EP1712580B1 - Additive d'huiles fluorées - Google Patents

Additive d'huiles fluorées Download PDF

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Publication number
EP1712580B1
EP1712580B1 EP06006673A EP06006673A EP1712580B1 EP 1712580 B1 EP1712580 B1 EP 1712580B1 EP 06006673 A EP06006673 A EP 06006673A EP 06006673 A EP06006673 A EP 06006673A EP 1712580 B1 EP1712580 B1 EP 1712580B1
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Prior art keywords
equal
different
formula
perfluoropolyether
range
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German (de)
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EP1712580A1 (fr
Inventor
Antonio Russo
Patrizia Maccone
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Solvay Specialty Polymers Italy SpA
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Solvay Solexis SpA
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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
    • 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
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/40—Six-membered ring containing nitrogen and carbon only
    • C10M133/42—Triazines
    • 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
    • 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
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/102—Silicates
    • C10M2201/103—Clays; Mica; Zeolites
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/1256—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids used as thickening agent
    • 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
    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/06—Perfluoro polymers
    • C10M2213/0606—Perfluoro polymers 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
    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/06—Perfluoro polymers
    • C10M2213/062—Polytetrafluoroethylene [PTFE]
    • C10M2213/0626—Polytetrafluoroethylene [PTFE] used as thickening agents
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C10M2215/222—Triazines
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/045—Polyureas; Polyurethanes
    • C10M2217/0456—Polyureas; Polyurethanes used as thickening agents
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • 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
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention relates to additives for lubricating oils and greases capable to improve their thermal stability in the presence of metals and in oxidative environment (for example air) and their preparation process.
  • the invention relates to additives having a perfluoropolyether structure capable to stabilize lubricants, such as oils and greases, preferably having a perfluoropolyether structure, in combination with to the capability of conferring good anti-rust properties and good stability (high shelf life) to storage at 25°C, i.e. without phase separation.
  • perfluoropolyethers have a good chemical and thermal stability, and are used as lubricating oils and greases, or as hydraulic fluids in applications where a broad thermal rating is required, and in particular severe conditions, for example in contact with corrosive compounds or with ionizing radiations.
  • these lubricants show the drawback that in some extremely drastic operating conditions, as for example at temperatures higher than 280°C, in oxidative environment (for example air) and in the presence of metals, tend to decompose showing a limited thermal stability.
  • the decomposition process in the above described conditions brings to the fragmentation of the perfluoropolyether chains or, in some cases, to the total decomposition of the lubricant itself, thus compromizing the lubricant performances.
  • fluid decomposition is generally associated with a progressive corrosion of the metal itself.
  • USP 4,681,693 describes stabilizers for perfluoropolyether lubricants having a backbone formed of arylphosphines units, or their derivatives, linked to perfluoropolyether chains through oxygen or sulphur atoms. These compounds are prepared with a multistep process comprising intermediates difficult to be prepared. Therefore this process is hardly industrially usable.
  • EP 597,369 describes stabilizers for phosphazene derivatives based perfluoropolyether lubricants, having contemporaneously on the phosphazene ring both aromatic groups and (per)fluoropolyether chains.
  • the synthesis of the stabilizers is not selective and does not allow to obtain an additive having a well defined chemical structure.
  • the phosphazene precursor is very expensive and therefore disadvantageous from an industrial point ov view. Tests carried out by Applicant have shown that these compounds have a low stability to storage.
  • USP 5,326,910 describes perfluoropolyether phosphotriazines as stabilizers for perfluoropolyether oils. These derivatives are obtained by a synthesis requiring many steps and reactants difficult to prepare, as perfluorinated epoxides.
