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WO1993007240A1 - Procede de production de fluides ayant une stabilite thermique amelioree - Google Patents

Procede de production de fluides ayant une stabilite thermique amelioree Download PDF

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Publication number
WO1993007240A1
WO1993007240A1 PCT/US1992/008315 US9208315W WO9307240A1 WO 1993007240 A1 WO1993007240 A1 WO 1993007240A1 US 9208315 W US9208315 W US 9208315W WO 9307240 A1 WO9307240 A1 WO 9307240A1
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Prior art keywords
ester
lubricant
carbon atoms
acid
thermal stability
Prior art date
Application number
PCT/US1992/008315
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English (en)
Inventor
Richard Henry Schlosberg
James Zielinski
John Wand Chu
Gerald Dennis Dupre
Theresa Kathleen Natishan
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Exxon Chemical Patents Inc.
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Application filed by Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Publication of WO1993007240A1 publication Critical patent/WO1993007240A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating 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
    • C10M169/04—Mixtures of base-materials and additives
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/36—Esters of polycarboxylic acids
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/284—Esters of aromatic monocarboxylic acids
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/285—Esters of aromatic polycarboxylic acids
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/285—Esters of aromatic polycarboxylic acids
    • C10M2207/2855—Esters of aromatic polycarboxylic acids used as base material
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/28—Esters
    • C10M2207/286—Esters of polymerised unsaturated acids
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
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    • C10M2215/066—Arylene diamines
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    • C10M2215/068—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings having amino groups bound to polycyclic aromatic ring systems, i.e. systems with three or more condensed rings

