EP1051463A1 - Huiles pour turbines, resistant a la rouille, contenant des aminophosphates monobasiques et des acides dicarboxyliques - Google Patents

Huiles pour turbines, resistant a la rouille, contenant des aminophosphates monobasiques et des acides dicarboxyliques

Info

Publication number
EP1051463A1
EP1051463A1 EP98919702A EP98919702A EP1051463A1 EP 1051463 A1 EP1051463 A1 EP 1051463A1 EP 98919702 A EP98919702 A EP 98919702A EP 98919702 A EP98919702 A EP 98919702A EP 1051463 A1 EP1051463 A1 EP 1051463A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
acid
phosphate
amine
amine phosphate
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.)
Withdrawn
Application number
EP98919702A
Other languages
German (de)
English (en)
Other versions
EP1051463A4 (fr
Inventor
Max J. Wisotsky
Morton Beltzer
Thomas L. Ashcraft, Jr.
Paul J. Berlowitz
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Priority claimed from PCT/US1998/000264 external-priority patent/WO1999035216A1/fr
Publication of EP1051463A1 publication Critical patent/EP1051463A1/fr
Publication of EP1051463A4 publication Critical patent/EP1051463A4/fr
Withdrawn legal-status Critical Current

Links

Definitions

  • This invention relates to polyol ester-based turbo oils which exhibit rust inhibition by use of additives. More p-articul-arly it relates to turbo oils comprising esters of pentaerythritol with fatty acids as base stock, and containing a combination of additives to impart rust resistance.
  • Co ⁇ osion and rust are conditions which are extremely harmful to sophisticated, close tolerance gas turbine engines. They are especially harmful, over time, to engines operated under severe stress, atmosphere, duration and maneuver conditions. Exposure to the elements, chemicals, wide temperature swings, water and corrosive moisture environments put a strain on the engines which impact on their reliability, shorten the intervals between servicing and increase the likelihood of major overhaul and key parts replacement.
  • U.S. Patent 4,320,018 is directed to a synthetic turbo oil comprising a major portion of an aliphatic ester base containing a phenylnaphthylamine, a dialkyldiphenylamine, a polyhydroxyanthraquinone, a hydrocarbylphosphate ester .and a dialkyldisulf ⁇ de compound.
  • This oil is described as useful over a wide range of temperatures and as exhibiting good thermal and oxidative stability.
  • WO 94/10270 is directed to a corrosion inhibiting lubricant composition
  • a corrosion inhibiting lubricant composition comprising a synthetic ester base stock, at least one aromatic amine antioxidant, a neutral organic phosphate, saturated or unsaturated dicarboxylic acids, a straight or branched chain saturated or unsaturated monocarboxylic acid which is optionally sulfurized or an ester of such an acid, and a tri.azole compound.
  • This formulation is described as meeting the latest revision of Military Specification MIL-L-23699D of the United States Navy designated XAS-L-5724 (MIL-L-23699E) with respect to anti-corrosion properties.
  • Figure 1 presents a comparison of the MIL-L-23699E Ball Corrosion Test Performance of turbo oils containing amine phosphate and diacid alone and in combination at three different total additive concentration ranges. In all instances the combination exceeded each component's individual performance as well as what would have been expected from combining each component's individual contribution.
  • the present invention resides in a turbo oil composition exhibiting enhanced resistance to rust and corrosion and to a method for achieving that result in turbo oils.
  • the gas turbine lubricating oil of the present invention comprises a major proportion of a synthetic polyol ester based base stock and a minor proportion of an antirust/corrosion additive comprising an amine phosphate and a diacid.
  • an antirust/corrosion additive comprising an amine phosphate and a diacid.
  • Other, conventional additives such as extreme pressure, pour point reduction, oxidative stability, anti-foaming, improved viscosity index performance, anti-wear, hydrolytic stability agents, corrosion inhibitor additives and others may also be employed.
  • Lubricating oil additives are described generally in “Lubricants and Related Products” by Dieter Klamann, Verlag Chemie, Deerfield Beach, Florida, 1984.
