US20120004153A1 - Lithium Complex Grease with Improved Thickener Yield - Google Patents

Lithium Complex Grease with Improved Thickener Yield Download PDF

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Publication number
US20120004153A1
US20120004153A1 US12/827,151 US82715110A US2012004153A1 US 20120004153 A1 US20120004153 A1 US 20120004153A1 US 82715110 A US82715110 A US 82715110A US 2012004153 A1 US2012004153 A1 US 2012004153A1
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United States
Prior art keywords
grease composition
composition
grease
thickener
copolymer
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Abandoned
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US12/827,151
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English (en)
Inventor
Samil Beret
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Chevron USA Inc
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Chevron USA Inc
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Application filed by Chevron USA Inc filed Critical Chevron USA Inc
Priority to US12/827,151 priority Critical patent/US20120004153A1/en
Assigned to CHEVRON U.S.A. INC. reassignment CHEVRON U.S.A. INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BERET, SAMIL
Priority to JP2013518389A priority patent/JP2013529722A/ja
Priority to CN201180032027.3A priority patent/CN102959064B/zh
Priority to AU2011276982A priority patent/AU2011276982A1/en
Priority to MX2012014546A priority patent/MX2012014546A/es
Priority to CA2801532A priority patent/CA2801532A1/en
Priority to KR1020137002571A priority patent/KR20130038357A/ko
Priority to PCT/US2011/034750 priority patent/WO2012005799A2/en
Priority to EP11803960.1A priority patent/EP2588583A4/en
Publication of US20120004153A1 publication Critical patent/US20120004153A1/en
Abandoned legal-status Critical Current

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    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06Mixtures of thickeners and additives
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    • C10M117/02Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
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    • C10M123/00Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential
    • C10M123/04Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential at least one of them being a macromolecular compound
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    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/021Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/1256Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids used as thickening agent
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C10M2207/1265Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic used as thickening agent
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    • C10M2207/10Carboxylix acids; Neutral salts thereof
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    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
    • C10M2207/1276Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic used as thickening agent
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    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C10M2207/1285Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
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    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
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    • C10N2010/00Metal present as such or in compounds
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2050/10Semi-solids; greasy

