Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
  • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
  • C07C211/55—Diphenylamines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
  • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
  • C07C211/58—Naphthylamines; N-substituted derivatives thereof
• • 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
  • 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
• • 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
  • 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
• • 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
  • 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
• • 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
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/041—Triaryl phosphates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants

Definitions

• Antioxidant and / or anti-corrosion agent, lubricating composition containing said agent and process for preparing same are provided.
• the present invention relates to the field of antioxidants and / or anti-corrosion agents, mainly useful as additives to lubricating compositions.
• the oxidation stability of the lubricating oils is further reduced by the dissolution of the metals in these oils under the extreme conditions of use described above. Indeed, the dissolved metals are capable of catalyzing the oxidative degradation of the lubricants, which leads to a reduction in their service life.
• antioxidant additives used in lubricating compositions fall into two broad categories: (i) hindered phenols, poorly effective on esters, and (ii) aromatic organic amines, which give good performance on esters.
• this second type of antioxidant additives mention may be made, for example, of the additives sold under the names Irganox® LO1, Irganox® LO6, and Naugalube® 348.
• a family of anti-oxidant additives that is sometimes used includes oligomers comprising combinations of diphenylamine derivative (DPA) units and phenyl- ⁇ -naphthylamine derivative (PAN) units.
• DPA diphenylamine derivative
• PAN phenyl- ⁇ -naphthylamine derivative
• antioxidant additives of the above type have been described, for example in US Pat. Nos. 3,509,214 and 3,573,206. These two patents describe, in particular, the preparation of antioxidant additives by reacting equimolar amounts of N-phenyl-2-naphthylamine and diphenylamine. presence of potassium permanganate.
• the final product additive comprised (a) 29.5% by weight unreacted diphenylamine, (b) 14.7% by weight unreacted N-phenyl-2-naphthylamine, (c) , 3% by weight of N-phenyl-2-naphthylamine dimers, and (d) 15.3% by weight of N-phenyl-2-naphthylamine and diphenylamine dimers, based on the total weight of the additive composition .
• antioxidant additives of a similar type in which an organic peroxide catalyst is used, have also been described.
• US Pat. No. 3,492,233 discloses additives prepared from diarylamines in the presence of certain organic peroxides.
• PCT Application published under No. WO 95/17488 discloses lubricating compositions consisting of products of the reaction between N-aryl naphthylamine compounds and diphenylamine compounds in the presence of an organic peroxide, in a molar ratio alkylated diphenylamine / N -aryl naphthylamine of at least 1/1, and experimentally illustrated up to 3/1.
• This document discloses the use, as organic peroxide, of di-tert-butyl peroxide.
• the final product additive consisted mainly of a mixture of homo-oligomers of diphenylamine and oligomers of N-aryl naphthylamine and diphenylamine.
• the final product additive is free of potassium permanganate catalyst or its reduction products.
• PCT application published under the number WO 95/16765 also describes antioxidant compositions consisting of reaction products of the reaction between N-aryl naphthylamine compounds and diarylamine compounds in the presence of an organic peroxide, in a ratio molar diarylamine / N-aryl naphthylamine of at least 1/1 and experimentally illustrated up to 3/1.
• This document discloses the use, as organic peroxide, of di-tert-butyl peroxide. The reaction is carried out in the absence of potassium permanganate.
• the final product additive preferably comprised at least 30 mol% of diarylamines reacted in the form of dehydrocondensation products with the solvent, at least 10 mol% of diarylamines in the form of homo-oligomers and at least 35% by weight. moles of diarylamines in the form of oligomers cross with diphenylamine and N-aryl naphthylamine. According to this document, any recourse to the use of potassium permanganate should be avoided, since the permanganate catalysts result in obtaining oligomeric products of diamines having reduced anti-oxidant effects.
• French Patent Application Publication No. FR 2,832,417 also describes lubricant compositions comprising a three-component antioxidant additive, respectively (1) a substituted diphenylamine (DPA), (2) a phenyl - ⁇ -naphthylamine (PANA) and (3) an oligomeric antioxidant prepared by reaction of a DPA and a PANA.