  • Such improved antirust/anticorrosion performance in turbo lube oils is achieved by adding to the synthetic polyol ester based lubricating oil an additive package containing a mixture of amine phosphate and dicarboxylic acid.
  • the amine phosphate is used in an amount in the range 25 to 500 ppm, preferably 50 to 250 ppm, most preferably 75 to 150 ppm, while the diacid is used in an amount in the range 25 to 1000 ppm, preferably 50 to 400 ppm, most preferably 75 to 200 ppm, the combination of amine phosphate and diacid being used in a total amount in the range 50 to 1500 ppm, preferably 100 to 400 ppm, most preferably 100 to 300 ppm.
  • a turbo lube having unexpectedly superior rust resistance and anticorrosion performance properties comprising a major portion of a synthetic polyol ester base oil and a minor portion of an antirust - anticorrosion additive package consisting essentially of a mixture of monobasic amine phosphate and dicarboxylic acid.
  • the synthetic polyol ester base oil is formed by the esterification of aliphatic polyols with carboxylic acids.
  • the aliphatic polyol reactant contains from 4 to 15 carbon atoms and has from 2 to 8 esterifiable hydroxyl groups.
  • Examples of polyols are trimethylolpropane, pentaerythritol, dipentaerythritol, neopentyl glycol, tripentaerythritol and mixtures thereof.
  • the carboxylic acid reactant used to produce the synthetic polyol ester base oil is selected from aliphatic monocarboxylic acids or a mixture of aliphatic monocarboxylic acids and aliphatic dicarboxylic acids.
  • the carboxylic acid contains from 4 to 12 carbon atoms and includes the straight and branched chain aliphatic acids, and mixtures of monocarboxylic acids may be used.
  • the preferred polyol ester base oil is one prepared from technical pentaerythritol and a mixture of C 4 - 2 carboxylic acids.
  • Technical penta- erythritol is a mixture which includes about 85 to 92% monopentaerythritol and 8 to 15% dipentaerythritol.
  • a typical commercial technical pentaerythritol contains about 88% monopentaerythritol having the formula
  • the technical pentaerythritol may also contain some tri and terra pentaerythritol that is normally formed as by-products during the manufacture of technical pentaerythritol.
  • esters from alcohols and carboxylic acids can be accomplished using conventional methods and techniques known and familiar to those skilled in the art.
  • technical pentaerythritol is heated with the desired carboxylic acid mixture optionally in the presence of a catalyst.
  • a slight excess of acid is employed to force the reaction to completion. Water is removed during the reaction and any excess acid is then stripped from the reaction mixture.
  • the esters of technical pentaerythritol may be used without further purification or may be further purified using conventional techniques such as distillation.
  • the term "technical pentaerythritol ester” is understood as meaning the polyol ester base oil prepared from technical pentaerythritol and a mixture of C 4 -C ⁇ 2 carboxylic acids.
  • polyol ester base stock is added a minor portion of an additive mixture comprising one or more amine phosphates and one or more dicarboxylic acids.
  • the monobasic amine phosphate(s) used include mono basic hydro- carbyl .amine salts of acid phosphates and preferably are those of the formula:
  • R and R 1 are the same or different .and are C 2 to C 24 linear or branched chain alkyl
  • Ri is H or C 4 to C 20 linear or branched chain alkyl or R ⁇ -aryl-Rs where R t and R 5 are the same or different and are H or -C 16 alkyl
  • R 2 is C -C 20 linear or branched chain alkyl or Rj-aryl-Rs where j and R 5 are the same or different and are H or C ⁇ -C ⁇ 6 alkyl
  • R 3 is C -C 2 o linear or branched chain alkyl or Rj-aryl-Rs where R 4 and R 5 are the same or different and are H or C ⁇ -C 16 alkyl
  • the preferred monobasic amino phosphates are those wherein R is straight or branched chain C 6 -C ⁇ 6 alkyl.
  • the monobasic amine phosphates are used in an amount in the range 25 to 500 ppm (based on polyol ester base stock) preferably 50 to 250 ppm, most preferably 75 to 150 ppm.
  • the dicarboxylic acid is a C ⁇ 0 to C 0 total carbon numbers dicarboxylic acid, or mixture thereof, preferably a C 2 to C 40 dicarboxylic acid, or mixture thereof, most preferably a C 6 dicarboxylic acid or mixture thereof.