Definitions

  • the present invention relates to a lithium complex grease having improved thickener yield. More particularly, a more economical yet effective lithium complex grease is provided having a higher weight of base oil incorporated into the grease matrix.
  • Lithium complex greases have been known and manufactured for quite some time. Such greases can be made from any of a wide number of different base stocks of lubricating oil viscosity, and combination and mixtures of such stocks. The resulting greases are all marked by varying levels of desirable grease characteristics including dropping point, penetration, mechanical and/or shear stability, oxidation resistance, etc., all of which in combination are taken into account when describing the lubricating life of the grease.
  • Lithium complex greases comprising a lithium complex thickener and a lubricating base oil are well known.
  • a grease composition comprising a major amount of a base oil of lubricating viscosity, and a minor amount of a lithium complex thickener.
  • the grease composition can further comprise a copolymer, for example, of styrene and butadiene.
  • the composition will comprise less than 25 wt % of the thickener in combination with the copolymer.
  • the present grease composition exhibits a higher thickener yield, believed due to the combination of the lithium complex thickener and the copolymer, which in one embodiment is comprised of styrene and butadiene.
  • a grease composition has been discovered which provides good mechanical properties, but also good economics.
  • the thickener yield for the grease is much higher due to the presence of the copolymer of styrene and butadiene.
  • the thickener yield can be at least 25% higher, 35% higher or even 50% higher than that of a composition without the copolymer.
  • the lubricant base oil used in the present invention can be selected from Group I, II, III, IV, and V lubricant base oils, and mixtures thereof.
  • the lubricant base oils of the present invention include synthetic lubricant base oils, such as Fischer-Tropsch derived lubricant base oils, and mixtures of lubricant base oils that are not synthetics and synthetics.
  • the specifications for Lubricant Base Oils defined in the API Interchange Guidelines (API Publication 1509) using sulfur content, saturates content, and viscosity index, are shown below in Table I:
  • Facilities that make Group I lubricant base oils typically use solvents to extract the lower viscosity index (VI) components and increase the VI of the crude to the specifications desired. These solvents are typically phenol or furfural. Solvent extraction gives a product with less than 90% saturates and more than 300 ppm sulfur. The majority of the lubricant production in the world is in the Group I category.
  • VI viscosity index
  • Facilities that make Group II lubricant base oils typically employ hydroprocessing such as hydrocracking or severe hydrotreating to increase the VI of the crude oil to the specification value.
  • hydroprocessing typically increases the saturate content above 90 and reduces the sulfur below 300 ppm.
  • Approximately 10% of the lubricant base oil production in the world is in the Group II category, and about 30% of U.S. production is Group II.
  • VGO waxy vacuum gas oil
  • SOG waxy vacuum gas oil
  • Fischer-Tropsch wax is an ideal feed for a wax isomerization process to make Group III lubricant base oils. Only a small fraction of the world's lubricant supply is in the Group III category.
  • Group IV lubricant base oils are derived by oligomerization of normal alpha olefins and are called poly alpha olefin (PAO) lubricant base oils.
  • PAO poly alpha olefin
  • Group V lubricant base oils are all others. This group includes synthetic esters, silicon lubricants, halogenated lubricant base oils and lubricant base oils with VI values below 80. For purposes of this application, Group V lubricant base oils exclude synthetic esters and silicon lubricants. Group V lubricant base oils typically are prepared from petroleum by the same processes used to make Group I and II lubricant base oils, but under less severe conditions.
  • Synthetic lubricant base oils meet API Interchange Guidelines but are prepared by Fisher-Tropsch synthesis, ethylene oligomerization, normal alpha olefin oligomerization, or oligomerization of olefins boiling below C 10 .
  • the lithium complex thickener used in the present grease composition can be any known lithium complex thickener.
  • the lithium complex thickener can comprise a lithium soap derived from a fatty acid containing an epoxy group and/or ethylenic unsaturation and a dilithium salt derived from a straight chain dicarboxylic acid and/or, in one embodiment, a lithium salt derived from a hydroxy-substituted carboxylic acid such as salicylic acid.
  • the thickener can be a complex of a lithium soap of a C 12 to C 24 hydroxy fatty acid and a monolithium salt of boric acid and can include a lithium salt of a second hydroxy carboxylic acid such as salicylic acid.
  • the complex can comprise a lithium soap of a C 12 to C 24 hydroxy fatty acid thickener antioxidant comprising an alkali metal salt of hydroxy benzoic acid and a diozime compound.
  • the alkali metal salt of hydroxy benzoic acid include dilithium salicylate.
  • the complex can be a lithium soap which is a combination of a dilithium salt of a C 4 to C 12 dicarboxylic acid, e.g., dilithium azelate, a lithium soap of a 9-, 10- or 12-hydroxy C 12 to C 24 fatty acid, e.g., lithium 12-hydroxy stearate; and a lithium salt formed in-situ in the grease from a second hydroxy carboxylic acid wherein the —OH group is attached to a carbon atom not more than 6 carbons removed from the carboxyl group and wherein either of those groups may be attached to either aliphatic or aromatic portions of the materials.
  • a lithium soap which is a combination of a dilithium salt of a C 4 to C 12 dicarboxylic acid, e.g., dilithium azelate, a lithium soap of a 9-, 10- or 12-hydroxy C 12 to C 24 fatty acid, e.g., lithium 12-hydroxy stearate; and a lithium salt formed in-s
  • the lithium complex can comprise a combination of a complex lithium soap thickener, a lithium salt of a C 3 to C 14 hydroxycarboxylic acid and a thiadiazole.
  • the grease may also optionally and preferably contain additional antioxidants, preferably amine type or phenol type anti-oxidants, most preferably amine type antioxidants.
  • the lithium complex thickener is simply a lithium salt of a carboxylic acid, and in particular a hydroxycarboxylic acid, such as hydroxystearic acid.
  • a thickener can be prepared, for example, by reacting lithium hydroxyl monohydrate with the hydroxystearic acid.
  • the greases will comprise a major amount, e.g., greater than 50% by weight of the base oil, and a minor amount of the thickener and any other additives, i.e., less than 50% by weight.
  • the greases of the present invention may, of course, contain any of the other, typical grease additives such as rust inhibitors, barium dinonyl naphtheline fulfonate, order modifiers, tackiness agents, extreme pressure agents, water shedding agents, dyes, etc.
  • typical additives and their function are described in Modem Lubricating Greases by C. J. Boner, Scientific Publication (G.B.) Ltd. 1976.
  • a copolymer is of particular significance as an additive.
  • the copolymer can be a hydrocarbon based copolymer such as a copolymer of styrene and butadiene or ethylene and propylene.
  • the copolymer additive is a copolymer of styrene and butadiene. It has been found that use of a small amount of such a copolymer, e.g. from 2-6 weight percent, or from 2-5 weight percent, or in another embodiment, from 3-4 weight percent, in combination with a lithium complex thickener, results in a 25-50% increase in thickener yield.
  • Grease thickener yield defined as the weight of base oil incorporated into the grease matrix per unit of weight of thickener, is a key determinant of grease mechanical properties, such as penetration, shear stability and water resistance as well as formula cost.
  • the incorporation of the copolymer of styrene and butadiene with the lithium complex thickener permits the use of a greater amount of base oil, thereby raising the grease thickener yield, while maintaining good mechanical properties. The result is a more economical yet still effective grease.
  • Such copolymers of styrene and butadiene are commercially available.
  • V-211 is a copolymer of styrene and butadiene available from Functional Products, Inc. of Cincinnati, Ohio.
  • the copolymer is a white-yellow rubber powder which is quick dissolving.
  • These copolymers of styrene and butadiene can be used in conjunction with other polymers, but they must be present in the grease compositions of the present invention.
  • the yield relating to the amount of base oil one incorporates into the grease matrix while still realizing good mechanical properties, can increase by at least about 25 weight percent, about 35 weight percent, or at least about 50 weight percent.
  • Such grease compositions have been shown to exhibit worked penetration properties of at least about 290, at least about 300, and even at least about 310.
  • the compositions can be used in any automotive grease or industrial grease application.
  • the grease compositions can be used for wheel bearings, an automotive chassis or for lubricating gears.
  • 1-50 wt % of formula amount of base oil(s) were mixed in an open kettle at room temperature.
  • Formula amount of mono and di-acids, emulsifier(s) are added with water [at 50% base oil amount] and stirred while heating to 200° F.
  • lithium hydroxide is added slowly. Once the lithium hydroxide had been added, the mixture was heated to 400° F. It was held at 400° F. while stirring for 20 minutes.
  • the grease is then cooled to 175° F. while stirring.
  • performance additives e.g., rust inhibitor, extreme-pressure and anti-wear agents and polymers, tackifiers are added.
  • the grease penetration was adjusted by adding base oil slowly while stirring. When penetration range was achieved, the grease was cooled to room temperature and stored suitably.
  • Lubrizol 528C, EC5426A rust inhibitor
  • glycerin, Lubrizol 5200 extreme-pressure, anti-wear agents
  • Lubrizol 2002D functionalized olefin polymer
  • V-2II copolymer of styrene-butadiene
  • V-207 copolymer of ethylene and propylene
  • Runs A and B are considered as base cases using a PIB polymer or a functionalized olefin polymer. In both cases, the base oil amount used is 80% of formula amount. In runs C and D, when these polymers are replaced with styrene-butadiene or ethylene-propylene copolymers, the used base oil amount increases to 157 and 132% of formula amount respectively. With an increasing amount of base oil in the formula, thickener yield increases accordingly. Runs E, F, G, and H show increased thickener yield with styrene-butadiene copolymer use in conjunction with PIB and functionalized polymers.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
US12/827,151 2010-06-30 2010-06-30 Lithium Complex Grease with Improved Thickener Yield Abandoned US20120004153A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US12/827,151 US20120004153A1 (en) 2010-06-30 2010-06-30 Lithium Complex Grease with Improved Thickener Yield
EP11803960.1A EP2588583A4 (en) 2010-06-30 2011-05-02 LITHIUM COMPLEX LUBRICANT WITH INCREASED THICKENER YIELD
MX2012014546A MX2012014546A (es) 2010-06-30 2011-05-02 Grasa de complejo de litio con rendimiento espesante mejorado.
CN201180032027.3A CN102959064B (zh) 2010-06-30 2011-05-02 具有改善的增稠效率的锂复合润滑脂
AU2011276982A AU2011276982A1 (en) 2010-06-30 2011-05-02 Lithium complex grease with improved thickener yield
JP2013518389A JP2013529722A (ja) 2010-06-30 2011-05-02 増粘剤収率が向上したリチウム錯体グリース
CA2801532A CA2801532A1 (en) 2010-06-30 2011-05-02 Lithium complex grease with improved thickener yield
KR1020137002571A KR20130038357A (ko) 2010-06-30 2011-05-02 개선된 증점제 수율을 지니는 리튬 복합체 그리스
PCT/US2011/034750 WO2012005799A2 (en) 2010-06-30 2011-05-02 Lithium complex grease with improved thickener yield

