EP0597712A1 - Schmierfettzusammensetzungen - Google Patents

Schmierfettzusammensetzungen Download PDF

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Publication number
EP0597712A1
EP0597712A1 EP93309028A EP93309028A EP0597712A1 EP 0597712 A1 EP0597712 A1 EP 0597712A1 EP 93309028 A EP93309028 A EP 93309028A EP 93309028 A EP93309028 A EP 93309028A EP 0597712 A1 EP0597712 A1 EP 0597712A1
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EP
European Patent Office
Prior art keywords
grease
boron
acid
phosphorus
phospholipid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP93309028A
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English (en)
French (fr)
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EP0597712B1 (de
Inventor
James Noel Vinci
Carmen Vincent Luciani
Syed Qalab Abbas Rizvi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lubrizol Corp
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Lubrizol Corp
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Publication of EP0597712A1 publication Critical patent/EP0597712A1/de
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    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/123Reaction products obtained by phosphorus or phosphorus-containing compounds, e.g. P x S x with organic compounds
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    • C10M117/04Lubricating 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 containing hydroxy groups
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Definitions

  • Metal soap thickened greases have provided exemplary performance. Performance of greases may be enhanced by incorporating therein various types of additives.
  • A.C. Witte, Lubrication , Vol. 77, No. 1, Texaco Inc., White Plains, N.Y., (1991), pp 2-3 is a discussion of additives for greases, including antioxidants, rust and corrosion inhibitors, EP (extreme pressure) additives, antiwear additives, lubricity agents, tackifiers and fillers.
  • Dropping point is one measure of the thermal stability of a grease.
  • One way to increase the dropping point of base greases is to convert a simple metal soap grease to a complex grease by incorporating therein certain acids, typically carboxylic acids such as acetic acid, alpha-omega-dicarboxylic acids and certain aromatic acids. This additional step necessarily consumes considerable time resulting in reduced production.
  • Doner et al in a series of US Patents, specifically, US Patents 5,084,194 5,068,045 4,961,868 4,828,734 4,828,732 4,781,850 4,780,227 4,743,386 4,655,948 4,600,517 4,582,617 teaches increased thickening of metal salt thickened base greases is obtained by employing certain boron-containing compounds.
  • Other additives contemplated by Doner et al for use with boron-containing compounds are phosphorus- and sulfur-containing materials, particularly zinc dithiophosphates.
  • an improved grease composition comprising a major amount of an oil based simple metal soap thickened base grease and a minor amount of at least one phosphorus and boron containing composition, said phosphorus and boron containing composition prepared by reacting a combination of (A) at least one boron compound and (B) at least one phospholipid.
  • the phosphorus and boron containing composition is present in amounts sufficient to improve the extreme pressure, antiwear and lubricity properties of the base grease.
  • the phosphorus and boron containing composition is present in amounts sufficient to increase the dropping point of the base grease, as determined by ASTM procedure D-2265, by at least 20°C.
  • the greases of this invention are useful for lubricating, sealing and protecting mechanical components such as gears, axles, bearings, shafts, hinges and the like.
  • mechanical components are found in automobiles, trucks, bicycles, steel mills, mining equipment, railway equipment including rolling stock, aircraft, boats, construction equipment and numerous other types of industrial and consumer machinery.
  • greases must provide, to varying degrees, lubricity, extreme pressure and antiwear properties and depending upon the application, acceptable thermal stability (heat resistance).
  • Extreme pressure performance of a grease permits the grease to perform under high load conditions, particularly, under boundary conditions.
  • a base grease without extreme pressure property improving additives, is unable to provide acceptable extreme pressure properties.
  • a lubricating grease should provide protection against undesirable wear of the lubricated parts.
  • Chemical additives are frequently used to enhance antiwear performance of a base grease.
  • Oil-based greases inherently provide a certain degree of lubricity. Lubricity properties of a base grease may be enhanced by incorporating therein certain lubricity improving additives.
  • Heat resistance of greases is measured in a number of ways.
  • One measure of heat resistance is the dropping point.
  • Grease typically does not have a sharp melting point but, rather, softens until it no longer functions as a thickened lubricant.
  • ASTM D-2265 The American Society for Testing and Materials (1916 Race Street, Philadelphia, Pennsylvania) has set forth a test procedure, ASTM D-2265, which provides a means for measuring the dropping point of greases.
  • the dropping point of a grease is the temperature at which the grease passes from a semisolid to a liquid state under the conditions of the test.
  • the dropping point is the temperature at which the first drop of material falls from the test cup employed in the apparatus used in ASTM procedure D-2265.