Definitions

  • the present invention relates to a process for improving the thermal stability of fluids, particularly ester-based lubricants.
  • esters as lubricating oils in such applications as fiber lubricants, aviation turbo oils, automotive oils, metal working fluids, gear oils, refrigerant oils and the like is well known. These esters vary from simple esters derived from mono-, di- or polycarboxylic acids, mono alcohols or polyols to complex esters such as derived from half esters or ethers of glycols and di or polycarboxylic acids.
  • Lubricants for use in aircraft and in gas turbines require special properties which are not possessed by conventional lubricants. Thus, they must possess a high viscosity index in order to provide adequate lubrication over a wide range of temperatures. They must have a low pour point in order that they may function at low temperatures and high flash points to avoid risk of fire at high temperature operation and minimize loss of lubricant by evaporation.
  • Lubricating fluids therefore, need to be both effective and stable at ever increasing temperatures.
  • Synthetic ester lubricants such as described above are not essentially pure but contain trace to minor amounts (less than 10% by weight) of difficult to remove synthesis impurities which can be less thermally stable than the pure ester itself.
  • These impurities can include branched or straight chain olefins, alcohols, acetals, formals, etc. and/or acids which are either residual feedstock reactants used to make the ester lubricant or the products of side reactions during manufacture. Many of these impurities are less thermally stable than the lubricant ester compounds themselves and tend to degrade more rapidly than the esters at a given temperature and at lower temperatures.
  • antioxidants as an additive to ester lubricants to further enhance thermal stability at higher operating temperatures.
  • Typical of such antioxidant materials are phenolic compounds such as butylated hydroxy toluene or amines such as phenyl alpha-naphthyl amine. These materials tend to retard oxidative degradation of the lubricant, but because they offer little lubricating value on their own, there is a limit on the amount of antioxidant which can be added to the ester before lubrication properties of the fluid are seriously diminished.
  • the impurities present in the ester lubricants are frequently less thermally stable than the pure ester components, impurities tend to be more reactive with oxygen and with the antioxidant species present in the ester composition. This higher reactivity results in a more rapid consumption of the antioxidant species under operating temperatures resulting in a diminution in the overall thermal stability of the ester lubricant composition and lubricating value thereof.
  • the present invention provides for synthetic ester lubricants having enhanced thermal stability prepared by oxidatively treating a substrate comprising an ester lubricant with air or oxygen at elevated temperatures in excess of 200°C for a period of time sufficient to substantially oxidize impurities present in the lubricant, but insufficient to substantially oxidize the ester or to substantially decompose it.
  • the process results in a predecomposition of the most reactive species of the substrate to more stable species, species which will react less readily with antioxidant additives.
  • ester lubricants so treated are found to exhibit enhanced thermal stability at temperatures of 375°C and above, thereby rendering them more effective as lubricants in high temperature applications and more stable over longer periods of time.
  • the thermal stability of synthetic ester lubricants as described herein may be improved by subjecting the ester to a preoxidation step prior to the incorporation of any antioxidant material which is to be added to the ester.
  • Preoxidation conditions are such that reactive impurities present in the ester composition are substantially oxidized while leaving the less reactive ester component of the lubricant essentially unoxidized.
  • This preoxidation step renders the impurities more stable and less reactive with antioxidant materials added to the lubricant thereby enhancing thermal stability, extending the life of the lubricant and permitting the use of less antioxidant in the composition than would otherwise be required.
  • Ester lubricants which may be treated in accordance with the process of this invention may be generally characterized by the formula I: A3
  • E is an ester linkage selected from COO or OOC
  • A is the residuum of a substituted or unsubstituted aliphatic, cycloaliphatic or aromatic divalent, trivalent or tetravalent organic radical having from 1 to 32 carbon atoms
  • a ⁇ , A2, A 3 , A and A5 are the same or different organic radicals containing from 2 to 32 carbon atoms
  • n, m and p are independently 0 or 1 and p is 1 when is 0.
  • Suitable esters wherein E is COO include di-, tri- and tetraesters prepared by reacting saturated or unsaturated di, tri or tetra carboxylic acids with monohydric alcohols containing 2 to 32 carbon atoms.
  • Suitable esters wherein E is OOC are di-, tri- and tetra- esters prepared by reacting a diol, triol or tetraol with a saturated or unsaturated monocarboxylic acid having from 2 to 32 carbon atoms.
  • ester lubricants are tri and tetraesters prepared by forming the esterification product of at least one polyol and at least one monocarboxylic acid.
  • Suitable polyols include those polyhydric alcohols having from 2 to 8 hydroxy groups per molecule and 2 to about 25 carbon atoms.
  • Preferred polyols include neopentyl glycol. glycerol, trimethylolpropane, pentaerythritol, di- pentaerythritol and the like as well as mixtures thereof.
  • Suitable monocarboxylic acids are those having from about 4 to 32 carbon atoms.
  • Preferred monocarboxylic acids include butyric, valeric, enanthic and eicosanoic acids.
  • ester lubricants are diesters prepared by reacting a saturated or unsaturated dicarboxylic acid and a monohydric alcohol and which satisfy the general formula II.
  • R is a substituted or unsubstituted hydrocarbon radical having from 1 to 12 carbon atoms and R ⁇ and R 2 are the same or different and are each selected from the group consisting of substituted or unsubstituted hydrocarbon radicals containing from 4 to 32 carbon atoms.
  • the acids from which the above described esters are derived can be either saturated or unsaturated polycarboxylic acids, preferably dicarboxylic acids.
