WO2023076178A1 - Graisses de lubrification comprenant des copolymères d'oxyde de tétrafluoroéthène et d'oxyde d'hexafluoropropylène - Google Patents

Graisses de lubrification comprenant des copolymères d'oxyde de tétrafluoroéthène et d'oxyde d'hexafluoropropylène Download PDF

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WO2023076178A1
WO2023076178A1 PCT/US2022/047597 US2022047597W WO2023076178A1 WO 2023076178 A1 WO2023076178 A1 WO 2023076178A1 US 2022047597 W US2022047597 W US 2022047597W WO 2023076178 A1 WO2023076178 A1 WO 2023076178A1
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grease
mol
copolymer
range
units
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PCT/US2022/047597
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English (en)
Inventor
Alexander Borisovich Shtarov
Pelin HACARLIOGLU
Jon Lee Howell
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The Chemours Company Fc, Llc
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Priority to CN202280069827.0A priority Critical patent/CN118139951A/zh
Priority to KR1020247017004A priority patent/KR20240090772A/ko
Publication of WO2023076178A1 publication Critical patent/WO2023076178A1/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
    • 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
    • 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
    • C10M169/02—Mixtures of base-materials and thickeners
    • 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
    • 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
    • C10N2020/02—Viscosity; 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
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/085—Non-volatile compounds
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/74—Noack Volatility
    • 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

Definitions

  • the present invention relates to lubrication greases and more particularly to lubrication greases containing copolymers of tetrafluoroethylene oxide and hexafluoropropylene oxide and a thickener.
  • the commercial oils containing -CF(CFs)CF 2 O- units produced from HFP by photo-oxidation polymerization, and available under the trade name Fomblin® Y (Solvay Specialty Polymers, Milan, IT) also contain difluoroformyl (-CF 2 O-) groups, which lower their stability compared to PFPE-K and promote rapid decomposition in the presence of Lewis acids; metal halides, such as AlCh; metal oxides; or metals, such as aluminum or iron.
  • Fomblin® M and Fomblin® Z oils are mostly CF3O- groups, which also lowers their stability compared to the longer CF 3 CF 2 O-, CF 3 CF 2 CF 2 O-, and (CF3) 2 CFO- end groups in the presence of metal halides and oxides [see, for example, Kasai, “Perfluoropolyethers: Intramolecular Disproportionation”, Macromolecules, Vol. 25, pp. 6791- 6799 (1992)]. Therefore, oils with a reduced amount of CFsO- end groups are desired to achieve higher stability.
  • Oils that contain difluoroformyl (-CF 2 O-) groups such as Fomblin® M, Fomblin® Z, and Fomblin® Y oils, also have a lower thermo-oxidative stability in the presence of metals [see, for example, Koch et al., “Thermo-Oxidative Behaviour of Perfluoropolyalkylethers”, Journal of Synthetic Lubrication, Vol. 12, pp. 191-204 (1995)].
  • metals and metal oxides such as aluminum oxide (AI 2 Os) and titanium oxide (TiO 2 ), have a catalytic effect on the degradation of Fomblin® Y oils [Sianesi et al., “Perfluoropolyethers: Their Physical Properties and Behavior at High and Low Temperatures”, Wear, Vol. 18, pp. 85-100 (1971)].
  • a grease in an exemplary embodiment, includes a perfluoropolyether oil copolymer and a thickener mixed with the copolymer.
  • the copolymer includes about 20 mol% to about 80 mol% of - CF2CF2O- units, about 20 mol% to about 80 mol% of -CF(CF3)CF2O- units, and about 0 mol% to about 45 mol% of one or more additional perfluoroalkyleneoxy units.
  • the copolymer has a viscosity index in the range of about 120 to about 220.
  • the copolymer has an average TFEO run length of less than about 6.
  • a process of forming a grease includes mixing a perfluoropolyether oil copolymer with a thickener to form the grease.
