Title of Invention

THE LUBRICATING GREASE COMPOSITION

Abstract

Lubricating grease compositions based on mixed base complex thickeners in which Titanium complex thickener is one component in mineral/synthetic oils have been prepared for the first time. Process for preparing mixed based lubricating grease compositions from these mixed soaps viz. Titanium complex-Lithium, Titanium complex-Lithium complex, Titanium complex-Aluminum complex-Clay, Titanium complex-Ca-sulfonate complex with or without additives have been disclosed. High performance Grease compositions thus resulted have exhibited improved properties in term of drop point, extreme pressure, antiwear, oil separation, shelf life, good performance in actual application.

Full Text

FORM-2 THE PATENTS ACT, 1970 (39 of 1970) COMPLETE SPECIFICATION (See Section 10) THE LUBRICATING GREASE COMPOSITION INDIAN OIL CORPORATION LTD. of the address: G-9, Ali Yavar Jung Marg, Bandra(East) Mumbai-40005l(lndia). The following specification particularly describes and ascertains the nature of this invention and the manner in which it has to be performed: 1501 3^ MUM 5 DEC 2005 Field of invention: This invention relates to the development of mixed base complex greases in which Titanium complex grease is one component and Lithium, Aluminium complex, sulphonate complex, clay or Lithium complex grease is the other component along with additives. Novel process for preparing these greases disclosed in this invention , has given synergistic effect in physico-chemical and performance characteristics. Best emerged combination in these mixed base have been observed to exhibit improved properties in shelf life, at high temperature application, extreme pressure, anti-wear properties. Back ground of the invention: In prior art, metallic soaps, their complex soaps and mixed soaps of Na -Al, or Li -Ca have generally been reported as thickeners in lubricating grease industry. Use of mixed base soap is an upcoming trend. The use of mixed soaps provides added advantage in actual application areas because of mixed characteristics of both the soaps. Polishuk in 'Brief history of lubricating greases' described different type of mixed base greases viz, Al-Ca, Al-complex-clay base, Ba-Al base, Al-complex-Na base, Ca-Al, Ca-Pb, Li-Ca (US Patent Nos: 2379245, 2332247, 2209500, 3595789) etc. Some of the mixed base greases prepared by many researchers could not get commercial appreciation may be due to compatibility of two soaps, antagonistic effect of two different soaps or commercially not viable. Polishuk reported (US 3620975) preparation of Al-complex-clay base grease for passenger car application which consist of stearic acid 2.1%, benzoic acid 1.2%, a derivative of Al-alkoxide 5.0%, Baragel clay 1% and additives. This grease was reported to perform better in wheel bearing application. Zimmer and Morway (U.S. 2062346) prepared Ca-Al base grease by use of Ca-Soap 12%, Al-Soap 10-15%, Glycerine 1% and mineral oil (300 SUS @ at 100°F) and reported to be improved in adhesive and water resistant properties. Morway and Ramsden (US 3223633) reported Li-Ca greases for channeling application which was consisting of LiOH (4.1%) , hydrofol acid 51 (15%), hydrated lime (2.0%), Azelaic acid (3.0%), acetic acid (3.0%). This grease was reported to have penetration 245 and drop point over 450° F. Over a period of time Li-Ca base grease became more popular probably because of their excellent water resistance characteristics and commercial reasons. 2 It was found interesting to note hereinto that majority of soap or complex soap thickeners of commercial significance for formulating lubricating greases are either metals derived from alkali or alkaline earth metals. Also metallic soap thickener from transition metal elements viz titanium for formulating, lubricating greases have been reported in US Patent 5387351 of the Applicants herein. However, the mixed thickener base greases of transition metal like Titanium with other metallic soaps have at all not been reported in literature. However it expected if mixed soaps based on Titanium as one of the component is formed, may exhibit high performance properties. Object of Invention:- o In accordance with this invention the lubricating grease composition comprising titanium complex grease which consists of 2-20% by weight of titanium alkaoxide, 2-20% by weight of carboxylic acids other than fatty acids, 5-35% by weight of fatty acids, 0-5% by weight of water, 20-90% by weight of an oil selected from the group consisting of mineral and synthetic oils and 10-60 % by weight of sulfonate complex soap/grease and 0-10 % by weight of additives. o