  • Complex metal soap greases provide increased dropping point, but have a number of significant drawbacks.
  • Complex thickeners have incorporated therein, in addition to a fatty acid component, a non-fatty acid, e.g., benzoic, organic dibasic acids, etc. component.
  • the formation of the complex grease typically involves the additional step of reaction of the non-fatty acid with the simple metal soap, and requires extended heating periods, sometimes several times that required to prepare a simple metal soap thickened grease. Accordingly, it is desirable to provide a means for preparing a simple metal soap thickened grease composition having dropping points approaching or even exceeding those possessed by complex greases.
  • the grease compositions of this invention display improved extreme pressure properties when compared to the base grease. In another embodiment, the grease compositions display improved antiwear properties and in a still further embodiment, they display improved lubricity.
  • Particularly useful acids are the hydroxy-substituted fatty acids such as hydroxy stearic acid wherein one or more hydroxy groups may be located at positions internal to the carbon chain, such as 12-hydroxy-, 14-hydroxy- etc. stearic acids.
  • Preferred metals are lithium, sodium, calcium, magnesium, barium and aluminum. Especially preferred are lithium, sodium and calcium; lithium is particularly preferred.
  • the grease compositions of this invention comprise compositions prepared by reacting a combination of (A) a boron compound and (B) a phospholipid.
  • the boron compounds include boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boron acids such as boronic acid (i.e., alkyl-B(OH)2 or aryl-B(OH)2), including methyl boronic acid, phenyl-boronic acid, cyclohexyl boronic acid, p-heptylphenyl boronic acid and dodecyl boronic acid, boric acid (i.e., H3BO3), tetraboric acid (i.e., H2B4O7), metaboric acid (i.e., HBO2), boron anhydrides, boron amides and various esters of such boron acids.
  • Ethylene polyamines such as some of those mentioned above, are useful. Such polyamines are described in detail under the heading Ethylene Amines in Kirk Othmer's "Encyclopedia of Chemical Technology", 2d Edition, Vol. 7, pages 22-37, Interscience Publishers, New York (1965). Such polyamines are most conveniently prepared by the reaction of ethylene dichloride with ammonia or by reaction of an ethylene imine with a ring opening reagent such as water, ammonia, etc. These reactions result in the production of a complex mixture of polyalkylenepolyamines including cyclic condensation products such as the aforedescribed piperazines. Ethylene polyamine mixtures are useful.
  • the combination which forms the compositions employed in the grease compositions of the present invention, may also include a carboxylic ester.
  • carboxylic ester These compounds are prepared by reacting at least one of the above described hydrocarbyl-substituted carboxylic acylating agents with at least one organic hydroxy compound.
  • the ester dispersant is prepared by reacting the acylating agent with the above-described hydroxyamine. The carboxylic ester may be further reacted with any of the above-described amines.
  • the combination may also include a Mannich product.
  • Mannich products are formed by the reaction of at least one aldehyde, at least one of the above described amine and at least one hydroxyaromatic compound.
  • the reaction may occur from room temperature to 225°C, usually from 50° to about 200°C (75°C-125°C most preferred), with the amounts of the reagents being such that the molar ratio of hydroxyaromatic compound to aldehyde to amine is in the range from about (1:1:1) to about (1:3:3).
  • Mannich products are described in the following patents: U.S. Patent 3,980,569; U.S. Patent 3,877,899; and U.S. Patent 4,454,059 (herein incorporated by reference for their disclosure to Mannich products).
  • these block copolymers for reasons of oxidative stability, contain no more than about 5 percent and preferably no more than about 0.5 percent residual olefinic unsaturation on the basis of the total number of carbon-to-carbon covalent linkages within the average molecule. Such unsaturation can be measured by a number of means well known to those of skill in the art, such as infrared, NMR, etc. Most preferably, these copolymers contain no discernible unsaturation, as determined by the aforementioned analytical techniques.
  • the combination may also include neutral, or basic metal salts.
  • the salts include alkali, alkaline earth or transition metal salts.
  • metals of the salts include sodium, potassium, magnesium, calcium, barium, titanium, manganese, cobalt, nickel, copper, zinc, preferably sodium, potassium, calcium, magnesium, copper and zinc, more preferably zinc or magnesium cation, most preferably zinc.
  • the boron and phosphorus containing composition may be prepared by reacting (A) a boron compound with (B) a phospholipid to form an intermediate reaction product. The intermediate product is then reacted with one of the above-described (C) through (H).