  • the copolymer includes about 20 mol% to about 80 mol% of -CF2CF2O- units, about 20 mol% to about 80 mol% of - CF(CF3)CF2O- units, and about 0 mol% to about 45 mol% of one or more additional perfluoroalkyleneoxy units.
  • the copolymer has a viscosity index in the range of about 120 to about 220.
  • the copolymer has an average TFEO run length of less than about 6.
  • exemplary greases of thickeners and inert PFPE oils having a relatively small change in viscosity over a wide temperature range, a low pour point, a low volatility, and a high thermal stability.
  • the PFPE oils have a relatively small change in viscosity over a wide temperature range, a low pour point, a low volatility, and a high thermal stability.
  • the operating conditions generally make a high thermal stability of the PFPE oil less important, particularly for operation at low temperatures, than if the oil is used alone as a lubricant without a thickener.
  • the greases have lower torque values for lubricated ball bearings than greases of conventional PFPE oils of similar International Standards Organization (ISO) grade and/or have great weatherability.
  • ISO International Standards Organization
  • the greases are useful in severe conditions, including, but not limited to, high temperatures, very low pressures coupled with very low temperatures, applications requiring low torque, environments containing aggressive chemicals and solvents, and/or environments containing oxygen or chloride.
  • the provided PFPE oils are copolymers of tetrafluoroethylene oxide (TFEO) and hexafluoropropylene oxide (HFPO) that offer high thermal and chemical stability, low volatility, and improved viscosity change (e.g., lower 40°C/100°C viscosity ratios and higher viscosity indexes).
  • TFEO tetrafluoroethylene oxide
  • HFPO hexafluoropropylene oxide
  • TFEO/HFPO copolymers containing 20-80 mol% of - CF(CFS)CF20- units have a lower pour point than Fomblin® Y, - CF(CF3)CF2O-CO-CF2O- lubricants, poly-HFPO KrytoxTM lubricants, and poly-TFEO homopolymers.
  • viscosity index (VI) is a unitless value for a subject polymer or copolymer oil based on its kinematic viscosities at 40°C and 100°C and calculated by the following formula: where U is the subject oil’s kinematic viscosity at 40°C and L and H are values of kinematic viscosity at 40°C for reference oils having a VI of 0 and a VI of 100, respectively, and having the same kinematic viscosity at 100°C as the subject oil, where values for L and H are found in ASTM D2270.
  • ISO viscosity grade refers to the ISO VG that corresponds to the kinematic viscosity of oil at 40°C reported in centistokes.
  • pour point refers to the temperature, below which the polymer or copolymer loses its ability to be poured down from a beaker, following the American Society for Testing and Materials (ASTM) D97 standard test method.
  • stability refers to the temperature at which 50% weight loss is observed in the presence of 2% aluminum oxide (neutral 0C-AI2O3), as Lewis acid, in a standard 10°C/min ramp TGA test, with a higher temperature indicating a greater stability.
  • volatility refers to % weight loss of the oil from room temperature to 300°C observed in a standard 10°C/min ramp TGA test, with a lower mass loss indicating a lower volatility.
  • average TFEO run length refers to the average number of consecutive -CF2CF2O- units in a copolymer formed by the ring-opening of TFEO monomer.
  • TFEO has the following chemical structure: which becomes a -CF2CF2O- perfluoroalkyleneoxy unit in the copolymer.
  • HFPO has the following chemical structure: which becomes a -CF(CF3)CF2O- perfluoroalkyleneoxy unit in the copolymer.
  • the PFPE oil copolymer contains randomly distributed HFPO and TFEO repeat units.
  • the PFPE oil copolymer has the following chemical formula:
  • R 1 is -F or -CFs, z is 1-2, and x and y are independently 0-30, such as, for example, 1-30, 2-30, 3-30, 5-30, 5-25, 5-20, 10-20, or any value, range, or sub-range therebetween.
  • the ratio of monomers in the gas stream is selected to improve and change the lubricant properties of the resulting copolymer.