• the conditions of preparation of the antioxidant additive are similar, if not identical, to those described for the preparation of the additives disclosed in PCT applications Nos. WO 95/17488 and WO 95/16765 discussed above.
• the additive described in application FR 2 832 417 is prepared in the presence of one or more organic peroxides, di-tert-butyl peroxide being the only exemplified organic peroxide.
• the known anti-oxidant additives for lubricating compositions have satisfactory properties, making it possible to increase the stability of these compositions and to extend their life.
• the present invention provides a process for the preparation of novel anti-oxidants and / or anti-corrosion agents constituting novel products of the reaction between a diphenylamine compound (DPA) and a phenyl- ⁇ -naphthylamine compound (PAN).
• DPA diphenylamine compound
• PAN phenyl- ⁇ -naphthylamine compound
• the new anti-oxidant and / or anticorrosion agents prepared in accordance with the process of the invention have improved properties, compared to the known additives.
• the invention also provides lubricating compositions, particularly for turbine, comprising the above novel anti-oxidant and / or anti-corrosion agents, said lubricant compositions having improved stability properties, compared to known lubricating compositions.
• FIG. 1 represents a supercritical phase chromatogram of the antioxidant agent according to the invention.
• the Applicant has focused on the development of new anti-oxidant and / or anti-corrosion agent compositions, based on a reaction product between at least one diphenylamine (DPA) and at least one phenyl- ⁇ naphthylamine (PAN), which have an excellent ability to stabilize the characteristics of oil compositions for the transmission of energy and lubricating oil compositions, particularly lubricating oil compositions for use at high temperature, such as turbine oils for aircraft engines.
• DPA diphenylamine
• PAN phenyl- ⁇ naphthylamine
• the present invention therefore relates to a process for the preparation of an antioxidant used in lubricating compositions, and more particularly in lubricating compositions for jet engine turbines.
• an antioxidant having a quantitative and qualitative composition of monomers and oligomers imparting excellent properties of stabilization of industrial oils could be prepared from a diphenylamine compound (DPA) of formula (I) and a phenyl- ⁇ -naphthylamine compound (PAN) of formula (II), using a DPA / PAN specific molar ratio and using potassium permanganate as a reaction reagent of the condensation reaction.
• DPA diphenylamine compound
• PAN phenyl- ⁇ -naphthylamine compound
• the subject of the invention is a process for the preparation of an antioxidant and / or anti-corrosion lubricating oil agent comprising the following steps: a) reacting
• DPA diphenylamine compound
• the group R 3 denotes a linear or branched alkyl group having from 4 to 12 carbon atoms, in a compound (1) / compound (II) molar ratio ranging from 2/1 to 5/1, preferably from 2, 5/1 to 4/1, in the presence of potassium permanganate, in a solvent and at a temperature ranging from 85 ° C to 150 ° C; b) cooling the reaction mixture to a temperature of at most 80 ° C; c) filtering the cooled reaction mixture in step b),
• alkyl is meant according to the invention a linear or branched chain of a saturated hydrocarbon radical monovalent and having the specified number of carbon atoms. In a branched alkyl group, the linear hydrocarbon chain is substituted with one or more alkyl groups.
• Alkyl groups include butyl, pentyl, hexyl and octyl groups.
• the R 1 and R 2 groups of the diphenylamine compound (DPA) are the same.
• Diphenylamine compounds (DPA) include dioctylphenylamine, didecylphenylamine, didodecylphenylamine or dihexylphenylamine.
• the R 1 and R 2 groups of the diphenylamine compound (DPA) each consist of an octyl group and the DPA is di-octyl di-phenylamine or DODPA, which is well known in the art. skilled person.
• the phenyl- ⁇ -naphthylamine compounds include in particular para-tert-octylphenyl- ⁇ -naphthylamine, para-tert-dodecylphenyl- ⁇ -naphthylamine and para-tert-butyl- ⁇ -naphthylamine.
• the R 3 group of the phenyl- ⁇ -naphthylamine compound (PAN) is an octyl group and the PAN is octyl-phenyl- ⁇ -naphthylamine or N- (para).
• -tertioctylphenyl) - ⁇ -naphthylamine also known as OPAN, well known to those skilled in the art.