In accordance with this invention the lubricating grease composition comprising titanium complex grease which consists of 2-20% by weight of titanium alkaoxide, 2-20% by weight of carboxylic acids other than fatty acids, 5-35% by weight of fatty acids, 0-5% by weight of water, 20-90% by weight of an oil selected from the group consisting of mineral and synthetic oils and 10-60 % lithium base soap/ grease and 0-10 % by weight of additives. o In accordance with this invention the lubricating grease composition comprising titanium complex grease which consists of 2-20% by weight of titanium alkaoxide, 2-20% by weight of carboxylic acids other than fatty acids, 5-35% by weight of fatty acids, 0-5% by weight of water, 20-90% by weight of an oil selected from the group consisting of mineral and synthetic oils and 10-60 % by weight of lithium complex soap/ grease and 0-10 % by weight of additives. 3 o Further this invention covers a lubricating grease composition comprising titanium complex grease which consists of 2-20% by weight of titanium alkaoxide, 2-20% by weight of carboxylic acids other than fatty acids, 5-35% by weight of fatty acids, 0-5% by weight of water, 20-90% by weight of an oil selected from the group consisting of mineral and synthetic oils and 10-60 % by weight of Aluminium complex soap/ grease and 0-10 % by weight of additives. o Moreover this invention also extends its scope to a lubricating grease composition comprising titanium complex grease which consists of 2-20% by weight of titanium alkaoxide, 2-20% by weight of carboxylic acids other than fatty acids, 5-35% by weight of fatty acids, 0-5% by weight of water, 20-90% by weight of an oil selected from the group consisting of mineral and synthetic oils and 0.5-10% by weight of clay base soap/grease and 0-10 % by weight of additives. Further according to this invention, there is provided a process for the preparation of a lubricating grease composition which comprises by forming a mix by adding together carboxylic acid and mineral or synthetic oil, stirring and heating such a mix to a temperature of 70 to 100 deg C, adding titanium alkoxide which maintaining said temperature raising the temperature to 100 to 170 deg C, to form a thickened grease product, cooling said product, adding water thereto 0-2% and adding the other lubricating grease component at 140 to 60 deg C followed by additives and then subjecting the mixture to the step of shearing. In accordance with this invention, a vessel equipped with a stirrer of rpm 0-150, is charged with 5 to 25% by weight of fatty acid, 2 to 20% by weight of carboxylic acid, 20 to 90% by weight of mineral or synthetic oil, 2 to 20% titanium alkoxide and 50% of total oil. Mixture is vigorously agitated for 1-2 hrs and vacuum of 300-500 mm Hg is applied to remove volatile components. The temperature of mixture is now raised to 50-120 deg C and is continuously mixed and held at 70-120 deg C for 1-2 hours, temperature being raised further very slowly to 120-200 C, duration of maintaining at this temperature is 2-6 hours. During this period the product gives grease structure and converts to a thickened mass. The product is then cooled with continuous stirring to 140-100 deg C and at this stage 0-2% by weight of water is added in the mixture. The other lubricating grease component is also added at this stage. The mixture is further cooled to 100-70 deg C followed by addition of additive and sheared with the help of colloid mill or 4 homogenizer to have interaction with titanium-complex soap moiety and conventional soap moieties leading to synergistic effect and compatibility between the two soaps. The resulting product of NLGI No. 1 to 3 is obtained. Further according to this invention there is provided a process for the preparation of a lubricating grease composition which comprises in preparing a mix by adding together fatty acid, carboxylic acid, titanium alkoxide and mineral or synthetic oil heating such a mixture to a temperature of 160 to 200 deg C, cooling the resultant mix, adding water thereto and adding other lubricating grease component or their soap described above, stirring the cooled mix and then further cooling said mix and subjecting it to the step of shearing. Further according to this invention the Ti-complex grease is prepared as described above and while cooling at 140-80 deg C clay either as such or soaked in base fluid is added in the mixture followed by addition of additives. The mixture is sheared to get a NLGI 1-3 consistency product. In order to describe more fully the nature of the present invention, specific examples will hereinafter be described. It should be