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CN (1) CN102959064B (ko)
AU (1) AU2011276982A1 (ko)
CA (1) CA2801532A1 (ko)
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WO2015172846A1 (en) 2014-05-16 2015-11-19 Ab Nanol Technologies Oy Additive composition for lubricants
CN110643415A (zh) * 2019-10-22 2020-01-03 新疆福克油品股份有限公司 一种利用再生底线油的开式齿轮油组合物及其制备方法
WO2020139333A1 (en) * 2018-12-26 2020-07-02 Exxonmobil Research And Engineering Company Formulation approach to extend the high temperature performance of lithium complex greases
CN112877121A (zh) * 2019-11-29 2021-06-01 中石油克拉玛依石化有限责任公司 一种润滑脂及其制备方法和应用
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CN113862061B (zh) * 2021-10-09 2023-10-13 中国石油化工股份有限公司 一种润滑脂组合物、润滑脂及其制备方法和应用

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EP2695932A1 (en) 2012-08-08 2014-02-12 Ab Nanol Technologies Oy Grease composition
WO2014023707A1 (en) 2012-08-08 2014-02-13 Ab Nanol Technologies Oy Grease composition
US11781086B2 (en) * 2014-05-15 2023-10-10 Equus Uk Topco Ltd Lubricating oils and greases
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CN110643415A (zh) * 2019-10-22 2020-01-03 新疆福克油品股份有限公司 一种利用再生底线油的开式齿轮油组合物及其制备方法
CN112877121A (zh) * 2019-11-29 2021-06-01 中石油克拉玛依石化有限责任公司 一种润滑脂及其制备方法和应用

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AU2011276982A1 (en) 2013-02-07
CA2801532A1 (en) 2012-01-12
JP2013529722A (ja) 2013-07-22
KR20130038357A (ko) 2013-04-17
EP2588583A4 (en) 2014-01-08
EP2588583A2 (en) 2013-05-08
WO2012005799A2 (en) 2012-01-12
MX2012014546A (es) 2013-02-11

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