  • the copolymer has about 20 mol% to about 80 mol% of -CF2CF2O- units and about 20 mol% to about 80 mol% -CF(CFs)CF2O- units, alternatively about 20 mol% to about 75 mol% of -CF2CF2O- units and about 25 mol% to about 80 mol% of -CF(CFs)CF2O- units.
  • the copolymer has at least about 20 mol% of -CF2CF2O- units, alternatively at least about 25 mol% of -CF2CF2O- units, alternatively at least about 30 mol% of -CF2CF2O- units, alternatively at least about 35 mol% of -CF2CF2O- units, alternatively at least about 40 mol% of -CF2CF2O- units, or any value, range, or sub-range therebetween.
  • the copolymer has at least about 20 mol% of -CF(CFs)CF2O- units, alternatively at least about 25 mol% of -CF(CFs)CF2O- units, alternatively at least about 30 mol% of -CF(CFs)CF2O- units, alternatively at least about 35 mol% of -CF(CFs)CF2O- units, alternatively at least about 40 mol% of -CF(CFs)CF2O- units, alternatively at least about 45 mol% of -CF(CFS)CF2O- units, alternatively at least about 50 mol% of -CF(CFS)CF2O- units, alternatively at least about 55 mol% of -CF(CFS)CF2O- units, or any value, range, or sub-range therebetween.
  • the copolymer has about 55 mol% or more of -CF2CF2O- units and -CF(CFs)CF2O- units, in combination, such as, for example, about 60 mol% or more, about 65 mol% or more, about 70 mol% or more, about 75 mol% or more, about 80 mol% or more, about 85 mol% or more, about 90 mol% or more, about 95 mol% or more, about 99 mol% or more, essentially 100 mol%, or any value, range, or sub-range therebetween.
  • the copolymer may also include up to about 45 mol% of one or more additional perfluoroalkyleneoxy units other than the -CF2CF2O- and -CF(CFS)CF2O- perfluoroalkyleneoxy units, alternatively about 5% to about 45%, alternatively about 5% to about 35%, alternatively about 5% to about 25%, alternatively about 5% to about 10%, alternatively about 10% to about 40%, alternatively up to about 5%, alternatively up to about 10%, alternatively up to about 25%, alternatively up to about 35%, or any value, range, or sub-range therebetween.
  • the additional perfluoroalkyleneoxy unit is (-CF2-CF2-CF2-O-).
  • (-CF2-CF2-CF2-O-) units are introduced by co-polymerization of TFEO, and optionally HFPO, with 2,2,3,3-tetrafluorooxetane to make (-CH2-CF2- CF2-O-) containing polyfluorinated ether, followed by fluorination with elemental fluorine to form -CF2-CF2-CF2-O- containing polymers.
  • the copolymer has a number average molecular weight (M n ), as determined by 19 F NMR, in the range of about 1 ,500 Daltons (Da) to about 20,000 Da, alternatively about 3,500 Da to about 13,000 Da, alternatively about 2,500 Da to about 10,000 Da, or any value, range, or sub-range therebetween.
  • M n number average molecular weight
  • the copolymer has a viscosity index in the range of about 100 to about 220, alternatively about 120 to about 220, alternatively about 135 to about 200, alternatively about 100 to about 210, alternatively about 150 to about 220, alternatively about 150 to about 200, or any value, range, or sub-range therebetween.
  • the copolymer has an average TFEO run length of less than about 6, alternatively less than about 5.5, alternatively less than about 5, alternatively less than about 4.5, alternatively less than about 4, or any value, range, or sub-range therebetween.
  • a shorter average TFEO run length reduces the likelihood of crystallization of the copolymer upon cooling.
  • the copolymer has a pour point of about -20°C or less, alternatively about -30°C or less, alternatively about - 40°C or less, alternatively about -50°C or less, or any value, range, or subrange therebetween.
  • the end groups of the copolymer contain primarily CF3CF2CF2O- and CF3CF2O- end groups, thereby avoiding the high amount of CF3O- end groups typical for a perfluoropolyether containing -CF2CF2-O- units made by photo-oxidation polymerization of TFE, and giving a lubricant with a high stability and low volatility.
