WO2018185026A1 - Compositions de fluide de travail - Google Patents

Compositions de fluide de travail Download PDF

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Publication number
WO2018185026A1
WO2018185026A1 PCT/EP2018/058288 EP2018058288W WO2018185026A1 WO 2018185026 A1 WO2018185026 A1 WO 2018185026A1 EP 2018058288 W EP2018058288 W EP 2018058288W WO 2018185026 A1 WO2018185026 A1 WO 2018185026A1
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Prior art keywords
polymer
group
composition
composition according
equal
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PCT/EP2018/058288
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English (en)
Inventor
Giovanni Boccaletti
Sara Rovinetti
Ugo De Patto
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Solvay Specialty Polymers Italy S.P.A.
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Application filed by Solvay Specialty Polymers Italy S.P.A. filed Critical Solvay Specialty Polymers Italy S.P.A.
Priority to CN201880036936.6A priority Critical patent/CN110709494A/zh
Priority to US16/500,809 priority patent/US20210324291A1/en
Priority to EP18715643.5A priority patent/EP3607033A1/fr
Priority to JP2019554351A priority patent/JP2020515697A/ja
Publication of WO2018185026A1 publication Critical patent/WO2018185026A1/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
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/38—Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen
    • 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
    • C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
    • 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
    • C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
    • C10M147/04—Monomer containing carbon, hydrogen, halogen and oxygen
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/102—Polyesters
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2213/003—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions 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
    • C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
    • 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
    • C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
    • C10M2213/043—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen 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
    • 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]
    • C10M2213/0623—Polytetrafluoroethylene [PTFE] 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/026—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrile group
    • 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
    • C10M2217/044—Polyamides
    • 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
    • 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
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/36—Release agents or mold release agents

Definitions

  • the present invention relates to a composition suitable to be used as
  • Working fluids are gases or liquids that, when pressurized, actuate a
  • Typical examples include steam in a steam engine, air in a hot air engine and hydraulic fluid in a hydraulic motor or hydraulic cylinder. More generally, in a thermodynamic system, the working fluid is a liquid or gas that absorbs or transmits energy.
  • thermodynamic systems Among the large number of suitable physical properties, their viscosity is of particular importance for use in applications such as hydrodynamic coupling, notably viscous couplings, and damping.
  • ITALY S.P.A. disclosed a method for counteract vibrations and/or shocks in a device, wherein the method comprises:
  • damper device comprising at least one (per)fluoropolyether copolymer [polymer (P)] having a viscosity higher than 2,000 mm/s and comprising recurring units derived from (per)fluoropolyether and recurring units derived from at least one olefin, the viscosity being measured at 20°C according to standard method ASTM D445, or with a dynamical mechanical spectrometer Anton Paar MCR 502 rheometer equipped with parallel plates 25 mm, at 1 rad/s and at 25°C.
  • This application teaches to provide a fluid suitable for use in a damper device, wherein the fluid is obtained by reacting a (per)fluoropolyether polymer and at least one olefin.
  • compositions comprising a (per)fluoropolyether (PFPE) polymer as base oil and at least one perfluoropolymer, typically in the form of suspensions or dispersions, have been disclosed in the art.
  • PFPE perfluoropolyether
  • US 6100325 discloses a composition in the form of dispersion, which comprises 0.1 -30 wt.% of a
  • polytetrafluoroethylene or of tetrafluoroethylene (TFE) copolymers 50-90 wt.% of a fluorinated liquid, 0.01 -5 wt.% of a surfactant and a polar solvent (water and/or alcohol) in an amount complement to 100 wt.%.
  • TFE tetrafluoroethylene
  • 6025307 discloses a fluorinated grease, in the form of dispersions, comprising 15-50 wt.% of polytetrafluoroethylene or tetrafluoroethylene copolymers, 30-84.5 wt.% of perfluoropolyether oil having a viscosity comprised between 20 and 4000 cSt at 20°C; 0.5-10 wt.% of surfactant or dispersant having perfluoropolyether or
  • perfluoroalkylic chain optionally an anti-corrosion or anti-wear additive.