understood, that this is done solely by way of example and is intended neither to delineate nor limit the ambit of the appended claims. Example No 1 The lubricating grease composition has been prepared consisting ingredients with proportions as described below. Phthalic acid 2-5 % Ti-alkoxide 2 - 10 % Stearic acid 3 - 9 % Total mineral base oil 75 - 85 % Effective Li-soap 2- 9 % 5 Lubricating grease was prepared by the method described above. Lubricating grease thus prepared exhibited physico-chemical characteristics indicated in Table - 1. Table-1 S.No Property ASTM/IP Method Results 1 Penetration at 25 deg C, after 60 strokes D-217 NLGI2 2 Drop point, deg C D-2265 278 3 Four ball wear EP test weld load, Kg. IP-239 250 4 Four ball wear test 40 Kg, 75 deg C, 1200 rpm & 1 hr, wear scar dia, mm D-2266 0.6 max 5 Storage life > 1 year The effectiveness of the lubricating grease composition described above demonstrates its high drop point, good EP and antiwear properties. Example No 2 This example has a variation as lithium complex grease in place of lithium base grease and terephthalic acid in place of Phthalic acid, otherwise all other conditions and ingredients are the same as started in example No. 1 The resultant grease exhibited the following physico-chemical characteristics as indicated in Table - 2. Table-2 S.No Property Method Results 1 Penetration at 25 deg C, strokes after 60 D-217 278 2 Drop point, deg C D-566 277 3 Weld load, Kg IP-239 250 4 Wear scar dia, mm D-2266 0.55 5 Storage Life > 1 year This example has demonstrated high drop point and good EP/AW properties. This composition has indicated improved results in terms of wear sear dia of 0.55 mm compared to 0.6 mm in case of above either Ti-complex or Li-complex grease. This composition has exhibited shelf life more than a year. Example No 3 This example illustrates the preparation of lubricating grease with ingredients as indicated hereinabove in example 2. The conventional lubricating grease used is Ca-sulphonate complex grease and other ingredients are the same as titanium isopropoxide, terephthalic acid, stearic acid, mineral base oil and water. The lubricating grease prepared as per described method and ingredients without any performance additive exhibited following physico-chemical characteristics in Table-3 Table-3 S.No Property ASTM/IP Method Results 1 Penetration D-217 290 2 Drop point, deg C D-566 +290 3 Four ball wear test mm wear scar dia, D-2266 0.45 4 Four ball EP test weld load, Kg IP-239 315 7 The effectiveness of the lubricating grease composition described above demonstrates its high drop point, excellent EP and antiwear properties which fulfil the objective to be a high performance lubricating grease capable of commercial applications. Example No 4 This example illustrates the preparation of lubricating grease with proportions indicated in example no-1. The polycarboxylic acid used is terephthalic acid, monocarboxylic acid is stearic acid, titanium alkoxide is titanium isopropoxide, mineral oil and water. The conventional lubricating grease used is aluminium complex The formulated grease by the procedure described above exhibited the following physico chemical characteristics as shown in Table-4. Table-4 S.No Property ASTM/IPMethod Result 1 Penetration at 25 deg C after 60 D-217 strokes 320 2 Drop point, deg C D-2265 282 3 Weld load, Kg IP-239 250 This improved process for making lubricating grease has shown high drop point & good EP properties. Example No 5 The lubricating grease composition has been prepared consisting the ingredients with the proportions indicated hereinabove. This example consists commercial titanium isopropoxide, terephthalic acid, stearic acid mineral base oil and water. The conventional clay is added in 2% concentration and without the use of binder. The composition prepared as per procedure described above has the following characteristics as shown in Table-5. 8 Table-5 S.No Property ASTM/IP Method Result 1 Penetration at 25 deg C after 60 strokes D-217 278 2 Drop point, deg C D-566 300 3 Weld load, Kg IP-239 250 4 WSD, mm D-2266 0.6 The effectiveness of the lubricating grease with clay has shown good thickening capacity, high drop point, good EP characteristics besides reducing the % of soap to make NLGI-2 by 2-3% and without addition of binding agents like propylene carbonate. Example-6 The lubricating grease composition has been prepared by addition of ingredients in proposition as desired in example no 2. Conventional EP and Antiwear additives (3%) are added to evaluate the response of additives in this new composition. The resulted composition has exhibited following