  • about 31 mol% or less of the end groups are CF3O- end groups, alternatively about 16 mol% or less, alternatively about 10 mol% or less, alternatively about 5 mol% or less, or any value, range, or sub-range therebetween.
  • about 69 mol% or more of the end groups are selected from CF3CF2CF2O-, (CF 3 ) 2 CFO-, and CF3CF2O- end groups, alternatively about 84 mol% or more, alternatively about 90 mol% or more, alternatively about 95 mol% or more, or any value, range, or sub-range therebetween.
  • the stability of the copolymer is about 250°C or greater, alternatively about 250°C to about 450°C, alternatively about 275°C or greater, alternatively about 300°C or greater, alternatively about 325°C or greater, alternatively about 350°C or greater, alternatively about 350°C to about 450°C, alternatively about 375°C or greater, or any value, range, or sub-range therebetween.
  • the volatility of the copolymer at a useful temperature range is about 5% or less, alternatively about 1 % to about 5%, alternatively about 4% or less, alternatively about 3% or less, alternatively about 2% or less, alternatively about 1 % to about 2%, or any value, range, or sub-range therebetween.
  • the ISO viscosity grade of the copolymer is about 20 or greater, alternatively about 20 to about 170, alternatively about 25 or greater, alternatively about 25 to about 170, alternatively about 25 to about 110, alternatively about 50 or greater, alternatively about 95 or greater, alternatively about 95 to about 170, or any value, range, or sub-range therebetween.
  • the copolymer is formed by a process that includes feeding a gas stream containing TFEO and HFPO into a reactor containing a fluorinated solvent, an alkali metal fluoride salt, a polyethylene glycol) dialkyl ether, a short chain perfluoroalkyl polyether acid fluoride, a perfluoroalkyl acid fluoride, such as, for example, CF 3 C(O)F or CFSCF2C(O)F, or a perfluoroalkyl ketone or its corresponding alkoxide, such as, for example, CF3CF2O; CF3CF2CF2O; (CFs CFO; or CF3CF2CF2CF2O; to form an acid fluoride-containing polymer.
  • a fluorinated solvent such as, for example, CF 3 C(O)F or CFSCF2C(O)F
  • a perfluoroalkyl ketone or its corresponding alkoxide such as, for
  • the TFEO and HFPO may be provided in relative amounts in the gas stream such that the copolymer includes any of the relative amounts -CF2CF2O- units and -CF(CFS)CF2O- units disclosed herein. Maintaining the TFEO and HFPO ratio relatively constant during the polymerization provides a consistent co-polymer composition. To reduce the percentage of CF3O- end groups, the relative amount of HFPO may be increased at the end of polymerization.
  • the gas stream is adjusted to contain a mole ratio of HFPO:TFEO of at least 4:1 at the end of polymerization such that about 5 mol% or less of the end groups of the perfluoroalkyl polyether copolymer are CF3O- end groups.
  • the method further includes working up the acid fluoride-containing polymer to form the copolymer.
  • the work-up includes hydrolyzing the acid fluoride-containing polymer or a solution of the acid fluoride- containing polymer in a fluorinated solvent with water or an aqueous solution of base to form a perfluoroalkyl polyether carboxylic acid or carboxylate salt.
  • fluorinated solvents may include, but are not limited to, a partially fluorinated ether, such as, for example, perfluorobutyl methyl ether.
  • the reactor is an autoclave.
  • the reaction occurs at a temperature in the range of about -35°C to about 30°C, alternatively about -25°C to about - 15°C, or any value, range, or sub-range therebetween, over a period of about 14 to about 18 hours.
  • the hydrolysis is with an aqueous sodium hydroxide solution to reach a pH in the range of about 1 to 4.
  • the treatment is with 25% elemental fluorine at a stepwise increasing temperature from about 20°C to about 150°C, alternatively from about 25°C to about 150°C, alternatively from about 80°C to about 150°C, alternatively from about 20°C to about 80°C, alternatively from about 25°C to about 80°C, or any range or sub-range therebetween.