  • the dicarboxylic acids can be any n-alkyl, branched alkyl, aryl, or alkyl substituted aryl dicarboxylic acid or mixture thereof having a total number of carbons falling within the above recited ranges.
  • Preferred dicarboxylic acids are selected from the group consisting of the commercially available di-oleic acids known as "dimer acids", sebacic acid, azelaic acid and mixtures thereof.
  • the dicarboxylic acids are used in an amount in the range 25 to 1000 ppm (based on polyol ester base stock) preferably 50 to 400 ppm, most preferably 75 to 200 ppm.
  • the mixture of amine phosphate and dicarboxylic acid is used in an amount in the range 50 to 1500 ppm (based in polyol ester base stock), preferably 100 to 400 ppm, most preferably 100 to 300 ppm.
  • the amine phosphates and the decarboxylic acids are used in a ratio in the range 5: 1 to 1 :5, preferably 2: 1 to 1:2.
  • the synthetic polyol ester - rust inhibiting additive containing turbo oil may also contain one or more of the following classes of additives: anti- oxidants, antiwear agents, extreme pressure additives, antifoamants, detergents, hydrolytic stabilizers and metal deactivators. Total amounts of such other additives can be in the range .5 to 15 wt%, preferably 2 to 10 wt%, most preferably 3 to 8 wt%.
  • Antioxidants which can be used include aryl amines, e.g., phenyl- naphthylamines and dialkyl diphenyl amines and mixtures thereof, hindered phenols, phenothiazines, and their derivatives.
  • the antioxidants are typically used in an amount in the range 1 to 5 ⁇ %.
  • Antiwear/extreme pressure additives include hydrocarbyl phosphate esters, particularly trihydrocarbyl phosphate esters in which the hydrocarbyl radical is an aryl or alkaryl radical or mixture thereof.
  • Particular antiwear/ extreme pressure additives include tricresyl phosphate, triaryl phosphate and mixtures thereof.
  • Other or additional anti wear/extreme pressure additives may also be used.
  • the antiwear/extreme pressure additives are typically used in an amount in the range 0 to 4 wt%, preferably 1 to 3 wt%.
  • Such known corrosion inhibitors include the various triazols.
  • tolyltriazol 1,2,4 benzene triazol, 1,2,3 benzene triazol, carboxy benzotriazole, alkylated benzotri.azol.
  • the standard corrosion inhibitor additive can be used in an amount in the range 0.02 to .5 wt%, preferably .05 to .25 wt%.
  • other additives can also be employed including hydrolytic stabilizers pour point depressants, anti foaming agents, viscosity and viscosity index improver, etc.
  • turbo oils of the present invention meet or exceed the requirements set out by the United States Navy in MIL-L-23699E for corrosion inhibition type 5 cSt turbo oils.
  • Phosphate alone a monobasic phosphate amine where the alkyl substituents on the phosphate were primarily ethyl hexyl or octyl, but also contained some chains form C 6 to C ⁇ 6 in length. (Ortholeum 535).
  • Diacid alone Commercial dimerized oleic acids or Sebacic acid. The dimerized oleic acids contain many specific chemicals including cyclic and aromatic structures and which have a small amount ( ⁇ 3%) of undimerized acids and a small amount 2-10% of trimerized acids.
  • Figure 1 shows the total percentage of balls passing over all experiments for the three corrosion inhibitor systems over the concentration ranges shown. In all three cases there was not a statistically significant trend over the three ranges shown at the 95% confidence level. Neither the phosphate or diacid ingredient used alone provided reliable protection from rust with fewer than half of the tests passing the minimum 75% specification. However, the combination of the two ingredients, used at the same total additive treat rate exhibited a synergistic effect, and increased the likelihood of a pass result greatly. The results are shown below in Table 1.
  • Example 2 a series of turbo oils was used similar to those in Example 1, with the following differences.
  • the phosphate amines used were the commercial products Vanlube-692 and Vanlube-672 which are mixed methyl and butyl mono and di-basic phosphates.
  • the Vanlube-692 is primarily butyl, while the Vanlube-672 has more methyl groups.