  • phosphoric esters in particular arylphosphates, wherein at least one of the substituents is a perfluoropolyether chain.
  • aromatic chloroesters are used. These compounds have the drawback to be very expensive.
  • the phosphoric esters are obtained by reaction of aromatic alcohols with POCl 3 , which is toxic and scalding, thus requiring specific equipments for the use on industrial scale.
  • the stabilizers containing phosphor described so far are however obtained with synthesis processes comprising various steps, some of them require the use of expensive and/or difficult to prepare reactants, requiring operating conditions or technological solutions of difficult management on industrial scale. Besides some of them show a poor stability to storage.
  • oligomers having a perfluoroalkylenether-triazine structure are described, as lubricants having a good stability to the oxidation in the presence of metals. These oligomers can also be used as stabilizing additives for oils and greases having a perlfuoropolyether structure.
  • their synthesis requires various steps, some of them require the use of precursors of difficult preparation, with a yield in the final product lower than 40%, and therefore disadvantageous also from an economic point of view. None is said on the anti-rust properties of said compounds.
  • the preferred perfluoropolyether chain R f is selected from the following structures:
  • R f structures in the compounds of formula (I) are selected between the structures (A) and (B).
  • the compounds of the invention can be used as additives of perfluorinated lubricants, as perfluoropolyether oils or perfluoropolyether base greases, to confer an improved thermal stability to the lubricant in oxidative environment and in the presence of metals in combination with good anti-rust properties and good shelf life at 25°C.
  • the pefluoropolyether compounds having at least one aryltriazine end group are transparent and odourless viscous liquids.
  • a further object of the present invention are lubricating compositions comprising:
  • perfluoropolyether oils are those belonging to the following classes:
  • the preferred perfluoropolyether oils are those of the class (1), (4), (5) and (8).
  • perfluoropolyethers of the classes from (1) to (8) have perfluoroalkyl end groups, are liquid with a very low vapour pressure value and have a viscosity, at 20°C, generally between 10 and 100,000 cSt, preferably between 40 and 2,000 cSt.
  • perfluoropolyethers usable for preparing oils and greases are available on the market as for example FOMBLIN® (Solvay Solexis).
  • the lubricant compositions of the present invention have a high shelf life at room temperature and do not visually show any substantially phase separation for long periods of time.
  • compositions of the present invention can also contain other additives commonly used in perfluoropolyether lubricant formulations, as for example anti-wear additives.
  • a further object of the present invention is a process to obtain the triazine compounds of formula (I) comprising the following stages:
  • the inert solvent is preferably selected from toluene, xylene, hexafluoroxylene, acetone, diethyl-ketone, etc.
  • the used solvent amount is depending on the reactant solubility in the solvent itself.
  • inorganic base NaOH, KOH, Na 2 CO 3 , K 2 CO 3 can be used;
  • organic base 2,6-dimethylpyridine, 2-methylquinoline, 2,4,6-trimethylpyridine (collidine) can be used.
  • base 2,4,6-trimethylpyridine is used.
  • the ratio between the equivalents of the base and the sum of the equivalents of compounds (II) and (IV) used in the above mentioned three steps of stage (A) is in the range 1:1-2:1, preferably 1:1-1.5:1.
  • reaction times for each step are between 2 and 8 hours, preferably between 4 and 6 hours.
  • the reactants having the structure (III), (IV) are known and commercially available.
  • the process of the present invention results particularly advantageous as the selective substitution of only one halogen atom of the triazine ring (III) which takes place in each step i), ii), iii) of stage A) allows the highly selective substitution of the halogen atoms of the triazine reactant (III) obtaining additives having a predetermined chemical structure.
  • Said selective process allows furthermore to obtain the triazine compounds of formula (I) with a yield higher than about 90%.
  • the additives of the present invention do not contain phosphor, are obtainable with a defined chemical structure in high yields by a simple and highly selective process. Said additives allow furthermore to broaden the application field of the perfluoropolyether lubricants in thermooxidative environment in the presence of metals, in particular at temperatures higher than 280°C, in combination with anti-rust properties and high shelf life at 25°C.
  • the lubricating compositions comprising the additives of the present invention can be used in the presence of metals and in oxidative environment (in the presence of air and oxygen) at high temperatures, higher than 200°C, without any substantial lubricant degradation phenomenon.