  • the resulting PFPE oil copolymer has a low volatility such that the temperature at which 5 wt% loss is observed is at least about 200°C, alternatively at least about 250°C, alternatively at least about 300°C, or any value, range, or sub-range therebetween. In some embodiments, the PFPE oil copolymer has a low volatility such that the temperature at which 50 wt% loss is observed is at least about 300°C, alternatively at least about 350°C, alternatively at least about 400°C, or any value, range, or sub-range therebetween.
  • the resulting PFPE oil copolymer is combined with one or more thickeners to form a grease.
  • the PFPE oil and the thickener in combination, make up at least about 95 wt% of the grease, such as, for example, at least about 96 wt%, at least about 97 wt%, at least about 98 wt%, at least about 99 wt%, at least about 99.5 wt%, or any value, range, or sub-range therebetween.
  • the thickener is in the form of particles that are chemically inert or substantially chemically inert.
  • the thickener is polytetrafluoroethylene (PTFE), talc, silica (SiC ), fluorinated ethylene propylene (FEP), perfluoroalkoxy alkane (PFA), clay, graphite, surface-treated silica, boron nitride, calcium carbonate, or a combination thereof.
  • the amount of the thickener in the grease is in the range of about 1 wt% to about 50 wt%, alternatively about 1 wt% to about 35 wt%, alternatively about 10 wt% to about 50 wt%, alternatively about 15 wt% to about 35 wt%, alternatively about 15 wt% to about 25 wt%, alternatively about 20 wt% to about 22 wt%, or any value, range, or sub-range therebetween.
  • the thickener is added in the form of a powder.
  • the powder is a micropowder.
  • the thickener is added by milling the oil with the thickener.
  • the thickener particles have a surface area in the range of about 2 m 2 /g to about 35 m 2 /g, alternatively about 7 m 2 /g to about 25 m 2 /g, alternatively about 10 m 2 /g to about 20 m 2 /g, or any value, range, or sub-range therebetween.
  • the thickener particles have an average particle size in the range of about 30 nm to about 300 nm, alternatively about 50 nm to about 250 nm, or any value, range, or subrange therebetween.
  • the average particle size refers to the average primary particle size.
  • the PTFE When the thickener is PTFE, the PTFE preferably has a number average molecular weight M n , as determined based on a total number of endgroups on the PTFE per 10 6 CF2 groups as determined by Fourier- transform infrared (FTIR) spectroscopy, of at least about 10,000 Da, alternatively about 10,000 to about 10,000,000 Da, alternatively at least 100,000 Da, alternatively at least 1 ,000,000 Da, or any value, range, or sub-range therebetween.
  • M n number average molecular weight
  • the grease has a starting torque at -40 °C of less than 1500 g-cm, alternatively less than 1100 g-cm, alternatively less than 1000 g-cm, or any value, range, or sub-range therebetween. In some embodiments, the grease has a running torque at -40 °C of less than 500 g-cm, alternatively less than 450 g-cm, alternatively less than 250 g-cm, or any value, range, or sub-range therebetween.
  • the grease also includes one or more additives.
  • the additives provide a specific benefit or property, such as, for example, anti-wear or anti-rust.
  • Appropriate additives may include, but are not limited to, molybdenum disulfide (moly disulfide), sodium nitrite, polyfluoropolyoxa-alkyl aryl phosphate esters, organic molybdenum compounds, or tungsten disulfide.
  • the greases disclosed herein may have nonflammability and high stability in oxygen environments, low vapor pressure, chemical inertness, high temperature stability, insolubility to many chemicals, good lubricity and resistance to oxidation, the ability to withstand constant temperatures up to about 550°F (about 288°C) and intermittent temperatures up to about 800°F (about 427°C), and/or an ability to remain fluid at very low temperatures, making them useful in any of a number of different applications, including, but not limited to, valve and O-ring lubrication in oxygen service, aircraft instrument bearing lubrication, seal lubrication in reactive chemical environments, life bearing seals, such as in electric motors, high-temperature grease applications, low-temperature grease applications, automotive applications, turbine applications, and/or aerospace applications.