• DPA compounds of formula (I) and the PAN compounds of formula (II) are products commonly found on the market.
• a DPA compound of formula (I) is used in which the groups R 1 and R 2 each consist of an octyl group and the DPA consists of di-octyl phenylamine or DODPA, which is well known to those skilled in the art.
• PAN compound of formula (II) in which the R 3 group consists of an octyl group and the PAN consists of octyl-phenyl- ⁇ -naphthylamine or N- (para-tert-octylphenyl) - ⁇ -naphthylamine also known as OPAN, well known to those skilled in the art.
• the reaction mixture comprises the compound DPA, the compound PAN and potassium permanganate dissolved in an organic solvent adapted to the reaction temperature.
• Suitable solvents include solvents of aliphatic hydrocarbon compounds, including alkanes having from 6 to 16 carbon atoms in a linear, branched or cyclic structure.
• a petroleum solvent of the solvent type Exxsol DSP 10/140 sold by the company ExxonMobil Chemical it is possible to use a petroleum solvent of the solvent type Exxsol DSP 10/140 sold by the company ExxonMobil Chemical.
• the weight ratio [PAN + DPA + potassium permanganate reagents] / [solvent, SVP] is about 1.
• step a) of the process is carried out in an inert gas atmosphere which is very depleted of oxygen in order to avoid undesirable oxidation reactions.
• step a) is carried out in a reactor under a nitrogen or argon atmosphere.
• the molar ratio DPA / PAN is preferably between 3/1 and 3.5 / 1, which is the optimum DPA / PAN molar ratio range for the formation of an antioxidant having the qualitative and quantitative composition also optimal in monomer (s) and oligomers conferring superior properties of stabilization of industrial oils.
• the temperature of the reaction is advantageously at most 100 ° C. In addition, the temperature of the reaction is preferably at least 30 ° C.
• step a) is a step performed under reflux conditions.
• step a) the compounds of formula (I) and the compounds of formula (II) are first added to the solvent and, after a period of preheating, the potassium permanganate catalyst is added. to initiate the actual condensation reaction.
• Said preheating period is carried out for the time necessary to bring the starting reaction mixture free of permanganate reagent to the desired reaction temperature.
• the duration of the preheating period can range from 1 minute to 1 hour, depending on the reaction conditions chosen, in particular in particular according to the installation and the volume of starting reaction mixture.
• step a) may comprise the following substeps: a) providing a reactor containing an appropriate volume of the selected solvent; a2) adding the appropriate amounts of each of the DPA compounds of formula (I) and PAN of formula (II); a3) optionally, placing the reactor under a low oxygen atmosphere, for example by nitrogen or argon injection; a4) pre-heating the reaction medium obtained at the end of step a2) or of step a3) at a temperature between 55 ° C and 85 ° C, preferably between 60 ° C and 80 ° C ; a5) adding the appropriate amount of potassium permanganate to the reaction mixture obtained at the end of step a4); a6) increasing the temperature of the reaction mixture until reaching the chosen reaction temperature; a7) maintaining the reaction medium at the chosen reaction temperature for the time necessary to obtain the desired final DPA content of formula (I).
• steps a3) to a5) above, or alternatively steps a4) and a5) above, is irrelevant, even if the optimal reaction conditions are obtained when the initial order ai) to a7) is respected. .
• the reaction medium is maintained in step a), and more particularly in step a7), at a temperature between 1 10 ° C and 125 ° C.
• step a7) the oxidation condensation reaction is initiated and it is important to tightly regulate the temperature value of the reaction medium because it is an exothermic reaction.
• the duration of step a) is advantageously at least 5 hours and is generally at least 10 hours.
• the duration of step a) is generally at most 30 hours, and is generally at most 20 hours, depending on the chosen reaction conditions, including the chosen temperature conditions.
• the duration of step a) is conditioned by the duration of step a7), which is the step during which the condensation reaction itself is carried out.
• step b) of the process the reaction mixture is cooled to a temperature of at most 80 ° C, for example by simply stopping the heating means.
• step c) the reaction mixture is filtered to remove any sediment that has been generated in the previous steps.