  • the lubricating compositions containing the additives of the present invention can be used even at temperatures of about 300°C.
  • compositions of the present invention have the advantage to be stable to storage at room temperature for long periods of time, thus overcoming the prior art drawbacks.
  • the compounds of the present invention although containing non fluorinated substituents as the phenol groups, are dispersible in fluorinated oils at room temperature and do not show any substantial phase separation, thus allowing stability to storage (i.e. high shelf life).
  • the additives of the present invention can be used in lubricating oils and greases.
  • the preferred greases are the fluorinated ones, more preferably perfluoropolyether base greases.
  • the compositions contain, besides the additive of the present invention and the perfluoropolyether oil belonging to one or more of the above mentioned classes, as an essential component, a thickener, in the amounts used in the prior art, as for example PTFE, sodium terephthalamate, calcium or lithium soaps, polyurea.
  • said compositions can also contain other additives commonly used in grease technology, as talc, inorganic fillers, anti-wear additives.
  • the polymer primary particle sizes measured by electronic scanning microscopy (SEM); are between 0.02 and 0.25 micron. Said particles can be obtained, for example, by known microemulsion, emulsion, suspension polymerization processes.
  • microoxidation test reported in the Examples has been carried out by using the equipment described in the following publication: Carl E. Snyder, Jr. and Ronald E. Dolle, Jr., ASLE Transactions, 13(3), 171-180 (1975) .
  • the used operating conditions were the following:
  • the lubricating composition to be tested is introduced in the glass test tube of the equipment shown in the reference Fig. 1, and the whole is weighed and brought to the test temperature. When 24, 48 or 72 hours have elapsed, depending on the test kind, the glass test tube, cooled at room temperture, is weighed again. The difference of weight before and after the heating determines the per cent weight loss of the composition under examination.
  • a series of carbon steel (C15) (UNI) sheets having 50x100x2 mm sizes are prepared by polishing with abrasive papers (400-800 mesh) followed by cleaning and degreasing with a cloth soaked in n-hexane, and then dried. These sheets are treated by dip-coating in the"test dispersion and then placed in the fog chamber.
  • the sheets are left in the chamber closed and saturated with moisture and are controlled at time regular intervals by visual inspection up to the appearance of stains on the surface.
  • the test evaluation is expressed according to the following classification:
  • the kinematic viscosity has been measured by capillary viscometer Cannon-Fenske according to the ASTM D445 method.
  • reaction mixture When the alcohol dripping is over, the reaction mixture is kept under these conditions for about 2 hours, then it is brought to room temperature and left under these conditions for further 2 hours.
  • the precipitated collidine hydrochloride is then removed from the reaction mixture by filtration.
  • the liquid organic mass is then washed with 150 g of an aqueous HCl solution at 2% by weight. After separation of the organic phase the solvent is distilled and the product stripped at 130°C/1mmHg for about 4 hours. 96.3 g of product with a yield equal to 92% are thus obtained.
  • Example 1 was repeated but by using 9.4 g (0.068 eq) of p-nitrophenol instead of phenol.
  • a is an integer such that T 1 '-CFW 1 -O(C 3 F 6 O) a -CFW 2 -T 2 ' has a number average molecular weight equal to 3770; W 1 and W 2 are equal to F or CF 3 ; T1' is equal to -F, -CF 3 , -C 2 F 5 ; T 2 ' is equal to a 60/40 mixture of -CH(CF 3 )O- and -CH 2 -O-.
  • reaction mixture When the alcohol dripping is over, the reaction mixture is kept under these conditions for about 2 hours, then it is brought to room temperture and left under these conditions for further 2 hours.
  • the precipitated collidine hydrochloride is then removed from the reaction mxiture by filtration.
  • a is an integer such that T 1 '-CFW 1 -O (C 3 F 6 O) a -CFW 2 -T 2 ' has a number average molecular weight equal to 1295; W 1 and W 2 are equal to F or CF 3 ; T1' is equal to -F, -CF 3 , -C 2 F 5 ; T 2 ' is equal to a 60/40 mixture of -CH(CF 3 )O and -CH 2 -O.
  • reaction mixture When the alcohol dripping is over, the reaction mixture is kept under these conditions for about 2 hours, then it is brought to room temperature and left under these conditions for further 2 hours.
  • the precipitated collidine hydrochloride is then removed from the reaction mixture by filtration.
  • T 1 '-CFW 1 -O(C 3 F 6 O) a -CFW 2 -T 2 ' has a number average molecular weight equal to 3770; W 1 and W 2 are equal to F or CF 3 ; T 1 ' is equal to -F, -CF 3 , -C 2 F 5 ; T 2 ' is equal to a 60/40 mixture of -CH(CF 3 )O- and -CH 2 -O- .