  • Lubricant compositions comprising a (per)fluoropolyether (PFPE) polymer characterized by high viscosity, for example in the form of paste, have been also disclosed in the art.
  • PFPE perfluoropolyether
  • US 5032302 (EXFLUOR RESEARCH CORPORATION) discloses a
  • lubricant comprising perfluoropolyether oils containing perfluoropolyether solids as fillers, which can be prepared by mixing the perfluoropolyether solid and the perfluoropolyether oil.
  • JP H0673370 discloses a damper sealant that is put in contact with a slidable member in order to prevent the leakage of an energy-absorbing fluid in a bumper or damper and is made of a lubricating rubber composition comprising (A) a thermoplastic fluororesin, (B) a fluororubber and (C) low molecular fluorine-containing polymer.
  • component (C) the following are mentioned: tetrafluoroethylene polymer, fluoropolyether and polyfluoroalkyl.
  • the fluoropolyethers have notably the following structures:
  • phase separation can occur when the working fluid is used in harsh conditions.
  • the Applicant perceived that the highly viscous silicone oils currently used as damping fluids suffer from some disadvantages, such as sensitivity to acids, bases and moisture and in particular thermal instability. Indeed, as a result of prolonged exposure to high temperatures (200°C or even higher) the highly viscous silicone oils gradually harden over time, until they become inoperable and must be replaced. Also, the Applicant noted that the thermal instability of the highly viscous silicone oils becomes more evident as the viscosity of the silicone oil increases.
  • the Applicant faced the problem to provide a composition intended for use as working fluid in several applications.
  • the Applicant faced the problem of providing a composition that can be prepared via a simple process, such that a wide range of viscosity can be provided depending on the final intended use.
  • the Applicant has surprisingly found that a composition in the form of a solution can be obtained by contacting at least one (per)fluoropolyether polymer and at least one amorphous polymer.
  • composition of the present invention is able to retain its viscous properties over a wide range of temperatures, without showing degradation even after use for long time in a harsh environment.
  • the present invention relates to a composition
  • composition (C) comprising at least one (per)fluoropolyether polymer [polymer (P)] and at least one amorphous polymer [polymer (F)], wherein said composition (C) is in the form of a solution.
  • said polymer (F) is selected in the group consisting of amorphous polymers characterized by a glass transition temperature (T g ) measured according to ASTM D3418, in the range from -100°C to 250°C. It will be apparent to those skilled in the art that said polymer (F), being amorphous, does not show a melting temperature (T m ) when analysed by thermal analysis following ASTM D3418.
  • composition (C) according to the present invention can be prepared having a wide range of viscosity, which can be modulated on the basis of the final use for which said composition (C) is intended.
  • said composition (C) is characterized by a viscosity in the range from 100 mm 2 /s and up to 2,000,000 mm 2 /s (measured at 20°C according to standard methods, such as ASTM D445, or with a dynamical mechanical spectrometer Anton Paar MCR 502 rheometer equipped with parallel plates 25 mm, at 1 rad/s and at 25°C).
  • composition (C) can be used as working fluid in several applications, with the advantage that phase separation cannot occur in a homogeneous solution, even after exposure at high
  • PFPE perfluoropolyether
  • (per)fluoropolymer is intended to indicate that the polyether or the fluoropolymer can be fully or partially fluorinated
  • solution is intended to indicate a homogeneous mixture composed of at least two components, i.e. at least one solute (preferably an amorphous polymer) that is dissolved in a solvent (preferably the (per)fluoropolyether polymer);
  • amorphous is intended to indicate polymer(s) that, when subjected to Differential Scanning Calorimetry (DSC) according to ASTM D3418, show(s) a glass transition (T g ) but does not show a melting transition (T m ).