• a fine filtration is carried out so as to reduce the amount of sediment to a maximum content of 1 mg per liter of reaction mixture, for example in accordance with the standard FTM-S-791 -3010 - Federal Test Method defined by the Government American.
• step c) the actual filtration may be followed by washing the reaction medium with an aqueous solution, usually demineralized water, so as to remove any residual impurities from the solvent. Then the aqueous solution is removed, for example by simple withdrawal, before performing step d) of desolvation.
• an aqueous solution usually demineralized water
• the antioxidant agent according to the invention may be in the form of a powder.
• the above process comprises the following additional step: d) removing the residual solvent, in order to obtain the antioxidant and or anticorrosion in the form of a powder.
• the residual solvent can be removed according to any known technique of desolvation, including by desolvation by heating under vacuum, the operating conditions being adapted according to the type of solvent used.
• vacuum desolvation can be carried out at a temperature of from 140 ° C to 170 ° C, preferably from 150 ° C to 160 ° C.
• the removal of the solvent can be completed by sweeping the reaction product with a neutral gas, for example nitrogen or argon.
• the solvent content of the reaction product obtained at the end of step d) is adjusted to a value of less than 50 mg of solvent per kg of final reaction product.
• the use of a compound (1) / compound (II) molar ratio of at least 2/1 and at most 5/1 in particular makes it possible to adjust the amount of DPA monomer unreacted which is found in the final product of the process, that is to say the antioxidant of the invention.
• a DPA / PAN molar ratio of less than 2/1 a final product is obtained whose final content of unreacted DPA is less than 20% by weight, relative to the total weight of said final desolvated product.
• a molar ratio DPA / PAN greater than 5/1 a product is obtained. final whose final content of unreacted DPA is greater than 30% by weight, relative to the total weight of the final product desolvated.
• a molar ratio of at least 2.5 / 1 and at most 4/1 is preferably used.
• a molar ratio of potassium permanganate / [compound (I) + compound (H)] of at least 0.25 / 1 and at most 0.35 / 1 is used.
• the molar ratio potassium permanganate / [compound (I) + compound (N)] is preferably at least 0.28 / 1.
• the molar ratio potassium permanganate / [compound (I) + compound (N)] is preferably at most 0.33 / 1.
• step a) of the process a potassium permanganate / [compound (I) + compound (N) ] ranging from 0.30 / 1 to 0.33 / 1.
• an antioxidant agent according to the invention which is in the form of powder, is obtained.
• the antioxidant of the invention can be used for the preparation of an antioxidant composition in liquid form.
• an appropriate amount of the antioxidant in the form of a powder, obtained at the end, is added. from step d) of the above process, to a suitable volume of an oil, preferably a synthetic ester type oil.
• said antioxidant composition is prepared according to a process comprising steps a) to c) of the process described above, said method also comprising the following additional steps: d) mixing between (i) the filtered reaction medium obtained at the end of step c) and (ii) an appropriate amount of an oil, preferably an oil of the synthetic ester type; e) removing the solvent, in order to obtain an antioxidant composition in liquid form.
• the antioxidant agent in an antioxidant composition in liquid form of the invention, whatever its mode of preparation, is present in the oily liquid at a content ranging from 10% to 60% by weight. weight of the anti-oxidant powder, and preferably at a content ranging from 20% to 50% by weight, relative to the total weight of the liquid composition. Most preferably, the content of the antioxidant is between 25% and 35% by weight, based on the total weight of the liquid antioxidant composition.
• the antioxidant agent according to the invention is intended to be used as an additive to industrial oils, in particular to energy transmission oils for hydraulic systems and lubricating oils, typically jet engine oils.
• the antioxidant of the invention and the above antioxidant compositions are for use as additives for synthetic gas-based gas turbine lubricants.
• the present invention also relates to an antioxidant and / or anticorrosion agent obtained by oligomerization of:
• DPA diphenylamine compound
• R 3 group means a linear or branched alkyl group having 4 to 12 carbon atoms
• said antioxidant and / or anti-corrosion agent comprising:
• the qualitative and quantitative composition of constituents (a) to (f) of the anti-oxidant agent defined above makes it possible to confer on said agent properties allowing a high level of oil stabilization. industrial, and especially aviation turbine oil.