  • reaction mixture temperature is slowly brought to 80°C and the reaction is allowed to continue for about 6 hours.
  • the precipitated collidine hydrochloride is then removed from the reaction mixture by filtration.
  • a perfluoropolyether oil of the class (5) having kinematic viscosity at 20°C of 260 cSt, commercially known as Fomblin® Z25, are added with 0.5 g of the additive of the Example 4 and then introduced in the glass test tube for the microoxidation test, in the presence of metals. After 24 hours at 300°C under the indicated operating conditions, a weight loss of 1.1% was determined.
  • the metals dipped in the fluid during the test did not show oxidation/attack signs, but resulted comparable with those not exposed to the treatment.
  • composition obtained by adding the perfluoropolyether oil with the additive of the Example 4 has resulted stable at room temperature and it does not visually show any separation after 168 hours.
  • Example 6 was repeated but increasing the time of the microoxidation test to 48 hours. At the end of the test a loss of 1.46% by weight was measured.
  • Example 6 was repeated by using 0.5 g of the additive of the Example 1. After 24 hours at 300°C under the indicated operating conditions a weight loss of 0.98% was measured.
  • the metals dipped into the fluid during the test (stainless steel and Ti, Al, V alloy) do not show oxidation/attack signs, but are comparable with those not exposed to the treatment.
  • composition obtained by adding the perfluoropolyether oil with the additive of the Example 1 resulted stable at room temperature and it did not visually show any phase separation after 168 hours.
  • Example 8 was repeated but increasing the time of the microoxidation test to 48 hours. At the end of the test a loss of 1.6% by weight was measured.
  • Example 8 was repeated but increasing the time of the microoxidation test to 72 hours. At the end of the test a loss of 2.2% by weight was measured.
  • Example 6 was repeated by using 0.5 g of the additive of the Example 3. After 24 hours at 300°C under the indicated operating conditions a weight loss of 0.47% was measured.
  • the metals dipped into the fluid during the test (stainless steel and Ti, Al, V alloy) do not show oxidation/attack sings, but are comparable with those not exposed to the treatment.
  • composition obtained by adding the perfluoropolyether oil with the additive of the Example 3 resulted stable at room temperature and it did not visually show any separation after 168 hours.
  • Example 6 was repeated by using 0.5 g of the additive of the Example 2. After 24 hours at 300°C under the indicated operating conditions a weight loss of 0.82% was measured.
  • the metals dipped into the fluid during the test (stainless steel and Ti, Al, V alloy) do not show oxidation/attack signs, but are comparable with those not exposed to the treatment.
  • composition obtained by adding the perfluoropolyether oil with the additive of the Example 2 resulted stable at room temperture and it did not visually show any separation after 168 hours.
  • Example 6 was repeated in the absence of stabilizing additives. During the test a development of white smokes was observed. After 24 hours at 300°C under the indicated operating conditions the oil was completely decomposed.
  • the metals dipped into the oil during the test show evident oxidation/attack signs and a remarkable darkening of the surface.
  • composition obtained by adding the perfluoropolyether oil with the additive having aryl end groups of EP 1,354,932 and not containing triazine rings shows evident phase separation at room temperature already within 24 hours.
  • Example 6 was repeated but by using as stabilizing agent 0.5 g of the compound of the Example 5 (comparative).
  • a lubricating composition is prepared containing 0,5 g of the additive of the Example 2, 9.5 g of a perfluoropolyether lubricant of structure (1), having kinematic viscosity at 20°C of 40 cSt, commercially known as Fomblin® Y04. Said composition is then diluted with 190 g of a fluorinated solvent commercially known as Galden® SV90.
  • a metal sheet cleaned according to what reported for the fog chamber test, is treated by dipping for 1 minute in said mixture. Said time elapsed, the sheet is taken and allowed to dry in a ventilated stove for 30 minutes at 60°C to remove the solvent. Then the sheet is placed in the fog chamber for the test.
  • Example 16 was repeated without adding the invention additive and by using a lubricating mixture formed of 10 g of Fomblin® Y04 oil and 190 g of fluorinated solvent Galden® SV90.
  • Example 16 was repeated without using the perfluoropolyether oil and by using a mixture formed of 0.5 g of the additive of the Example 2 and 199.5 g of fluorinated solvent Galden® SV90.
  • Example 16 was repeated by using only 200 g of fluorinated solvent Galden® SV90 (control test).