  • DSC Differential Scanning Calorimetry
  • said polymer (P) is a (per)fluoropolyether polymer comprising a (per)fluoropolyether chain [chain (R P f)] of formula:
  • a and b equal or different from each other, are equal to or higher than 1 , preferably from 1 to 10, more preferably from 1 to 3;
  • X and X' equal or different from each other, are -F or -CF3, provided that when a and/or b are higher than 1 , X and X' are -F;
  • Rf comprises, preferably consists of, repeating units R°, said repeating units being independently selected from the group consisting of:
  • b1 , b2, b3, b4 are independently integers ⁇ 0 such that the number average molecular weight is between 400 and 20,000, preferably between 1 ,000 and 10,000; preferably b1 is 0, b2, b3, b4 are > 0, with the ratio b4/(b2+b3) being >1 ;
  • c1 , c2, and c3 are independently integers ⁇ 0 chosen so that the number average molecular weight is between 400 and 20,000, preferably between 1 ,000 and 10,000; preferably d , c2 and c3 are all > 0, with the ratio c3/(c1 +c2) being generally lower than 0.2;
  • d is an integer >0 such that the number average molecular weight is between 1 ,000 and 20,000, preferably between 400 and 10,000;
  • c2 and c3 are independently integers > 0 chosen so that the number average molecular weight is between 400 and 20,000, preferably between 1 ,000 and 10,000; preferably the ratio c3/c2 is generally lower than 0.2; (Rf-V) -[(CF 2 CF2C(Hal*)2O)ei-(CF2CF2CH2O)e2-(CF2CF 2 CH(Hal * )O)e3]- wherein: - Hal*, equal or different at each occurrence, is a halogen selected from fluorine and chlorine atoms, preferably a fluorine atom;
  • said chain (Rf) complies with formulae (R f -VI-a) to (R f -VI-c):
  • f1 and f2 are independently integers ⁇ 0 such that the number average molecular weight is between 400 and 20,000, preferably between 1 ,000 and 10,000; preferably both f1 and f2 are integers higher than 0, with the ratio f1/f2 being >1 , more preferably higher than 1 ;
  • f3 is an integer higher than 0, such that the number average molecular weight is between 400 and 20,000, preferably between 1 ,000 and 10,000; (Rf-VI-c) -(CF 2 CF 2 CF 2 O) f4 - wherein
  • f4 is an integer higher than 0, such that the number average molecular weight is between 400 and 20,000, preferably between 1 ,000 and 10,000.
  • said chain (R P f) has two chain ends comprising perfluorooxyalkyl groups, more preferably comprising from 1 to 3 carbon atoms.
  • Suitable polymers (P) are commercially available under the trade name Fomblin® from Solvay Specialty Polymers Italy S.p.A. , Krytox® from Chemours Co., and Demn urn® from Daikin Ind., Ltd..
  • said polymer (F) is selected in the group comprising, more preferably consisting of:
  • polystyrene PS
  • ABS acrylonitrile/butadiene/styrene
  • SAN styrene/acrylonitrile
  • S/A styrene/acrylic
  • SMA maleic anhydride
  • PVC polyvinylchloride
  • CPVC chlorinated polyvinylchloride
  • PET polyethylene terephthalate glycol-modified
  • PAR polyarylate
  • PAI polyamideimide
  • PEI polyetherimide
  • polyethers such as polycarbonate (PC), polyphenylene oxide blends (PPO);
  • PSF polysulphone
  • PES polyethersulfone
  • PAS polyarylsulfone
  • TPU polyurethane
  • fluorinated polyurethane fluorinated polyurethane
  • acrylonitrile polymers fluorinated polyurethane
  • perfluoropolymer is intended to indicate a polymer consisting essentially of recurring units derived from at least one perfluorinated monomer
  • perfluorinated monomer is intended to indicate fully fluorinated monomers, which are free of hydrogen atoms
  • the expression "at least one perfluorinated monomer” is intended to indicate that the perfluoropolymer contains recurring units derived from one or more perfluorinated monomers.
