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Wo 2009/145825 A2 (12) INTERNATIONALAPPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date 3 December 2009 (03.12.2009) WO 2009/145825 A2 (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every ClOM 169/00 (2006.01) ClON 30/02 (2006.01) kind of national protection available): AE, AG, AL, AM, ClOM 169/02 (2006.01) ClON 40/00 (2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, ClON 20/06 (2006.01) ClON 50/10 (2006.01) CA, CH, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, (21) International Application Number: HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, KR, PCT/US2009/001984 KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, (22) International Filing Date: MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, 31 March 2009 (3 1.03.2009) NZ, OM, PG, PH, PL, PT, RO, RS, RU, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TJ, TM, TN, TR, TT, TZ, UA, (25) Filing Language: English UG, US, UZ, VC, VN, ZA, ZM, ZW. (26) Publication Language: English (84) Designated States (unless otherwise indicated, for every (30) Priority Data: kind of regional protection available): ARIPO (BW, GH, 61/072,433 31 March 2008 (3 1.03.2008) US GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, 12/378,466 13 February 2009 (13.02.2009) US ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, (71) Applicant (for all designated States except US): ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, EXXONMOBIL RESEARCH AND ENGINEERING MC, MK, MT, NL, NO, PL, PT, RO, SE, SI, SK, TR), COMPANY [US/US]; 1545 Route 22 East, P.O. Box OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, ML, 900, Annandale, NJ 08801-0900 (US). MR, NE, SN, TD, TG). (72) Inventor; and Published: (75) Inventor/Applicant (for US only): BAUM, William [US/ — without international search report and to be republished US]; 236 Tall Pines Drive, Sewell, NJ 08080 (US). upon receipt of that report (Rule 48.2(gf) (74) Agents: BAKUN, Estelle, C. et al; Exxonmobil Re search And Engineering Company, 1545 Route 22 East, P.O. Box 900, Annandale, NJ 08801-0900 (US). (54) Title: HIGH VISCOSITY INDEX PAO WITH POLYUREA THICKENERS IN GREASE COMPOSITIONS Figure 1 Comparison of Conventional Grease with New Candidate SRV Step Load 100 200 300 400 500 600 700 Load (N) (57) Abstract: The invention relates to grease compositions containing high viscosity index polyalphaolefins (HVI-PAO) and polyurea thickeners. The use of HVI-PAOs and polyurea thickeners in a bi-modal base stock grease application provides favorable factional properties and improved overall performance. HIGH VISCOSITY INDEX PAO WITH POLYUREA THICKENERS IN GREASE COMPOSITIONS FIELD OF THE INVENTION [0001] The invention relates to grease compositions containing high viscosity index polyalphaolefins ("HVI-PAO") and polyurea thickeners. BACKGROUND OF THE INVENTION [0002] Lubricating greases are homogeneous products of semi-liquid to solid consistency. Essentially, they consist of a dispersion of a thickener in a liquid lubricant or base oil. In general, the thickener is a significant determinant of the properties of the greases. [0003] ASTM D 288 defines lubricating greases as," a solid to semifluid product of dispersion of a thickening agent in a liquid lubricant. Other ingredients imparting special properties may be included." See ASTM "Standards on Petroleum Products," p. 156, 1950 [0004] A grease is a lubricant which has been thickened in order that it remain in contact with the moving surfaces and not leak out under gravity or centrifugal action, or be squeezed out under pressure. Thus a major practical problem is the provision or a structure which will stand up to shear and temperature stresses to which it may be subjected during use. See Void, Marjorie J., and Void Robert D., J, Inst. Petroleum Tech., 38, 155 - 163 (1952). [0005] Polyurea compounds are among the thickeners used in making greases. Often the polyurea compounds are prepared directly in the base oil by the reaction of amines with isocyanates. [0006] Polyalphaolefins ("PAOs") of different viscosity grades are known to be useful in synthetic and semi-synthetic industrial oil and grease formulations. See, for instance, Chapters 22 and 23 in Rudnick et al., "Synthetic Lubricants and High-Performance Functional Fluids", 2nd Ed.Marcel Dekker, Inc., N.Y. (1999). Compared to the conventional mineral oil-based products, these PAO- based products have excellent viscometrics, high and low temperature performance and energy efficiency under routine conditions and ordinary replacement schedules. [0007] The viscosity-temperature relationship of lubricating oil in a grease is one of the critical criteria, which must be considered when selecting a lubricant