  • the oil of the first inventive example (IE1 ) was about 44 mol% HFPO and about 56 mol% TFEO.
  • the oil of the second inventive example (IE2) was about 34 mol% HFPO and about 66 mol% TFEO.
  • the oil of the third inventive example (IE3) was about 43 mol% HFPO and about 57 mol% TFEO.
  • the oil of the first comparative example (CE1) was commercially available KrytoxTM VPF 1531 oil (The Chemours Company, Wilmington, DE), a homopolymer of HFPO.
  • the oil of the second comparative example (CE2) was commercially available KrytoxTM 143AA oil (The Chemours Company FC, LLC), a PFPE-based oil.
  • a grease containing 79 wt% oil and 21 wt% PTFE powder as a thickener was made by milling the oil with the PTFE powder.
  • the PTFE powder had an aggregate particle size D50 of 6.7 pm and a surface area of 24.4 m 2 /g (The Chemours Company, Wilmington, DE). The greases were tested for torque, wear, penetration, and separation.
  • test oil was subjected to a standard 10°C/minute ramp therm ogravimetric analyzer (TGA) test under an air or nitrogen atmosphere with a 60 mL/minute flow rate. Weight and temperature data was collected at a rate of 0.50 seconds/point. The volatility is reported as the temperatures at which 5 wt% and 50 wt% loss is observed. The resulting values are shown in Table 1.
  • TGA therm ogravimetric analyzer
  • the number average molecular weight (M n ) value for the comparative examples was the reported value for the commercial products.
  • oils of IE1 and IE3 had a more similar HFPO:TFEO ratio
  • the oils of IE1 and IE2 had a more similar molecular weight, resulting in viscosities and volatilities that were more similar to each other.
  • inventive oils had similar viscosities to the comparative oils at 40°C and 100°C and were generally less volatile than the comparative oils.
  • inventive oils had viscosities between those of the comparative oils at -40°C.
  • Table 2 shows that the inventive greases have good penetration and low oil separation.
  • One advantage of the inventive examples is a reduction in the low temperature torque measured at -40°C, which is not achieved by the poly-HFPO oil-based grease of CE1 .
  • the volatility demonstrated by TGA of the oil components of the inventive greases is substantially lower than that of similar ISO-grade (40°C viscosity) poly-HFPO oil components of greases such as CE1 .
  • the viscosity index of the oil components of the inventive greases is substantially higher than that of similar ISO- grade (40°C viscosity) poly-HFPO oil components of greases such as CE1.

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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)

Abstract

L'invention concerne une graisse qui comprend un copolymère d'huile de perfluoropolyéther et un épaississant mélangé au copolymère. Le copolymère comprend environ 20 % à environ 80 % en moles d'unités de –CF2CF2O– , environ 20 % à environ 80 % en moles d'unités de –CF(CF3)CF2O–, et environ 0 % à environ 45 % en moles d'une ou de plusieurs unités de perfluoroalkylèneoxy supplémentaires. Le copolymère présente un indice de viscosité dans la plage d'environ 120 à environ 220. Le copolymère présente une longueur moyenne d'écoulement de TFEO inférieure à environ 6. L'invention concerne également un procédé de formation d'une graisse qui comprend le mélange d'un copolymère d'huile de perfluoropolyéther avec un épaississant pour former la graisse.
PCT/US2022/047597 2021-10-25 2022-10-24 Graisses de lubrification comprenant des copolymères d'oxyde de tétrafluoroéthène et d'oxyde d'hexafluoropropylène WO2023076178A1 (fr)

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US6040277A (en) * 1993-09-13 2000-03-21 Dow Corning Corporation Grease compositions employing fluorinated polymer oils and hexagonal lattice boron nitride
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US8067344B2 (en) 2004-06-25 2011-11-29 Nok Kluber Co., Ltd. Lubricating grease composition
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