  • Suitable acids include citric acid; alonic acid; ethyl alonic acid; succinic acid; methyl-succinic acid, 1,1-diethylsuccinic acid; 1,2- diethylsuccinic acid; glutaric acid; methylglutaric acid; ethylglutaric acid; propylglutaric acid; isopropylglutaric acid; butylglutaric acid and its isomers; amlyglutaric acid and its isomers; di ethylglutaric acid; methylethylglutaric acid and its isomers; diethylglutaric acid; ethylpropylglutaric acid; adipic acid; 2-methyladipic acid; 2-ethyladipic acid; 2-butyl adipic acid; 2,2-dimethyladipic acid;
  • the alcohols from which the above esters are derived can be either aliphatic, araliphatic or cycloaliphatic alcohols of at least 4 carbon atoms, and preferably from about 4 to about 32 carbon atoms.
  • the saturated aliphatic alcohols are preferred. Both straight-chain and branched-chain saturated aliphatic alcohols are suitable, but branched chain alcohols are preferred. Commercial mixtures of alcohols containing substantial proportions of branched chain alcohols, such as prepared by the Oxo process, are also suitable. Guerbet di er alcohols may also be used, such as hexadecyl alcohol and eicosyl alcohol.
  • Suitable alcohols include the alkanols, such as butanol, isobutanol; tert-butanol; 1-methylpropanol; pentanol;
  • esters for use in the present invention are the esters of saturated aliphatic dicarboxylic acids in which the carboxyl radicals are separated by a chain of from about 4 to about 12 carbon atoms, and preferably from about 4 to about 8 carbon atoms, and alkyl alcohols, preferably branched-chain alcohols having from about 4 to about 20 carbon atoms, specifically from about 7 to about 18 carbon atoms.
  • Typical specific liquid esters which are preferred are: di(2-methylheptyl) adipate; di(3,5,5- trimethylhexyl) adipate and sebacate; di(3-ethylhexyl) adipate and sebacate; di(2-ethylhexyl) adipate and sebacate; dihexyl pimelate, diisobutyl sebacate; diisobutyl malonate; di(l-ethylpropyl) azelate; diisobutyl ethylmalonate; di(3-methylheptyl) pimelate; di(3,3-diisopropylhexyl) pimelate; dioctyl phthalate; ditridecyl adipate; diisodecyl adipate; isoeicosyl neodecanoate; isoeicosyl isoeicosanoate; ditridecy
  • liquid esters are neopolyol esters such as trimethylolpropane triheptanoate, trimethylolpropane tricaproate, trimethylolpropane tri- 2-methylbutyrate and similar esters based on pentaerythritol.
  • the ester lubricants may be oxidized by heating the material at a temperature in excess of 200 ⁇ C and contacting it with pure oxygen or air. Such contact may be carried out by passing a flow of air over the material, bubbling air through a bulk of the material or heating the material in an air-pressurized heated autoclave in a stirred tank reactor in the presence of air.
  • the temperature to which the ester lubricants are heated above 200°C during the oxidation process will vary depending on the identity of the ester lubricant and its physical properties, i.e., flash point and decomposition temperature.
  • the heating temperature should not exceed the temperature at which the ester lubricant itself decomposes as defined by an increase in the total level of impurities in the ester of more than about 1% by weight as measured by standard thermal gas chromatography techniques.
  • this temperature will generally range from about 200 to about 350°C, more preferably from about 225 to about 325°C.
  • the duration of the contact with oxygen or air will vary depending on the bulk of the material treated. Oxidation times may generally range from about 1 minute to about 10 hours or more. Generally speaking, the time should be sufficient to substantially oxidize impurities present in the ester material without oxidizing more than about 1% by weight of the ester material itself.
  • the product may be utilized directly in lubricant applications or all or a portion of the oxidized impurities may be removed prior to such use. Separation techniques such as fractional distillation may be facilitated by virtue of the fact that oxidation produces a heavier and lower boiling species of impurity.
  • the product may be formulated with conventional antioxidants used for ester lubricants such as hindered phenols or amines.
  • Suitable antioxidants include 2,6-di-t-buty1-4-methyl phenol, N,N '-di-sec-buty1-para-phenylenediamine, butylated hydroxytoluene, phenyl alpha naphthyl araine and like materials, added at a level of from about 0.05 to about 5% by weight.
  • preoxidation of the more thermally reactive impurity species present in the ester allows for the addition of less antioxidant to achieve lubricants of improved stability.
  • Example 1 is illustrative of the invention.
  • the thermal stability of an untreated sample of ditridecyl adipate was determined by thermal gas chromatography. A 0.2 ml sample was injected into the injector port of a chromatograph (DB-17 Megabore column, packed column inlet, no glass liner) heated to 250 ⁇ C. The residence time of the sample in the port was approximately 3 seconds. Thermal GC analysis showed the sample to be 99.13% pure ditridecyl adipate and 0.87% impurity.
  • Example 1 was repeated except that the material evaluated for thermal stability was diisodecyl adipate (DIDA) .
  • DIDA diisodecyl adipate
  • the content of impurity of the sample increased from 1.22% at the 250°c analysis temperature to 5.54% at the 375 ⁇ C temperature, resulting in a % decomposition of 4.32% over that range.
  • Example 2 An untreated sample of DIDA was oxidized by the method of Example 2 and the thermal stability was evaluated as in Example 2. Results showed that the sample had an impurity content at 250°C of 3.41% and at 375°C of 3.51%, resulting in a net decomposition of only 0.1% over that range. Results are shown in Table 1.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des lubrifiants d'esters synthétiques ayant une stabilité thermique améliorée et préparés par traitement par oxydation d'un substrat comprenant un lubrifiant d'ester à des températures élevées supérieures à 200 °C pendant une période de temps suffisante pour oxyder sensiblement les impuretés se trouvant dans le lubrifiant, mais insuffisante pour oxyder l'ester ou le décomposer. Le procédé a pour résultat la prédécomposition des espèces les plus réactives du substrat en espèces plus stables. Les lubrifiants d'esters obtenus ainsi traités ont une stabilité thermique améliorée à des températures de 375 °C et plus, les rendant ainsi plus efficaces en tant que lubrifiants dans des applications à haute température et plus stables pendant des périodes de temps plus longues.
PCT/US1992/008315 1991-10-03 1992-09-28 Procede de production de fluides ayant une stabilite thermique amelioree WO1993007240A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US770,683 1985-08-29
US77068391A 1991-10-03 1991-10-03