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

Claims (17)

  1. Composés comprenant des chaînes perfluoropolyéther et renfermant au moins un groupe terminal aryltriazine, de formule :
    Figure imgb0022
     dans laquelle
    - Rf est une chaîne (per)fluoropolyoxyalkylène formée d'un ou de plusieurs motifs récurrents, placés statistiquement le long de la chaîne, présentant la structure suivante : (CFXO), (CF2CF2O) (CF2CF2CF2O), (CF2CF2CF2CF2O), (CR6R7CF2CF2O), (CF(CF3)CF2O), (CF2CF(CF3)O), dans laquelle X est un atome de fluor, un groupe CF3 ; R6 et R7, identiques ou différents l'un de l'autre, sont choisis parmi un atome d'hydrogène, un atome de chlore ou un groupe perfluoroalkyle renfermant de 1 à 4 atomes de carbone, ledit Rf présentant un poids moléculaire moyen en nombre dans la plage de 500 à 10 000, de préférence de 500 à 5000 ;
    - W1, W2, identiques ou différents l'un de l'autre, sont un groupe -F ou un groupe -CF3 ;
    - T1 est un groupe -CHAa-Ba(CH2CH2O)na- dans lequel Aa est un atome d'hydrogène, un groupe CF3.
    Ba est un atome d'oxygène, un atome de soufre, un groupe NH ; na est un entier de 0 à 6, les extrêmes étant inclus ;
    - T2 est un groupe -F, un groupe -CF3, un groupe -C2F5, un groupe -(C2F4)Cl, ou un groupe de formule :
    Figure imgb0023
    - Q1, Q2, identiques ou différents l'un de l'autre, sont une chaîne perfluoropolyoxyalkylène de formule :

            -T1-CFW1-O-Rf-CFW2-T'2,

    dans laquelle T'2 est un groupe F, un groupe -CF3, un groupe -C2F5, un groupe -(C2F4)Cl ; T1, W1 et W2 présentent la signification ci-dessus ;
    ou un groupe de formule :
    Figure imgb0024
     dans laquelle B est un atome d'oxygène, un atome de soufre, un groupe NH ; R1, R2, R3, R4, R5, identiques ou différents les uns des autres, sont choisis parmi un atome d'hydrogène, un atome de fluor, un groupe NO2,
    un groupe CN, un groupe perfluoroalkyle en C1-C8 linéaire ou ramifié, un groupe carboxyle, un groupe phényle (Ph), un groupe O-Ph, un groupe NH-Ph, un groupe S-Ph ;
    à condition qu'au moins l'un parmi Q1 et Q2 soit un groupe :
    Figure imgb0025
  2. Composés selon la revendication 1, dans lesquels la chaîne perfluoropolyéther Rf est choisie parmi les structures suivantes :
    (A) -(CF2CF(CF3)O)a(CFXO)b- ou -(CF2CF(CF3)O)a(CFXO)b-CF2(R'f)CF2-O-(CF2CF(CF3)O)a (CFXO)b-
    dans lesquelles R'f est un groupe fluoroalkylène renfermant de 1 à 4 atomes de carbone ; X est un atome de fluor ou un groupe CF3 ; a et b sont des entiers tels que le poids moléculaire moyen en nombre soit dans la plage ci-dessus ; a/b est compris entre 10 et 100, b étant différent de 0 ;
    (B) -(CF2CF2O)c(CF2O)d(CF2(CF2)2O)h-
    dans laquelle c, d et h sont des entiers tels que le poids moléculaire moyen en nombre soit dans la plage ci-dessus ; c/d, d étant différent de 0, est compris entre 0,1 et 10 ; h/(c+d), (c+d) étant différent de 0, est compris entre 0 et 0,05 ; z vaut 2 ou 3 ; h peut également valoir 0 ;
    (C) -(CF2CF(CF3)O)e(CF2CF2O)f(CFXO)g-
    dans laquelle X est un atome de fluor ou un groupe CF3 ; e, f, g sont des entiers tels que le poids moléculaire moyen en nombre soit dans la plage ci-dessus ; e/(f+g) est compris entre 0,1 et 10, (f+g) étant différent de 0 ; f/g est compris entre 2 et 10 ;
    (D) -(CF2(CF2)zO)s-
    dans laquelle s est un entier tel qu'il donne lieu au poids moléculaire ci-dessus, z présente la signification déjà définie ;
    (E) -(CR6R7CF2CF2O)j'- ou