for a particular grease application. Viscosity index (VI) is an empirical, unit less number which indicates the rate of change in the viscosity of an oil within a given temperature range. Fluids exhibiting a relatively large change in viscosity with temperature are said to have a low viscosity index. A low VI oil, for example, will thin out at elevated temperatures faster than a high VI oil. Usually, the high VI oil is more desirable because it has higher viscosity at higher temperature, which translates into better or thicker lubrication films and better protection of the contacting machine elements. In another aspect, as the oil operating temperature decreases, the viscosity of a high VI oil will not increase as much as the viscosity of a low VI oil. This is advantageous because the excessively high viscosity of the low VI oil will decrease the efficiency of the operating machine. Thus a high VI oil has performance advantages in both high and low temperature operation. VI is determined according to ASTM method D- 2270-93 [1998]. VI is related to kinematic viscosities measured at 40°C and 100°C using ASTM Method D 445-01. [0008] Greases are required to ensure the following: good adhesion, low oil separation, low starting torques, compatibility with synthetic materials, and noise dampening (c.f., Rudnick et al., supra). Most importantly, grease requires good frictional properties. There is a need for a grease meeting all these requirements including improved or lower frictional properties. This invention satisfies that need. SUMMARY [0009] The invention is directed to oil and grease formulations for industrial use comprising a high viscosity index polyalphaolefin (HVI-PAO) and a polyurea thickener. In one embodiment a grease with favorable frictional properties is disclosed. In this embodiment, the grease comprises a first base stock comprising a PAO with a viscosity over 100 cSt KV 100 0C and a viscosity index over 100, a second base stock with a viscosity at least 25 cSt KV 100 0C less than the viscosity of the first base stock, the second base stock selected from the group consisting of Group II, Group III, PAO, GTL and any combination thereof, a polyurea thickener comprising at least 5 weight of the grease and less than 25 weight percent of the grease. [0010] In a second embodiment a method to improve frictional properties is disclosed. In this embodiment, the method comprises obtaining a grease comprising a first base stock comprising a PAO with a viscosity over 100 cSt KV 100 0C and a viscosity index over 100, a second base stock with a viscosity at least 25 cSt KV 100 0C less than the viscosity of the first base stock, the second base stock selected from the group consisting of Group II, Group III, PAO, GTL and any combination thereof, a polyurea thickener comprising at least 5 weight of the grease and less than 25 weight percent of the grease and lubricating with the grease. [0011] In a third embodiment a method to formulate a grease with improved frictional properties is disclosed. In this embodiment, the method comprises obtaining a first base stock comprising a PAO with a viscosity over 100 cSt KV 100 0C and a viscosity index over 100, a second base stock with a viscosity at least 25 cSt KV 100 0C less than the viscosity of the first base stock, the second base stock selected from the group consisting of Group II, Group III, PAO, GTL and any combination thereof, a polyurea thickener comprising at least 5 weight of the grease and less than 25 weight percent of the grease and lubricating with the grease and blending the first base stock, the second base stock, and thickener to form a grease with favorable frictional properties. BRIEF DESCRIPTION OF THE DRAWINGS [0012] The present invention and its advantages will be better understood by referring to the following detailed description and the attached drawing. [0013] Figure 1 is a graph illustrating the viscosity losses for several example formulations. DETAILED DESCRIPTION [0014] The invention involves a surprising discovery involving novel grease composition comprising a high viscosity index PAO (HVI-PAO) and polyurea thickeners. According to the invention, formulations for use as industrial oils and greases are provided comprising a high viscosity index PAO mixed with a second base stock with a lower viscosity than the high viscosity PAO and a polyurea thickener. The present invention also comprises grease compositions containing lubricant base stocks and additional additives known by persons skilled in the art to be useful for greases. [0015] Applicant has discovered novel combinations of base stocks that provide unexpected favorable improvements in frictional properties pf greases.
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