  • the acylated nitrogen-containing compound contains a substituent with no more than an average of about 40 carbon atoms, it must be understood that the acylated nitrogen-containing compound does not have to have a substituent with an average number of carbon atoms.
  • the substituent may have a specific single number of carbon atoms, e.g. 18 carbon atoms.
  • the substituent of the acylated nitrogen compound has no more than an average of about 30 carbon atoms. The average number of carbon atoms is based on number average molecular weight.
  • the reactions usually occurs at a temperature from about 60°C to about 200°C, about 90°C to about 150°C.
  • the reaction is typically accomplished in about 0.5 to about 10 hours, preferably about 2 to about 6, more preferably 4.
  • An inert organic diluent such as benzene, toluene, xylene, or mineral oil may be used.
  • the boron compound (A) and phospholipid (B) are reacted at an atomic proportion of boron to phosphorus of about (1:1) up to about (6:1), preferably about (2:1) up to about (4:1), more preferably about (3:1).
  • the boron compound (A) is reacted with the mixture of the phospholipid (B) and one or more of (C) through (H) in an amount of one atomic proportion of boron to equivalent of the mixture from about (1:1) to about (6:1), preferably about (2:1) to about (4:1), more preferably (3:1).
  • the equivalents of the mixture are based on the combined equivalents of phospholipid (B) based on phosphorus and equivalents of (C) through (H).
  • the equivalents of (C) through (G) are determined by the number of nitrogen atoms or hydroxyl groups.
  • the equivalents of (H) are based on base number.
  • Base number is the amount of hydrochloric acid expressed in terms of equivalent milligrams of potassium hydroxide per gram of sample, required to titrate a sample to a defined endpoint.
  • a reaction vessel is charged with a mixture of 2600 parts (1.66 equivalent) of lecithin and 600 parts of toluene. Boric acid (307 parts, 4.97 moles) is added to the mixture over 0.5 hour at 40°-60°C under nitrogen atmosphere. The reaction mixture is heated to reflux (130°C) while removing 180 parts of water over 4 hours. A vacuum is applied (20 millimeters of mercury) and toluene solvent removed while raising the reaction temperature to 110°C. The residue is filtered through diatomaceous earth. The filtrate contains 1.78% P (1.88% theory), 0.71% N (0.72% theory) and 2.05% B (2.10% theory).
  • a reaction vessel is charged with a mixture of 800 parts (0.5 equivalent) corn lecithin (available as Corn Goodness UB from ADM Ross and Rowe), 150 parts toluene and 141 parts of a 100 neutral mineral oil. Boric acid (104 parts (1.68 moles)) is added over 0.5 hour at 40°-60°C to the mixture. The reaction mixture is heated to reflux (125°-127°C) for 4 hours while removing 63 parts distillate.
  • corn lecithin available as Corn Goodness UB from ADM Ross and Rowe
  • Boric acid 104 parts (1.68 moles)
  • the reaction mixture is heated to reflux (125°-127°C) for 4 hours while removing 63 parts distillate.
  • a vacuum is applied (20 millimeters of mercury) and toluene solvent removed while raising the temperature to 120°C.
  • the residue is filtered through diatomaceous earth.
  • the filtrate contains 1.55% P, 0.62% N, 1.1% B and 15% oil.
  • a reaction vessel is charged with 1562 parts (1 equivalent) of a lecithin of Example 1, 200 parts toluene and 560 parts (1 equivalent) of a 40% oil solution of a succinimide, which has 2.5% nitrogen and a total base number of 65 and is prepared by reacting a polyamine with a polyalkene succinic anhydride wherein the polyalkene has a number average molecular weight of approximately 1000.
  • the mixture is heated to 50°C with nitrogen sparging at 1 scfh where 247 parts (4 moles) of boric acid are added to the mixture over 0.25 hour.
  • the mixture is heated to 120°C where 25 parts of water are removed over 1.5 hours.
  • the reaction is held at 120°-125°C for 4.5 hours while 115 milliliters of distillate are obtained.
  • the product is a clear, bright, deep red color.
  • the mixture is vacuum stripped to 80°C and 25 millimeters of mercury.
  • the residue is a product which has 1.3% phosphorus (1.37% theory), 1.07% nitrogen (1.14% theory), 1.86% boron (1.95% theory), and 15% 100 neutral mineral oil.
  • a reaction vessel is charged with 1568 parts (1 equivalent) of the lecithin of Example 1 and 200 parts of textile spirits.