• the antioxidant agent of the invention makes it possible to significantly reduce the variation of the acid number of the oils in which this agent is added, which indicates a stabilizing effect of these oils subjected to conditions. severe use.
• said antioxidant can significantly reduce the viscosity variation of the oils in which it is added, indicating that the antioxidant of the invention causes the maintenance of energy transfer qualities and maintaining the lubricating qualities of these oils.
• antioxidant agent of the invention or with a liquid antioxidant composition of the invention, it is possible to extend the life of industrial oils used under severe temperature and pressure conditions. which has many advantages both from the point of view of the safety of their use and from the economic point of view.
• the DPA and PAN compounds used in the process are chosen from the DPA and PAN compounds defined above in the present description.
• the presence of an amount of at least 20% by weight of diphenylamine of formula (I) in the antioxidant is favorable to the overall effect of said agent on the maintenance, with the duration of use, of the properties industrial oils to which this agent is added.
• Another advantage provided by this amount of DPA is an optimal molecular distribution of said agent, in particular with a limited content of oligomers which have a higher molecular weight. Indeed, the oligomers of high molecular weight have a thickening effect on the oil, which requires the use of a fluid base ester, resulting in a high evaporation and swelling of the elastomers
• the diphenylamine content of formula (I) is at most 30% by weight, relative to the total weight of constituents (a) to (f) of said agent.
• the dimer content is between 28% and 33% by weight, relative to the total weight of the constituents (a) to (f) of said agent.
• the dimers mainly comprise crossed dimers of DPA of formula (I) and of PAN of formula (II). It is necessary to start from the 2 components in order to obtain mono-, di-, tri- and tetramers, distributed in homo- and hetero-oligomers.
• the content of trimers is between 28% and 33% by weight, relative to the total weight of components (a) to (f) of the antioxidant.
• the content of tetramers is between 1 1% and 14% by weight, relative to the total weight of components (a) to (f) of the antioxidant.
• the content of the pentamers is between 3.5% and 5.5% by weight, relative to the total weight of the constituents (a) to (f) of the antioxidant.
• an antioxidant agent of the invention can be easily determined by those skilled in the art by any known technique.
• a person skilled in the art may use a high performance liquid chromatography (HPLC) technique or a vapor phase chromatography technique.
• HPLC high performance liquid chromatography
• vapor phase chromatography a technique that chromatography is used.
• SSC supercritical phase chromatography
• said agent is substantially free, or alternatively completely free, of a detectable amount of an organic peroxide, including an alkyl peroxide, and specifically of di-tert-butyl peroxide, as well as products of its decomposition, such as, for example, tert-butanol.
• said agent may contain detectable traces of potassium permanganate or its reduction products.
• the content can be measured by flame ion spectrometry (ICP)
• the invention also relates to antioxidant compositions in liquid form and which comprise the antioxidant agent as defined in the present description, or obtained according to the method described in detail above.
• the antioxidant compositions of the invention are in the form of an oily liquid, in which the constituents (a) to (f) are dissolved in an oil.
• the anti-oxidant agent powder is dissolved in an oil based on synthetic esters among the oils well known to those skilled in the field of lubricants for turbines. It may be in particular a diester oil and polyol esters of a known type.
• the antioxidant is present in the oily liquid at a content ranging from 10% to 60% by weight of the antioxidant powder agent, and preferably at a content of 30% by weight of antioxidant agent, relative to the total weight of the antioxidant composition.
• the antioxidant composition in liquid form in one embodiment in which the content of oxidizing agent is about 30% by weight, ranging from 20% to 50% by weight, based on the total weight of the liquid antioxidant composition, is in the form of a clear liquid having a density of about 0.989 kg / dm 3 at 20 ° C measured according to ISO 12185 ("Crude petroleum and petroleum products - Determination of mass volumic - Oscillating U-tube method ") ,.
• the content of the antioxidant is between 25% and 35% by weight, based on the total weight of the liquid antioxidant composition.
• said antioxidant composition in liquid form has kinematic viscosity values of about 14.8 mm 2 / s at 100 ° C and about 160 mm 2 / s at 40 ° C, as measured by the technique prescribed by ISO 3104 ("Petroleum products - Opaque and transparent liquids - Determination of kinematic viscosity and calculation of dynamic viscosity").