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WO1993007240A1 true WO1993007240A1 (fr) 1993-04-15

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000041515A2 (fr) * 1999-01-19 2000-07-20 Cargill, Incorporated Huiles a longueurs de chaines heterogenes
US6900709B2 (en) 2001-06-25 2005-05-31 Murata Manufacturing Co., Ltd. Surface acoustic wave device

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NL18746C (fr) *
GB783463A (en) * 1955-05-10 1957-09-25 Distillers Co Yeast Ltd Esters purification process
FR1256849A (fr) * 1960-05-12 1961-03-24 Chemische Werke Witten Gmbh Procédé de préparation d'esters thermiquement stables et incolores, propres à servir de plastifiants
BE675100A (fr) * 1965-01-15 1966-07-14
CA765853A (en) * 1967-08-22 Mitsubishi Chemical Industries Limited Method for purifying dimethylterephthalates
US3481873A (en) * 1967-08-11 1969-12-02 Emery Industries Inc Lubricant and method for lubricating a piston engine
SU684032A1 (ru) * 1977-12-01 1979-09-05 Волгодонский филиал Всесоюзного научно-исследовательского и проектного института поверхностно-активных веществ Способ получени сложных эфиров высокомолекул рных синтетических жирных кислот
WO1991003531A1 (fr) * 1989-09-01 1991-03-21 Henkel Kommanditgesellschaft Auf Aktien Nouvelle huile de base pour la production de lubrifiants

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Publication number Priority date Publication date Assignee Title
NL18746C (fr) *
CA765853A (en) * 1967-08-22 Mitsubishi Chemical Industries Limited Method for purifying dimethylterephthalates
GB783463A (en) * 1955-05-10 1957-09-25 Distillers Co Yeast Ltd Esters purification process
FR1256849A (fr) * 1960-05-12 1961-03-24 Chemische Werke Witten Gmbh Procédé de préparation d'esters thermiquement stables et incolores, propres à servir de plastifiants
BE675100A (fr) * 1965-01-15 1966-07-14
US3481873A (en) * 1967-08-11 1969-12-02 Emery Industries Inc Lubricant and method for lubricating a piston engine
SU684032A1 (ru) * 1977-12-01 1979-09-05 Волгодонский филиал Всесоюзного научно-исследовательского и проектного института поверхностно-активных веществ Способ получени сложных эфиров высокомолекул рных синтетических жирных кислот
WO1991003531A1 (fr) * 1989-09-01 1991-03-21 Henkel Kommanditgesellschaft Auf Aktien Nouvelle huile de base pour la production de lubrifiants

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DATABASE WPI Week 8018, Derwent Publications Ltd., London, GB; AN 80-32426C & SU,A,684 032 (VOLGODONSK SURFACTA) 7 September 1979 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000041515A2 (fr) * 1999-01-19 2000-07-20 Cargill, Incorporated Huiles a longueurs de chaines heterogenes
WO2000041515A3 (fr) * 1999-01-19 2000-11-30 Cargill Inc Huiles a longueurs de chaines heterogenes
US6278006B1 (en) 1999-01-19 2001-08-21 Cargill, Incorporated Transesterified oils
US6465401B1 (en) 1999-01-19 2002-10-15 Cargill Incorporated Oils with heterogenous chain lengths
US6943262B2 (en) 1999-01-19 2005-09-13 Cargill, Incorporated Oils with heterogenous chain lengths
US7514394B2 (en) 1999-01-19 2009-04-07 Cargill, Incorporated Oils with heterogenous chain lengths
US6900709B2 (en) 2001-06-25 2005-05-31 Murata Manufacturing Co., Ltd. Surface acoustic wave device

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