  • the mixture is heated to 60°C where 525 parts (3 equivalents) of a borated sodium sulfonate prepared by reacting 1 equivalent of boron with 1 equivalent of a sodium overbased alkylated benzene sulfonate having a metal ratio of 20 and containing 36% diluent (including 100 neutral mineral and unreacted alkylated benzene sulfonate) is added to the mixture.
  • the reaction temperature is maintained at 60-70°C for 3 hours.
  • the reaction mixture is vacuum stripped to 80°C and 25 millimeters of mercury.
  • the product contains 1.47% phosphorus (1.49% theory), 3.51% sodium (2.87% theory), 1.52% boron (1.57% theory) and a specific gravity of 1.04.
  • a reaction vessel is charged with 784 parts (0.5 equivalent) of the lecithin of Example 1, 124 parts (2.1 equivalents) of boric acid and 449 parts (1 equivalent) of a calcium overbased tall oil fatty acid having a metal ratio of 2, 58% 100 neutral mineral oil and a base number of 125.
  • the mixture is heated to 90°C and held for 1 hour.
  • the reaction mixture is heated to 120°C under 140 millimeters of mercury and the reaction is maintained at 120°C for 1 hour.
  • the reaction mixture is cooled to 60°C and vacuum stripped at 60°C and 40 millimeters of mercury.
  • the residue has 1.12% phosphorus (1.19% theory), 1.63% calcium (1.60% theory), 1.97% boron (1.79% theory) and specific gravity of 1.02.
  • reaction products of a boron compound and a phospholipid as described herein are useful as additives for lubricants, including greases, in which they can function as antiwear, extreme pressure and/or friction modifying agents. Additionally, when employed in sufficient amounts, they increase the dropping point of oil based, simple metal soap thickened, base greases. They can be employed in such greases based on diverse oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.
  • the borated phospholipid may be incorporated into the base grease directly or as a component of additive concentrates, by itself or in combination with any other known additives for oil based simple metal soap thickened base greases which include, but are not limited to, antioxidants, anti-wear agents, extreme pressure agents, friction modifiers, anti-rust agents, corrosion inhibitors, and dyes.
  • Viscosity improvers and pour point depressants are sometimes employed to improve the properties of the oil from which the base grease is derived.
  • Viscosity improvers include but are not limited to polyisobutenes, polymethyacrylate acid esters, polyacrylate acid esters, diene polymers, polyalkyl styrenes, alkenyl aryl conjugated diene copolymers, polyolefins and multifunctional viscosity improvers.
  • pour point of the oil component of the base grease may be an important consideration.
  • Pour point depressants are sometimes included in the lubricating oils described herein. See for example, page 8 of "Lubricant Additives" by C. V. Smalheer and R. Kennedy Smith (Lesius-Hiles Company Publishers, Cleveland, Ohio, 1967).
  • the boron- and phosphorus-containing compounds which provide increased dropping points of metal soap thickened greases are used in minor amounts effective to increase the dropping point of the base grease by at least 20°C.
  • Preferred minimum amounts of boron and phosphorus containing compound to employ depend to some extent upon the additive, for example, some higher molecular weight compounds may be needed in somewhat larger amounts to obtain the desired effect.
  • the minimum amount of boron and phosphorus containing additive consistent with attaining the desired effect such as extreme pressure, antiwear, etc. or dropping point elevation of at least 20°C.
  • the boron- and phosphorus- containing composition may be present during grease formation, i.e., during formation of the soap thickener in the oil of lubricating viscosity, or may be added after the base grease has been prepared. In many cases it is preferred to add the boron and phosphorus containing composition to the preformed base grease.
  • additives may be incorporated into the base grease to improve performance of the grease as a lubricant.
  • Such other additives including corrosion inhibitors, antioxidants, extreme pressure additives and others useful for improving specific performance characteristics of a base grease, are well-known and will readily occur to those skilled in the art.
  • a lithium 12-hydroxystearate thickened base grease shows a dropping point of 206°C. This is a typical simple lithium salt thickened base grease.
  • a base grease is prepared by mixing 92 parts of the base grease of Example A and 8 parts of mineral oil having a kinematic viscosity of 800 Saybolt Universal Seconds (172.6 centistokes) measured at 100°F (37.8°C). The dropping point of this grease is 204°C.
  • a grease composition is prepared by blending 4% by weight of the product of Example 1 into the grease composition of Example B. This grease has a dropping point of 277°C.
  • a grease composition is prepared by blending 2% by weight of the product of Example 1 into the base grease of Example B. This grease composition has a dropping point of 267°C.