• said antioxidant composition in liquid form has a value of open cup flash point (or COC for "Cleveland Open Cup") of about 264 ° C., as measured according to the prescribed technique. by ISO 2592 ("Determination of flash and fire points - Cleveland open cup method").
• said antioxidant composition in liquid form has an acid number of about 0.03 mg KOH / g, as measured according to the technique prescribed according to the standard ARP 5088 ("Total Acid Number”). (TAN) Measurement for OiI Samples ").
• the invention also relates to lubricating compositions having an increased resistance to deposition and improved oxidation stability, which comprise an appropriate amount of an antioxidant as defined above.
• said antioxidant agent is provided in the form of a liquid antioxidant composition as described above, the latter may comprise, as already indicated, a content of antioxidant agent ranging from 10% to 60% by weight of said antioxidant, relative to the total weight of said antioxidant composition.
• a lubricating composition comprising 2.5% by weight of antioxidant can be obtained by (i) directly adding the appropriate amount of antioxidant to the lubricating composition (e.g. 5 g of antioxidant added to 97.5 g of lubricating composition), or (ii) by adding the appropriate amount of antioxidant composition comprising said antioxidant in the lubricating composition (e.g. an antioxidant composition containing 10% by weight of antioxidant added to 75 g of lubricating composition).
• a lubricating composition comprising an antioxidant additive as defined in the present description, or obtainable according to the process of the invention, exhibits a variation of acid number after accelerated aging according to the standard FTM-S-791-5308 (test conditions: 72 h at 204 ° C.), such that measured according to ARP 5088, less than 1.0 mg KOH / g, preferably less than 0.9 mg KOH / g.
• said lubricating composition has a change in acid number of less than 0.9 mg KOH / g, 0.8 mg KOH / g, 0.7 mg KOH / g, or even lower at 0.65 mg KOH / g.
• a lubricating composition comprising an antioxidant additive as defined in the present description, or obtainable according to the process of the invention, exhibits a variation in kinematic viscosity after accelerated aging according to the invention.
• standard FTM-S-791-5308 72h at 204 ° C
• said lubricating composition has a kinematic viscosity change of less than 13%, 12%, 11%, 10%, 9% or even less than 8.5%.
• a lubricant composition according to the invention comprises an amount of antioxidant as defined above ranging from 0.1% to 10% by weight of the agent in powder form, relative to the total weight of said lubricating composition.
• the antioxidant content of the lubricating composition is calculated on the basis of the amount of initial powder of said antioxidant.
• a lubricant composition according to the invention comprises an amount of oxidizing agent ranging from 0.5% to 5% by weight, and is very preferably between 1.5% and 3% by weight, relative to to the total weight of said lubricating composition.
• the antioxidant can be added in various types of industrial oils, including energy transfer oils commonly used in transmission devices, and lubricating oils.
• the antioxidant is added to lubricating oils based on synthetic esters well known to those skilled in the art, in particular in the field of lubricants for water turbines. airplane engine.
• ester-based lubricating oils produced from monohydroxyl alcohols and mono-carboxylic acids or from alcohols may be used.
• monohydroxy and dicarboxylic acids Such esters are well known to those skilled in the art. They are described, for example, in US Pat. No. 3,432,433.
• the alcohols and acids used to prepare the esters may contain from one to six functional groups, which allows the production of mono-, di-, tri- and tetra-, penta- and hexa-esters.
• esters of alcohols, diols, triols and pentaerythritols said alcohols or polyols having 2 to 20 carbon atoms, and mono- and dicarboxylic acids having 2 to 20 carbon atoms, preferably 4 to 12 atoms of carbon.
• the polyols include trimethylolpropane, pentaerythritol, dipentaerythritol, neopentyl glycol, tripentaerythritol, di-TMP and mixtures thereof.
• esters which may be contained in a lubricant composition according to the invention include the monoesters of octyl acetate, decyl acetate, octadecyl acetate, methyl myristate, butyl stearate, methyl oleate, as well as polyesters of dibutyl phthalate, di-octyl adipate, di-2-ethylhexyl azelate and ethylhexyl sebacate.