characteristics. Table-6 S.No Property Method Data 1 Penetration D-217 278 2 Drop point, deg C D-566 275 3 Weld Load, Kg IP-239 560 4 Wear Scar dia, mm D-2266 0.55 This composition has indicated synergistic effect of EP and Anti-wear additives in terms of improving extreme-pressure, anti-wear properties as same dosage of additive in Li-complex grease gives only 280 Kg weld load. 9 Example 7: The lubricating grease composition has been prepared by addition of ingredients in proposition as described in example 2, conventional solid lubricants alongwith EP-AW additives have been added to evaluate the response of solid lubricants alongwith the EP-AW additives. The resultant composition has exhibited following properties. Table 7 S.No Property Method Data 1 Penetration D-217 282 2 Drop point, deg C D-566 270 3 Weld Load, Kg IP-239 620 4 Wear Scar dia, mm D-2266 0.55 This composition has exhibited synergistic response of additives on EP-AW properties of grease by increasing weld load from 250 kg to 620 Kg by addition of additives where by adding same dosage of additive in Li-base grease the weld is increased from 160 kg to 280 kg only. This indicats the synergistic response of additive with this novel thickener. Conventional Soaps/ Greases used in the invention: Table-8 Conventional Soaps/ Greases (i) Lithium-Simple & complex Soaps/ Greases (ii) Aluminium complex Soaps/ Greases (iii) Clay Grease (v) Ca-sulphonate complex Soaps/Greases 10 Comparative synergistic effect and compatibility of Ti complex grease with conventional soaps/ greases. Given below in table 9 to 14. Table-9: Test data of Titanium complex grease Table-10: Test data of Lithium grease vs TiC-Li mixed soap grease Table-11: Test data of Lithium complex grease vs TiC-LiC mixed soap grease Table-12: Test data of organoclay based grease vs TiC-Clay mixed soap grease Table-13: Test data of Aluminium complex grease vs TiC-AlC mixed soap grease Table-14: Test data of Ca-sulphonate complex grease vs TiC-Ca-sulphonate complex mixed soap grease Table-9 S.No Property ASTM / IP Method Result 1. Penetration at 25° C after 60 strokes D-217 292 2. Drop point, °C D-2265 280 3. Four ball weld load test, Kg IP-239 250 4. Four ball wear test, 40 kg 75°C, 1200rpm&lhr wear scar dia, mm D-2266 0.6 5 Storage life Conventional greases: Li- (Bl), LiC(B2), Clay(B3), AIC(B4), Ca-sulphonate(B5) greases Mixed soap greases CI: Li-+TiC, C2: LiC-+TiC, C3: clay+TiC, C4: AlC-+TiC and C5: Ca-sulphonate-+TiC 11 Table-10 s.No Property ASTM / IP Method Result (Bl) Result (CI) 1. Penetration at 25° C after 60 strokes D-217 285 280 2. Drop point, ° C D-2265/D-566 194 258 3. Four ball weld load test, Kg IP-239 140 250 4. Four ball wear test, 40 kg 75°C, 1200rpm&lhr wear scar dia, mm D-2266 0.65 0.6 5 Storage life - >1 yr > l yr Table-11 S.No Property ASTM / IP Method Result (B2)* Result (C2)** 1. Penetration at 25° C after 60 strokes D-217 280 275 2. Drop point, ° C D-2265 260 267 3. Copper Corrosion as 100°C after 24 hrs. IP-112 Pass Pass 4. Water washout characteristics At80°C,2hrs, %wt D-1264 2.4 2.2 5. Four ball weld load test, Kg IP-239 280 280 6. Four ball wear test, 40 kg 75°C, 1200rpm&lhr wear scar dia, mm D-2266 0.60 0.60 7 Storage life >l yrs 2 yrs * contains EP/AW additives ** does not contain EP/AW additives 12 Table-12 s.No Property ASTM / IP Method Result P3) Result (C3) 1. Penetration at 25° C after 60 strokes D-217 280 286 2. Drop point, ° C D-2265 280 + 280 + 3. Four ball weld load test, Kg IP-239 180. 250 4. Four ball wear test, 40 kg 75°C, 1200rpm&lhr wear scar dia, mm D-2266 0.60 0.55 5 Storage life > 1 yr >1 yr Table-13 s.No Property ASTM / IP Method Result (B4) Result (C4) 1. Penetration at 25° C after 60 strokes D-217 278 277 2. Drop point, ° C D-2265 266 277 3. Four ball weld load test, Kg IP-239 250 280 4. Four ball wear test, 40 kg 75°C, 1200rpm&l hr wear scar dia, mm D-2266 0.60 0.6 5 Storage life >1 yr >1 yr 13 Table-14 s.No Property ASTM / IP Method Result (B5) Result (C5) 1. Penetration at 25° C after 60 strokes D-217 280 275 2. Drop point, °C D-2265 303 289 3. Four ball weld load test, Kg IP-239 400 250 4. Four ball wear test, 40 kg 75°C, 1200rpm&l hr wear scar dia, mm D-2266 0.50 0.60 5 Storage life - >1 yr >1 yr Mineral oils/Synthetic oils used in the invention: The mineral oils and synthetic oils or mixtures thereof can be used depending upon the particular grease being prepared. Mineral oil used in preparing the greases can be any conventionally refined base stocks derive from paraffinic, naphthaneic and mixed base crudes. Synthetic oils that can be used include synthetic hydrocarbon such as polyalphaolefins. Additives used in the invention: The