            -(CR6R7CF2CF2O)p'-R'f-O-(CR6R7CF2CF2O)q'-

    dans lesquelles R6 et R7 sont identiques ou différents l'un de l'autre et sont choisis parmi un atome d'hydrogène, un atome de chlore ou un groupe perfluoroalkyle renfermant de 1 à 4 atomes de carbone ; R'f est un groupe fluoroalkylène renfermant de 1 à 4 atomes de carbone ; j', p' et q' sont des entiers tels qu'ils donnent lieu au poids moléculaire tel que celui mentionné ci-dessus ;
    (F) -(CF(CF3)CF2O)j"-
    j" étant un entier tel qu'il donne lieu au poids moléculaire ci-dessus.
  3. Composés selon la revendication 2, dans lesquels les structures Rf sont (A) ou (B).
  4. Utilisation des composés selon les revendications 1 à 3 en tant qu'agents stabilisants thermiques pour des huiles et des graisses fluorées dans des conditions thermo-oxydantes en présence de métaux.
  5. Utilisation des composés selon les revendications 1 à 3 en tant qu'additifs anti-rouille pour des huiles et des graisses fluorées.
  6. Utilisation selon la revendication 4 en tant qu'additifs anti-rouille.
  7. Compositions lubrifiantes comprenant :
    - de 99,95 à 90 % en poids, de préférence de 99,5 à 95 %, d'une huile de perfluoropolyéther ou d'une graisse à base de PFPE sur des huiles de perfluoropolyéther ;
    - de 0,05 à 10 % en poids, de préférence de 0,5 à 5 % en poids, d'au moins l'un des composés triazine de formule (I) selon les revendications 1 à 3.
  8. Compositions selon la revendication 7, dans lesquelles l'huile de perfluoropolyéther est choisie parmi les classes suivantes :
    (1) E-O-[CF2CF(CF3)O]m'(CFXO)n'-E'
    dans laquelle :
    X est un groupe -F ou un groupe -CF3 ;
    E et E', identiques ou différents l'un de l'autre, sont choisis parmi un groupe -CF3, un groupe -C2F5 ou un groupe -C3F7 ;
    m' et n' sont des entiers tels que le rapport m'/n' est compris entre 20 et 1000, n' étant différent de 0, et la viscosité du produit à 20°C est comprise entre 10 et 4000 cSt ; les motifs étant distribués statistiquement le long du squelette ;
    (2) C3F7O-[CF(CF3)CF2O]0'-D
    dans laquelle
    D est un groupe -C2F5 ou un groupe -C3F7 ;
    o' est un entier tel que la viscosité du produit soit dans la plage indiquée en (1) ;
    (3) {C3F7O-[CF(CF3)CF2O]p'-CF(CF3)-}2
    dans laquelle
    p' est un entier tel que la viscosité du produit soit dans la plage indiquée en (1) ;
    (4) E-O-[CF2CF(CF3)O]q'(C2F4O)r'(CFX)s'-E'
    dans laquelle
    X est un groupe -F ou un groupe -CF3 ;
    E et E', identiques ou différents l'un de l'autre, sont choisis parmi un groupe -CF3, un groupe -C2F5 ou un groupe -C3F7 ;
    q', r' et s' sont des entiers, y compris 0, de telle sorte que la viscosité du produit soit dans la plage indiquée en (1) ;
    (5) E-O-(C2F4O)t'(CF2O)u'-E'
    dans laquelle
    E et E', identiques ou différents l'un de l'autre, sont choisis parmi un groupe -CF3, un groupe -C2F5 ou un groupe -C3F7 ;
    t' et u' sont des entiers tels que le rapport t'/u' soit compris entre 0,1 et 5, u' étant différent de 0, et la viscosité du produit est dans la plage signalée ci-dessus en (1) ;
