a combination of phosphoric acid esters having 4 to 20 carbon atoms in each hydrocarbyl group, and (2) isobutylene sulfide, dibenzyl disulfide, terpene sulfide, phosphorodithionyl disulfide, and jojoba oil sulfide. A composition according to claim 1. 15. A composition according to claim 14 wherein the phosphite is dibutyl, dihexyl, dioctyl or didecyl phosphite or mixtures thereof. 16. The composition of claim 14 wherein the phosphate ester is tributyl, tridecyl, or tricresyl phosphate ester or mixtures thereof. 17. The ester is glycerol monooleate, the boron compound is boric acid, the thickening agent is lithium 12-hydroxystearate, and the sulfur component is zinc dialkylphosphorodithionate (where alkyl has 3 carbon atoms).
A composition according to claim 1, which is derived from a mixture of alkyls of 6 to 6). 18. The composition according to claim 1, wherein the grease vehicle is a mineral oil, a synthetic oil or a mixture thereof. 19. The boron compound is metaborate, boric acid, boron oxide and the following formula: (R ² O) _X B (OH) _Y (wherein X is 1 to 3 and Y is 0 to 2). And their sum is 3, and R ² is 1 to 3
A composition according to claim 1, which is selected from the group consisting of alkyl borates (which are alkyl groups having 1 carbon atom).