  • a grease composition is prepared by adding to the base grease of Example B 1% by weight of a composition prepared according to the procedure of Example 1 and 1% by weight of a product obtained by reacting 1000 parts of O,O' (di)-methylamyl dithiophosphoric acid prepared by reacting about 4 moles methylamyl alcohol with 1 mole of P2S5 with 183 parts of propylene oxide, reacting the product obtained thereby with 144 parts of P2O5 and neutralizing the acidic product thereby with 584 parts of a tertiary alkyl primary amine having from 11-14 carbon atoms in the tertiary alkyl group (Primene 81-R, Rohm and Haas).
  • This grease composition has a dropping point of 272°C.
  • a grease composition is prepared by adding to the base grease of Example B 1% by weight of a sulfurized isobutylene containing about 45% sulfur and 2% by weight of the product of Example 1. The dropping point of this grease composition is 228.5°C.
  • Example F To the grease composition of Example F is added 0.1% by weight of Reomet 39, an oil-soluble benzotriazole derivative marketed by Ciba-Geigy. The dropping point of this grease composition is 231°C.
  • Examples H-M are comparative Examples employing a phophorus containing additive that is free of boron.
  • Grease compositions are prepared by blending into a lithium 12-hydroxystearate base grease having a dropping point of 207°C the indicated percentages of a mixed phosphoric acid salt prepared by reacting 3 moles (based on OH) of CO1418 alcohol (a primary alcohol containing a mixture of C14, C16 and C18 carbon chains) with 1 mole P2O5 then reacting the acidic product obtained with 1.13 equivalents of Primene 81-R per equivalent of strong acid.
  • Grease compositions are prepared by blending into a lithium 12-hydroxystearate base grease the indicated percentages of dibutylhydrogen phosphite ((Butyl-0)2PHO).
  • a grease composition is prepared by blending into the grease of Example B, 4% by weight of the lecithin described in Example 1. The dropping point of this grease composition is 194°C.
  • Examples C and G are repeated replacing the lithium 12-hydroxy stearate base grease with a sodium tallowate thickened base grease.

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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)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)
  • Edible Oils And Fats (AREA)
EP93309028A 1992-11-12 1993-11-11 Schmierfettzusammensetzungen Expired - Lifetime EP0597712B1 (de)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3284409A (en) * 1965-06-22 1966-11-08 Lubrizol Corp Substituted succinic acid-boron-alkylene amine phosphatide derived additive and lubricating oil containing same
JPS57108196A (en) * 1980-12-17 1982-07-06 Tokai Rika Co Ltd Lubricating grease
US4522629A (en) * 1983-09-23 1985-06-11 Mobil Oil Corporation Borated phosphonates as lubricant and fuel additives
EP0151859A2 (de) * 1984-02-06 1985-08-21 Mobil Oil Corporation Fettzusammensetzung
US4784780A (en) * 1987-09-18 1988-11-15 Mobil Oil Corporation Lubricant additive comprising mixed hydroxyester or diol/phosphorodithioate-derived borates
WO1992018586A1 (en) * 1991-04-18 1992-10-29 The Lubrizol Corporation Reaction products of a boron compound and a phospholipid, and lubricants and aqueous fluids containing same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3284409A (en) * 1965-06-22 1966-11-08 Lubrizol Corp Substituted succinic acid-boron-alkylene amine phosphatide derived additive and lubricating oil containing same
JPS57108196A (en) * 1980-12-17 1982-07-06 Tokai Rika Co Ltd Lubricating grease
US4522629A (en) * 1983-09-23 1985-06-11 Mobil Oil Corporation Borated phosphonates as lubricant and fuel additives
EP0151859A2 (de) * 1984-02-06 1985-08-21 Mobil Oil Corporation Fettzusammensetzung
US4784780A (en) * 1987-09-18 1988-11-15 Mobil Oil Corporation Lubricant additive comprising mixed hydroxyester or diol/phosphorodithioate-derived borates
WO1992018586A1 (en) * 1991-04-18 1992-10-29 The Lubrizol Corporation Reaction products of a boron compound and a phospholipid, and lubricants and aqueous fluids containing same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8232, Derwent World Patents Index; AN 82-67226E[32] *

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CA2102650A1 (en) 1994-05-13
AU5043693A (en) 1994-05-26
EP0597712B1 (de) 1998-01-21
DE69316542D1 (de) 1998-02-26
AU667137B2 (en) 1996-03-07
CA2102650C (en) 2003-09-09
ATE162545T1 (de) 1998-02-15
MX9306991A (es) 1995-01-31
ES2113496T3 (es) 1998-05-01
DE69316542T2 (de) 1998-09-10

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