    (6) E-O-(CF2CF2CF2O)v'-E'
    dans laquelle :
    E et E', identiques ou différents l'un de l'autre, sont choisis parmi un groupe -CF3, un groupe -C2F5 ou un groupe -C3F7 ;
    v' est un nombre tel que la viscosité du produit soit dans la plage signalée ci-dessus en (1).
    (7) D-O-(CF2CF2O)z'-D'
    dans laquelle
    D et D', identiques ou différents l'un de l'autre, sont choisis parmi un groupe -C2F5 ou un groupe -C3F7 ;
    z' est un entier tel que la viscosité du produit soit dans la plage signalée ci-dessus en (1).
    (8) E1-O-(CF2O)n(CF2CF2O)m-(CF2CF2CF2O)p(CF2CF2CF2CF2O)q-E2
    dans laquelle
    E1 et E2 sont des groupes terminaux perfluoroalkyle identiques ou différents l'un de l'autre, de formule -(CF2)zCF3, dans laquelle z est un entier de 0 à 3 ; n, m, p, q sont des entiers tels que la viscosité soit telle que définie en (1), m/n est compris entre 2 et 20, n étant différent de 0, de préférence compris entre 2 et 10 ; le rapport (p+q)/(m+n+p+q) est compris entre 0,05 et 0,2, (m+n+p+q) étant différent de 0 ; n/(m+n+q+p) s'échelonne entre 0,05 et 0,4 (m+n+p+q) étant différent de 0.
  9. Compositions selon la revendication 8, dans lesquelles les huiles de perfluoropolyéther sont celles des classes (1), (4), (5) et (8).
  10. Compositions selon les revendications 7 à 9, comprenant les additifs couramment utilisés dans des formulations lubrifiantes de perfluoropolyéther, de préférence des additifs anti-usure.
  11. Procédé de préparation de composés triazine de formule (I) selon les revendications 1 à 3, comprenant les stades suivants :
    STADE A)
    i) la réaction d'un dérivé de perfluoropolyoxyalkylène de formule

            T"1-CFW1-O-Rf-CFW2-T"2     (II)

    dans laquelle
    Rf, W1 et W2 présentent la signification ci-dessus ;
    T"1 et T"2 peuvent être identiques ou différents l'un de l'autre, de formule générale -CHAa-Ba(CH2CH2O)na-H, dans laquelle Aa est un atome d'hydrogène, un groupe CF3 ; Ba est un atome d'oxygène, un atome de soufre, un groupe NH ; na est un entier de 0 à 6, les extrêmes étant inclus ; ou choisis parmi un atome de fluor, un groupe CF3, un groupe C2F5 ou un groupe (C2F4)Cl, à condition qu'au moins l'un des deux groupes terminaux T"1 et T"2 soit un groupe CHAa-Ba(CH2CH2O)na-H, de préférence choisi parmi un groupe O-CH2OH, un groupe O-CH2SH, un groupe O-CH2NH2, un groupe CH(OH)CF3 ;
    avec
    une trihalogéno-triazine de formule :
    Figure imgb0026
     dans laquelle J est un atome de chlore, un atome de fluor, de préférence un atome de chlore ;
    à une température comprise entre 0° et 10°C, où le rapport entre les équivalents du composé (II) et les moles de (III) est égal à 1:1, en présence d'un solvant inerte dans les conditions de réaction, capable de solubiliser les réactifs, et en présence d'une base organique ou inorganique, en maintenant de préférence le mélange réactionnel sous agitation ;
    ii) la réaction du produit obtenu en i) avec un équivalent d'un dérivé de formule :