  • Suitable perfluoropolymers according to the present invention comprise at least one recurring units comprising at least one perfluorinated monomer selected in the group comprising, preferably, consisting of:
  • each of Rf 4 , Rf5, Rf6, equal of different each other is independently a fluorine atom, a C1-C6 perfluoroalkyl group, optionally comprising one or more oxygen atom, e.g. -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3;
  • n 1 or 2;
  • n 1 or 2;
  • (B) C2-C8 perfluoroolefins, such as tetrafluoroethylene (TFE) and hexafluoropropene (HFP);
  • TFE tetrafluoroethylene
  • HFP hexafluoropropene
  • (Rf-i*) C1-C6 perfluoroalkyl group such as -CF3, -C2F5, -C3F7; or
  • Rf2 is a linear or branched C1-C6 perfluoroalkyl group, e.g. -CF3, -C2F5, -C3F7; a cyclic C5-C6 perfluoroalkyl group, or a linear or branched C1-C12 (per)fluorooxyalkyl group comprising one or more ether groups, such as -CF2CF2OCF3 and -CF(CF3)OCF3.
  • said polymer (F) is a copolymer of tetrafluoroethylene (TFE), i.e.
  • copolymer comprises recurring units derived from TFE and recurring units derived from at least one perfluorinated monomer different from TFE [co-monomer (F)].
  • copolymer is intended to indicate also TFE terpolymer and TFE tetrapolymer, comprising recurring units derived from TFE and from two and three perfluorinated monomers different from TFE, respectively.
  • said at least one co-monomer (F) is selected from the group consisting of:
  • each of Rf 4 , Rf5, Rf6, equal of different each other is independently a fluorine atom, a C1-C6 perfluoroalkyl group, optionally comprising one or more oxygen atom, e.g. -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3; more preferably, Rf 4 is -OCF3 or F and Rf5 and Rf6 are both a fluorine atom or both a methyl group;
  • n 1 or 2;
  • n 1 or 2;
  • polymer (F) preferably comprises more than 50% by moles, more preferably more than 75% by moles of recurring units derived from said at least one co-monomer selected from those of formula (A1 ) to (A3) above.
  • polymer (F) preferably comprises up to 99% by moles, more preferably up to 95% by moles of recurring units derived from said at least one co-monomer selected from those of formula (A1 ) to (A3) above.
  • polymer (F) preferably comprises from 77% by moles to 95% by moles of recurring units derived from said at least one co-monomer selected from those of formula (A1 ) to (A3) above and recurring units derived from TFE, such that the sum of the percentages of recurring units from said monomer and from TFE is equal to 100% by moles.
  • said at least one co-monomer (F) is selected in the group consisting of:
  • Rf2 is a linear or branched C1-C6 perfluoroalkyl group, cyclic C5-C6 perfluoroalkyl group, a linear or branched C2-C6 perfluoroxy- alkyl group; more preferably, R f2 is -CF2CF3 (MOVE1 ), -CF2CF2OCF3 (MOVE2), -CF(CF 3 )OCF 3 (MOVE2a) or -CF 3 (MOVE3); and
  • polymer (F) preferably comprises more than 5% by moles, more preferably more than 15% by moles of recurring units derived from said at least one co-monomer selected from those of formula (C).
  • polymer (F) preferably comprises up to 50% by moles, more preferably up to 45% by moles of recurring units derived from said at least one co-monomer selected from those of formula (C) above.
  • polymer (F) preferably comprises from 15% by moles to 45% by moles of recurring units derived from said at least one co-monomer selected from those of formula (C) above and recurring units derived from TFE, such that the sum of the percentages of recurring units from said co-monomer and from TFE is equal to 100% by moles.
  • said polymer (F) is a
  • each of Rf 4 , Rf5, Rf6, equal of different each other, are as defined above; more preferably, Rf 4 is -OCF3 or F and Rf5 and Rf6 are both a fluorine atom or both a methyl group.
  • said polymer (F) is a
  • said polymer (F) from polymers commercially available under the trade name of HYFLON ® AD, Tecnoflon ® PFR-LT (both commercially available from Solvay Specialty Polymers Italy S.p.A.), Teflon ® AF (commercially available from Chemours Co.) and Cytop ® (commercially available from
  • composition (C) can be prepared according to known techniques of the prior art.
  • the composition according to the present invention is prepared by solvent mixing or dry mixing.