Landscapes

  • Lubricants (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

La présente invention concerne une huile pour turbine présentant des propriétés accrues d'inhibition de la rouille, que l'on produit en mélangeant des quantités mineures d'aminophosphates monobasiques et d'acides dicarboxyliques à l'huile de turbine de base. L'utilisation dudit mélange permet de donner à l'huile une résistance à la rouille étonnamment supérieure en comparaison de ce qui est obtenu lorsque les composants sont utilisés séparément. L'huile pour turbine à laquelle l'additif confère ledit comportement est, de préférence, une huile à base d'esters de polyols.
EP98919702A 1998-01-09 1998-01-09 Huiles pour turbines, resistant a la rouille, contenant des aminophosphates monobasiques et des acides dicarboxyliques Withdrawn EP1051463A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1998/000264 WO1999035216A1 (fr) 1996-02-09 1998-01-09 Huiles pour turbines, resistant a la rouille, contenant des aminophosphates monobasiques et des acides dicarboxyliques

Publications (2)

Publication Number Publication Date
EP1051463A1 true EP1051463A1 (fr) 2000-11-15
EP1051463A4 EP1051463A4 (fr) 2002-01-30

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP98919702A Withdrawn EP1051463A4 (fr) 1998-01-09 1998-01-09 Huiles pour turbines, resistant a la rouille, contenant des aminophosphates monobasiques et des acides dicarboxyliques

Country Status (3)

Country Link
EP (1) EP1051463A4 (fr)
JP (1) JP2002500261A (fr)
CA (1) CA2311385A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2773032A (en) * 1954-05-13 1956-12-04 Gulf Oil Corp Rust inhibiting lubricating oil compositions
US3720612A (en) * 1969-06-25 1973-03-13 Exxon Research Engineering Co Synthetic ester lubricating oil compositions
US5391307A (en) * 1989-07-07 1995-02-21 Tonen Corp. Lubricating oil composition
US5587355A (en) * 1995-12-22 1996-12-24 Exxon Research And Engineering Company High load-carrying turbo oils containing amine phosphate and thiophene carboxylic acid derivatives
US5681506A (en) * 1992-10-30 1997-10-28 Castrol Limited Corrosion inhibiting lubricant composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2773032A (en) * 1954-05-13 1956-12-04 Gulf Oil Corp Rust inhibiting lubricating oil compositions
US3720612A (en) * 1969-06-25 1973-03-13 Exxon Research Engineering Co Synthetic ester lubricating oil compositions
US5391307A (en) * 1989-07-07 1995-02-21 Tonen Corp. Lubricating oil composition
US5681506A (en) * 1992-10-30 1997-10-28 Castrol Limited Corrosion inhibiting lubricant composition
US5587355A (en) * 1995-12-22 1996-12-24 Exxon Research And Engineering Company High load-carrying turbo oils containing amine phosphate and thiophene carboxylic acid derivatives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9935216A1 *

Also Published As

Publication number Publication date
CA2311385A1 (fr) 1999-07-15
EP1051463A4 (fr) 2002-01-30
JP2002500261A (ja) 2002-01-08

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