LUBRICATING GREASE

Abstract: A lubricating grease having a high dropping point, good stability against oxidation and long life contains a thickener comprising essentially the three components: lithium soap of C 12-24 hydroxy fatty acid; lithium phosphate salt produced from phosphoric or phosphorous acid ester and dilithium borate. The amounts of hydroxy fatty acid and phosphoric or phosphorous acid ester are 3-100 parts by weight and 0.05-15 parts by weight per part by weight of boric acid respectively.

Description: The present invention relates to lubricating grease, particularly to high quality lithium complex-based lubricating grease having a high dropping point, good heat-resistance, durability and water-resistance. Lithium soap-based grease is widely used, constituting more than 50% of the market, due to its excellence in heat-resistance, water-resistance, and since it can be dispersed in various base oils. Conventionally, a lithium soap-based grease containing C 12-24 oxyfatty acid soap of lithium and monolithium borate has been proposed (Japanese published examined patent application No. 2250/1979). Furthermore, a lithium complex-based grease having a high dropping point 482 °F (250 °C) or higher has been obtained not by adding 12-hydroxy-stearate soap and dilithium borate, but lithium 12-hydroxystearate soap and monolithium borate (Japanese published examined patent application No. 47235/1982). In addition, a grease having a high dropping point has been proposed which contains lithium dicarboxylate and lithium phosphate or phosphite (Japanese published unexamined patent application No. 212298/1982). The upper temperature limit for lithium-based greases which are available is 120-130 °C. Higher temperature, e.g., 150 °C or higher can cause such difficulties as the destruction of micelles in the grease due to oxidative degradation, softening of the grease and a reduction in its lubricating property due to an increase in exsolution. In recent years, machines and apparatus have come to be operated at higher temperatures or at higher speeds and heavier loads. For instance, the temperature of an automobile wheel bearing often reaches 150-200 °C due to friction heat from the use of a disc-brake. Under these circumstances, there is a need for a grease which is resistant to higher temperatures and which has a long life. EP-A-96 919 discloses high dropping point lithium-complex grease compositions comprising a lubricating oil and the following components: (a) at least one lithium soap of a C₁₂ to C₂₄ hydroxy fatty acid, (b) at least one lithium salt of a boric acid, and (c) at least one metal salt selected from the group consisting of 1) a potassium salt of a boric acid, 2) a sodium salt of a boric acid, 3) an alkaline earth metal salt of a boric acid, and 4) zinc salt of a boric acid. In such grease compositions, use can be made, in addition to the three components (a), (b) and (c) above, of other metal borates or other lubricant-additives, such as neutral or basic metallic detergents, such as basic Ca salicylate, or ashless dispersants, rust inhibitors (e.g., paraffin oxide, amino imidazoline or barium dinonylnaphthalenesulphonate), oxidation inhibitors (e.g. 2,6-ditertiary butyl-4-methylphenol), N-phenyl -α-naphthylamine or diphenylamine octylate) and conventional extreme-pressure additives (e.g. zinc naphthenate or other zinc compounds such as zinc dithiophosphates or zinc-oxide, lead naphthenate, sulphurized oils and fats, or tricresyl phosphate), in the proportions ordinarily employed. According to the present invention, there is provided a lubricating grease comprising a base oil in which there is distributed about 2-30 %wt of a thickener, the thickner comprising: a lithium soap (or salt) of C 12-24 hydroxy fatty acid; lithium phosphate salt produced from a phosphoric and/or phosphorous acid ester and; dilithium borate, the amounts of the hydroxy fatty acid and phosphoric and/or phosphorous acid ester(s) being in the range of 3-100 parts by weight and in the range of 0.05-15 parts by weight per part by weight boric acid, respectively. Such a grease has a high dropping point and a long life and is superior in its lubricating properties and its mechanical stability. Substantially the same consistency may be obtained with a smaller amount of a thickener than that required for known types of lithium complex-base greases. The C 12-24 hydroxyfatty acid for the lithium salt thereof may include a straight, saturated or unsaturated aliphatic monocarboxylic acid having a hydroxyl group in the molecule, for example, 2-hydroxydodecanoic acid, 2-hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid, 11-hydroxyhexadecanoic acid, ambrettolic acid, ricinoleic acid, ricinostearolic acid, 9-hydroxystearic acid, 10-hydroxystearic acid and 12-hydroxystearic acid. 12-Hydroxystearic acid and ricinoleic acid are particularly preferable. Any one of the above lithium salts of hydroxyfatty acid may be used alone or mixtures thereof may be used. The lithium phosphate or phosphite may be made by reacting phosphoric acid, phosphorous acid, or an ester thereof with lithium hydroxide; the ester form is preferable from the point of view of dispersion in the base oil. The phosphoric acid ester used as the starting material may be for example, trimethyl phosphate, triethyl phosphate, triisopropyl phosphate, tributyl phosphate, trilauryl phosphate, tristearyl phosphate, triphenyl phosphate, tricresyl phosphate, tri-2-ethylhexyl phosphate, tri-decyl phosphate, trinonylphenyl phosphate, diphenyl monodecyl phosphate, trithiotrilauryl phosphate, tri-chloroethyl phosphate, phosphite esters of the above or acidic esters of the above. Their respective phosphorous acid esters are used when phosphorous acid ester is used as the starting material. When such an ester is used as one of the starting materials, trilithium phosphate, trilithium phosphite or acid salts thereof are produced together with an alkyl alcohol or an aryl alcohol. The alcohols should be distilled off since they may give a somewhat unfavourable influence to the stability of the product grease. Accordingly, the starting ester material is preferably an ester of a lower alcohol. The base oil may be any mineral oil, a synthetic hydrocarbon oil or a synthetic ester oil. A suitable ester oil may be dioctyl sebacate. Suitable synthetic oils are pentaerythritol ester of aliphatic monocarboxylic acid, poly-α-olefinic oligomer such as octene-1/decene-1 copolymer, polyglycol oil, silicone oil, polyphenylether oil, halogenated hydrocarbon oil and alkylbenzene oil. The synthetic oil may be used alone or mixed with mineral oil. Any oil which may be used should have a kinematic viscosity of about 2-500 mm²/s, preferably about 20-200 mm²/s, at 40 °C. The lubricating grease preferably contains 5-20% by weight of thickener. The thickener preferably contains about 5-80 parts by weight of hydroxyfatty acid, about 0.1-10 parts by weight of phosphoric and/or phosphorous acid ester per part by weight of boric acid. The grease may also contain various additives such as anti-oxidants, anti-rusts, extreme pressure agents, tackiness agents, etc. The invention may be carried into practice in various ways and a number of embodiments will now be specifically described in the following non-limiting Examples. EXAMPLES One half of purified mineral oil to be used (paraffin base, viscosity index = 96, pour point = -12.5 °C, kinetic viscosity = 104.9 and 11.50 mm²/s at 40 °C and 100 °C respectively), 12-hydroxystearic acid and triethyl phosphate were mixed and heated up to 80 °C until the 12-hydroxystearic acid was dissolved. Then, aqueous solution of boric acid and of lithium hydroxide monohydrate was added. The amount of lithium hydroxide monohydrate was stoichiome trically equivalent to produce lithium 12-hydroxystearate, trilithium phosphate and dilithium borate. After dehydration the mixture was heated to 200-220 °C with stirring. The remaining purified mineral oil was added and the whole mixture was cooled to 80 °C and homogenised. The grease obtained was designated "Grease Z-1". Similar greases were prepared in the same way but with various additives. These are designated "Grease Z-2 to Z-10". Comparison 1 and 2 A similar grease to the above was prepared by omitting the phosphate (this is referred to a "Grease 1"). The similar grease was further prepared by using an amount of lithium hydroxide monohydrate resulting lithium 12-hydroxystearate, trilithium phosphate and trilithium borate (this is referred to as "Grease 2"). The compositions of the greases are given in Table 1 together with their dropping points and consistencies. The properties of the trial Grease Z-1 is given in Table 2.