  • At least one polymer (F) is dissolved in at least one solvent [solvent (S)], preferably a (per)fluorinated solvent, and mixed with a stirrer machine.
  • solvent (S) preferably a (per)fluorinated solvent
  • Said at least one solvent (S) is preferably selected from
  • perfuoroalkanes such as, perfuorohexane, perfuoroheptane and the like
  • hydrofluoroethers such as, hydrofluoroethers, and mixtures thereof.
  • a heating step is performed at a temperature lower than the solvent (S) boiling point. More preferably, said heating step is performed at a temperature between 20 and 100°C. Even more preferably, said heating step is performed for at least 1 hour.
  • composition (C A )] in the form of a solution comprising said polymer (F) and said at least one solvent (S).
  • composition (C A ) and at least one polymer (P) are contacted, to form a composition [composition (C AA )] and a mixing step is performed.
  • said mixing step is performed at room temperature, more preferably for about 1 hour.
  • said composition (C AA ) is heated to remove said at least one solvent (S), preferably by treatment under vacuum, to obtain the composition (C) according to the present invention.
  • At least one polymer (P) and at least one polymer (F) are first contacted and then mixed together with a stirrer machine. Then, a heating step is performed, at a temperature of about 150-200°C, preferably for more than 1 hour, even more preferably from 2 to 5 hours.
  • said composition (C) comprises at least one polymer (P) in an amount higher than 50 wt.% and up to 99.99 wt.%, more preferably from 60 wt.% to about 99.95 wt.%, even more preferably from 70 to 99.90 wt.% based on the total weight of said composition (C).
  • said composition (C) comprises at least one polymer (F) in an amount of from 0.01 to less than 50 wt.%, more preferably from 0.05 to 40 wt.%, even more preferably from 0.10 to 30 wt.% based on the total weight of said composition (C).
  • said composition (C) comprises at least one polymer (F) in an amount of from 0.1 to 20 wt.% based on the total weight of said composition (C).
  • Composition (C) according to the invention has a viscosity in the range from 100 mm 2 /s to 2,000,000 mm 2 /s - measured at 20°C according to standard methods, such as ASTM D445, or with a dynamical mechanical spectrometer Anton Paar MCR 502 rheometer equipped with parallel plates 25 mm, at 1 rad/s and at 25°C.
  • compositions (C) according to the present invention can further comprise additional ingredients, selected in the group comprising heat-resistance improving agents, anti-oxidant agents, anti-wear agents and the like.
  • each of the additional ingredients is added to the composition in an amount from 0.0001 wt.% and up to 5 wt.% based on the total weight of composition (C).
  • composition (C) according to the present invention can be used as hydraulic fluid in viscous couplings, shock absorbers, pumps, brake cylinders; damping media in speed regulators, fluid clutches (e.g., for fans), nautical and aero-nautical instruments, gyro-compasses, shock- absorbing struts, recording instruments, time regulators, pneumatic valves, overload relays, sound pickups; lubricants; release agents
  • composition (C) is used as working fluid within a viscous coupling.
  • Viscous couplings are mechanical devices typically composed of a
  • composition (C) according to this invention is used, a viscous coupling is provided also comprising said composition (C) within the housing.
  • composition (C) is used as working fluid within a damper device.
  • Suitable damper devices are selected in the group comprising dash pots; shock absorbers such as twin-tube or mono-tube shocks absorbers, positive sensitive damping (PSD) shock absorbers, acceleration sensitive damping (ASD); rotary dampers; tuned mass dampers; viscous couplings; viscous fan clutches and torsional viscous dampers.
  • shock absorbers such as twin-tube or mono-tube shocks absorbers, positive sensitive damping (PSD) shock absorbers, acceleration sensitive damping (ASD); rotary dampers; tuned mass dampers; viscous couplings; viscous fan clutches and torsional viscous dampers.