Extreme pressure and Antiwear additives, structure modifiers additives and solid lubricants additives are selected from one or more of the following:- EP/AW additives: (i.) substituted dimercapto-thiadiazole; (ii.) Antimony dialkyl dithiocarbamate, (iii.) Zn diisopropyl dithiophosphate tetra-methylenediamine and (iv). Sulphurised fat Structure Modifiers: (i.) Methacrylate-styrene copolymer and (ii).Ethylene-propylene copolymers grafted with glycidyl methacrylates. Solid Lubricants: (i.) Colloidal graphite and (ii.) Molybdenum disulphide 14 Carboxylic acids used in the invention: Table-15 S.No. Carboxylic acid Structure 1. Tartaric acid 2. Citric acid 3. Salicylic acid C6H4(OH)COOH 4. Phthalic acid (ortho- benzene dicarboxylic acid) C6H4(COOH)2 5. Terephtalic acid (para- benzene dicarboxylic acid) C6H4(COOH)2 6. Cinnamicacid C6H5CH=CH-COOH Titanium alkoxides used in the Invention: Titanium alkoxides used in the invention are alkoxide of C3 to C6 alcohol having titanium metal content of approximately 17% by weight e.g. titanium isopropoxide Clays used in the invention: Bentonite and hectorite are most widely used clays for the manufacture of clay greases. Fatty acids used in invention: The sources of fatty acids employed in this invention are alkyl carboxylic acids from vegetable sources, which may have few double bonds in the structure. For instance, it includes stearic acid, hydroxystearic acid, oleic acid, mahuwa oil, etc. 15 WE CLAIM: 1. A lubricating grease composition comprising titanium complex grease which consists of 2-20% by weight of titanium alkaoxide, 2-20% by weight of carboxylic acids other than fatty acids, 5-35% by weight of fatty acids, 0-5% by weight of water, 20-90% by weight of an oil selected from the group consisting of mineral and synthetic oils and 10-60 % by weight of conventional soap/ grease and 0-10 % by weight of additives. 2. A lubricating grease composition as claimed in claim 1 wherein conventional soap/grease is lithium base soap/ grease. 3. A lubricating grease composition as claimed in claim 1 wherein conventional soap/grease is lithium complex soap/ grease. 4. A lubricating grease composition as claimed in claim 1 wherein conventional soap/grease is Ca-sulfonate complex soap/ grease. 5. A lubricating grease composition as claimed in claim 1 wherein conventional soap/grease is Aluminium complex soap/ grease. 6. A lubricating grease composition as claimed in claim 1 wherein conventional soap/grease is clay base grease in 0.5 to 10%. 7. A lubricating grease composition as claimed in claim 1 wherein the said synthetic base oil is poly alpha olefins. 8. A lubricating grease composition as claimed in claim 1 wherein the said mineral base oil are paraffinic oils and naphthenic oils. 16 9. A lubricating grease composition as claimed in claim 1 wherein the said additives are extreme pressure additives, antiwear additives, structure modifiers and solid lubricants. 10. Process of preparation of lubricating grease composition as claimed in claim 1 which comprises steps of: (a) Charging a vessel equipped with a stirrer of rpm 0-150 with 5 to 35% by weight of fatty acid, 2 to 20% by weight of carboxylic acid, 20 to 90% by weight of mineral or synthetic oil, 2 to 20% titanium alkoxide and 50% of total oil, (b) agitating the mixture so obtained vigorously for 1 -2 hours under vacuum of 300-500 mm Hg to remove volatile components, (c) raising the temperature of mixture so obtained to 50-120°C and continuously mixing at 70-120 deg C for 1-2 hours, followed by further raising the temperature very slowly to 120-200° C, maintaining this temperature for 2-6 hours resulting in a product having grease structure and a thickened mass, (d) cooling the product so obtained with continuous stirring to a temperature between 140 to 100 deg C, adding 0-2% by weight of water and other said conventional soap/grease at this stage in the mixture, (e) cooling further the mixture so obtained to 100-70 deg C followed by addition of additives and shearing the mixture with the help of colloid mill or homogenizer. 11. A lubricating grease composition substantially as herein described with reference to the foregoing description, examples and the accompanying tables. 17 12. A Process of preparation of lubricating grease composition substantially as herein described with reference to the foregoing description, examples and the accompanying tables. Dated this 3rd day of December 2005 SHARADVABEHRA OFKANANDKRISHME ATTORNEY FOR THE APPLICANT 18

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1501-mum-2005-correspondence(ipo)-(11-10-2011).pdf

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