            Q-H     (IV)

    dans laquelle Q présente la signification signalée ci-dessus pour Q1 et Q2 ;
    à une température dans la plage de 25° à 35°C ;
    iii) la réaction du produit obtenu en ii) avec un équivalent d'un composé de formule (IV), identique ou différent de celui utilisé dans l'étape ii), à une température dans la plage de 65°C à 100°C, de préférence de 70°C à 90°C ;
    STADE B)
    la séparation de la phase organique du mélange réactionnel obtenu en A) de la phase aqueuse et la séparation subséquente, de préférence par filtration, de la phase organique en vue d'éliminer les sels insolubles organiques ou inorganiques résiduels ;
    STADE C)
    plusieurs lavages de la phase organique liquide avec de l'eau acide et la séparation subséquente du composé obtenu de formule (I) du solvant organique, par exemple, par évaporation.
  12. Procédé selon la revendication 11, dans lequel dans le stade A), le solvant inerte est choisi parmi le toluène, le xylène, l'hexafluoroxylène, l'acétone, la diéthylcétone.
  13. Procédé selon les revendications 11 à 12, dans lequel dans le stade A), la base inorganique est choisie parmi le NaOH, le KOH, le Na2CO3, le K2CO3 ; la base organique est choisie parmi la 2,6-diméthylpyridine, la 2-méthylquinoléine, la 2,4,6-triméthylpyridine (collidine).
  14. Procédé selon les revendications 11 à 13, dans lequel la base est la 2,4,6-triméthylpyridine.
  15. Procédé selon les revendications 11 à 14, dans lequel le rapport entre les équivalents de base et la somme des équivalents des composés (II) et (IV) utilisés dans les trois étapes du stade (A) est dans la plage de 1:1 à 2:1, de préférence de 1:1 à 1,5:1.
  16. Graisses lubrifiantes présentant une base de perfluoropolyéther comprenant l'additif selon les revendications 1 à 3, une huile de perfluoropolyéther et un agent épaississant, de préférence choisi parmi le PTFE, le téréphtalamate de sodium, des savons de calcium ou de lithium, la polyurée, plus préférablement le PTFE.
  17. Graisses selon la revendication 16, comprenant du talc, des charges inorganiques, des additifs anti-usure.
EP06006673A 2005-04-14 2006-03-30 Additive d'huiles fluorées Not-in-force EP1712580B1 (fr)

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DE112009005504B4 (de) 2008-02-01 2017-03-09 Nok Klueber Co. Ltd. Verwendung einer fluorhaltigen Diamid-Verbindung als Rostschutzzusatz einer Schmiermittelzusammensetzung
GB0917450D0 (en) * 2009-10-06 2009-11-18 3M Innovative Properties Co Triazine containing fluoropolyether elastomers having very low glass transition temperatures, compositions containing them and methods of making them
US8405929B2 (en) 2009-12-29 2013-03-26 HGST Netherlands B.V. Inhibiting oxidation of organic contaminants in a hard disk drive (HDD)
WO2012072532A1 (fr) 2010-12-03 2012-06-07 Solvay Specialty Polymers Italy S.P.A. Dérivé de triazine
US8685548B2 (en) 2011-03-31 2014-04-01 Seagate Technology Llc Lubricant compositions
US11661478B2 (en) 2017-03-02 2023-05-30 Showa Denko K.K. Magnetic recording medium, fluorine-containing ether compound and lubricant for magnetic recording medium

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IT1231758B (it) * 1989-04-20 1991-12-21 Ausimont Srl Fluoropolieteri funzionalizzati
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