Claims: A lubricating grease comprising a base oil in which there is distributed 2-30 %wt of a thickener, the thickener comprising: a lithium soap of C 12-24 hydroxy fatty acid; lithium phosphate salt produced from a phosphoric and/or phosphorous acid ester and; dilithium borate, the amounts of the hydroxy fatty acid and phosphoric and/or phosphorous acid ester(s) being in the range of 3-100 parts by weight and in the range 0.05-15 parts by weight per part by weight boric acid, respectively. A lubricating grease as claimed in claim 1 in which the thickener is in the range of 5-20% by weight. A lubricating grease as claimed in claim 1 or claim 2 in which the hydroxy fatty acid is in the range of 5-80 parts by weight and the phosphoric and/or phosphorous acid ester(s) are in the range of 0.1-10 parts by weight, per part by weight boric acid. A lubricating grease as claimed in any preceding claim in which the phosphoric acid ester is trimethyl phosphate, triethyl phosphate, triisopropyl phosphate, tributyl phosphate, trilauryl phosphate, tristearyl phosphate, triphenyl phosphate, tricresyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, trinonylphenyl phosphate, diphenyl monodecyl phosphate, trithiolauryl phosphate or trichloroethyl phosphate, or an acid ester of any of the foregoing. A lubricating grease as claimed in any preceding claim in which lithium phosphate salt contains lithium salt of phosphoric and/or phosphorous acid. A lubricating grease as claimed in any preceding claim in which the hydroxyfatty acid is a straight, saturated or unsaturated aliphatic monocarboxylic acid having a hydroxyl group in the molecule. A lubricating grease according to any of claims 1 to 5 in which the hydroxy fatty acid is 2-hydroxydodecanoic acid, 2-hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid, 11-hydroxyhexadecanoic acid, ambrettolic acid, ricinoleic acid, ricinostearic acid, 9-hydroxystearic acid or 10-hydroxystearic acid. A lubricating grease according to any of claims 1 to 5 in which the hydroxyl fatty acid is 12-hydroxystearic acid or ricinoleic acid. A lubricating grease as claimed in any preceding claim in which the base oil is a mineral oil, a synthetic hydrocarbon oil or synthetic ester oil.

Inventors: KOIZUMI, TAKEHIRO, MATSUZAWA, HIDEO
Applicants: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1987
Main classification: C10M123
IPC codes: C10N10, C10M123, C10N30, C10N50, C10N40