• the polyol ester base oil may be an oil prepared from technical pentaerythritol or trimethylol propane and a mixture of carboxylic acids having from 4 to 12 carbon atoms.
• Technical pentaerythritol is a mixture which comprises from about 85% to 92% by weight of monopentaerythritol and from 8% to 15% by weight of dipentaerythritol.
• a typical commercial technical pentaerythritol contains about 88% by weight of monopentaerythritol and about 12% by weight of dipentaerythritol, based on the total weight of said ester base oil.
• Technical pentaerythritol may also contain a certain amount of tri- and tetra-pentaerythritol which are usually formed as by-products during the production of technical pentaerythritol.
• the antioxidant in a lubricant composition according to the invention, can be used in combination with other additives, such as detergents, antifoaming agents, anti-wear agents, additives adapted to extreme pressures stabilizers against hydrolysis, bulking agents or viscosity modifiers, such additives being well known to those skilled in the art and commonly available commercially.
• additives such as detergents, antifoaming agents, anti-wear agents, additives adapted to extreme pressures stabilizers against hydrolysis, bulking agents or viscosity modifiers, such additives being well known to those skilled in the art and commonly available commercially.
• a lubricant composition according to the invention because of the presence of the antioxidant agent defined in the present description, consists of a composition intended to be used under severe conditions of use, in particular to extreme temperatures, for example in the range of -50 ° C to +250 ° C, and which have excellent stability properties, including properties of oxidation stability, stability of viscosity characteristics, stability to chemical degradation and reduction of deposition formation.
• the stability to chemical degradation is particularly illustrated by a small variation in the acid number, even after a long period of use of the lubricant composition under conditions of use at high pressure and high temperature.
• a lubricating composition based on pentaerythritol ester and comprising 1.5 to 3% by weight of an antioxidant according to the invention. for which an acid number change of less than 1 mg KOH / g and a change in kinematic viscosity of less than 8% have been determined according to the corrosion oxidation test defined by FTM-S-791 -5308.
• the solvent is removed under vacuum and hot: depending on the form chosen final - solid or liquid (in dilution) and the material used, the final temperature desolvantation may vary (example: in dilution 150-160 ° C final under 2 to 3 mm / Hg).
• a sample of the reaction medium during oxidation at -50% is taken in DSP 100/140 which is diluted 50 times with ethyl acetate and 5 ⁇ l is injected in SFC.
• % DODPA Surf, from the DODPA peak to be measured * 20 / Surf, from the peak of the standard DODPA
• the comparative commercial oil is BP Turbo OiI 2197 marketed by Air BP, the test results are those mentioned in the commercial literature
• the accelerated aging is carried out via the corrosion oxidation test according to the FTM-S-791-5308 standard, carried out under standard test conditions (72h at 204 ° C).
• the acid value values were measured on each of the two lubricating compositions compared, respectively before and after the aging simulation of these compositions. Acid value values were measured according to ARP 5088.
• the results show that the acid number variation value is about 1.0 mg KOH / g for the comparative lubricating composition, while the acid number variation value is about 0, 6 mg of KOH / g for the lubricant composition containing the antioxidant according to the invention.
• the lubricant composition containing an antioxidant according to the invention has a better stability and less degradation, compared to the comparative lubricating composition, which comprises a separate antioxidant also prepared from DPA and PAN.
• the kinematic viscosity values were measured on each of the two lubricating compositions compared, respectively before and after the aging simulation of these compositions.
• the kinematic viscosity values were measured according to ISO 3104. The results show that the kinematic viscosity variation value is about 14.8% for the comparative lubricating composition, while the kinematic viscosity variation value is about 8.3% for the lubricant composition containing the agent. antioxidant according to the invention.
• the lubricant composition containing an antioxidant according to the invention has a better stability and less degradation, compared to the comparative lubricating composition, which comprises a separate antioxidant also prepared from DPA and PAN.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Lubricants (AREA)

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• 2007
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• 2008
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  • 2008-11-28 WO PCT/FR2008/052156 patent/WO2009071857A1/fr not_active Ceased
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