  • Typical apparatus wherein the damper devices can be used are selected in the group comprising: mechanical or electric device for wheeled vehicles (such as suspensions installations, carburettors, internal combustion devices, engines, transmissions, crankshafts), for work boats (such as engines), for aircrafts and spacecraft (such as aircraft carrier decks), for power transmission lines, for wind turbine, for consumer electronics (such as mobile phones and personal computers), for off-shore rig, for oil & gas distribution systems (such as pumps); compressors (such as reciprocating compressors for gas pipelines); devices for buildings and civil structures (such as bridges, towers, elevated freeways).
  • wheeled vehicles such as suspensions installations, carburettors, internal combustion devices, engines, transmissions, crankshafts
  • work boats such as engines
  • aircrafts and spacecraft such as aircraft carrier decks
  • power transmission lines for wind turbine
  • consumer electronics such as mobile phones and personal computers
  • off-shore rig for oil & gas distribution systems (such as pumps)
  • compressors such as reciprocating compressors for gas pipelines
  • the present invention relates to a
  • Base oils 1 to 3 Polymers A to E and Galden ® HT55 perfluoropolyether polymer were obtained from Solvay Specialty Polymers Italy S.p.A..
  • Base oil (P1) Fomblin ® Y06 PFPE
  • branched PFPE oil having the following chemical formula: CF 3 O-[(CF2CF(CF3)O)m-(CF2O)n]-CF 3
  • TTD 1,3-dioxide
  • TFE tetrafluoroethylene
  • TTD 2,2,4-trifluoro-5-trifluoromethoxy- 1 ,3-dioxide
  • TFE tetrafluoroethylene
  • Viscosity index (VI) was determined according to ASTM D2270.
  • compositions according to the invention were prepared according to the following procedure.
  • Galden ® HT55 as solvent.
  • the mixture was put under stirring at 40°C for one hour. At the end of the stirring, the mixture was analysed by visual inspection. The solution was homogeneous.
  • the final composition consisted of a single phase clear, viscous and
  • compositions was submitted to further characterization and analysis.
  • compositions according to the invention were prepared following the procedure described above, by using the Base Oils, the Polymers provided in the following Table 1.
  • Table 1 also shows the properties of each of the Base Oils.
  • compositions comprising Base Oil (P3) and each of polymer D and polymer E were prepared following the same procedure described above for the compositions according to the invention.
  • compositions thus obtained were analysed by visual inspection and found to be completely opalescent.
  • compositions thus obtained were centrifuged for about 5 minutes in order to improve their mixing. After this centrifugation, two phases appeared showing a separation between the solid polymer and the Base Oil.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne une composition appropriée pour être utilisée en tant que fluide de travail, ladite composition étant sous la forme d'une solution et comprenant au moins un polymère (per)fluoropolyéther [polymère (P)] et au moins un polymère amorphe [polymère (F)].
PCT/EP2018/058288 2017-04-03 2018-03-30 Compositions de fluide de travail WO2018185026A1 (fr)

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CN201880036936.6A CN110709494A (zh) 2017-04-03 2018-03-30 工作流体组合物
US16/500,809 US20210324291A1 (en) 2017-04-03 2018-03-30 Working fluid compositions
EP18715643.5A EP3607033A1 (fr) 2017-04-03 2018-03-30 Compositions de fluide de travail
JP2019554351A JP2020515697A (ja) 2017-04-03 2018-03-30 作動流体組成物

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CN112410099A (zh) * 2019-08-23 2021-02-26 佳能株式会社 润滑剂组合物、滑动设备、定影设备和图像形成设备
WO2021170521A1 (fr) 2020-02-24 2021-09-02 Solvay Specialty Polymers Italy S.P.A. Compositions polymères de (per)fluoropolyéther
WO2021170520A1 (fr) 2020-02-24 2021-09-02 Solvay Specialty Polymers Italy S.P.A. Polymères de (per)fluoropolyéther

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CN112410099A (zh) * 2019-08-23 2021-02-26 佳能株式会社 润滑剂组合物、滑动设备、定影设备和图像形成设备
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WO2021170520A1 (fr) 2020-02-24 2021-09-02 Solvay Specialty Polymers Italy S.P.A. Polymères de (per)fluoropolyéther

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