EP0244838B1 - Verwendung eines flüssigen Perfluorpolyethers mit sehr hoher Viskosität als Schmiermittel - Google Patents

Verwendung eines flüssigen Perfluorpolyethers mit sehr hoher Viskosität als Schmiermittel Download PDF

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Publication number
EP0244838B1
EP0244838B1 EP87106528A EP87106528A EP0244838B1 EP 0244838 B1 EP0244838 B1 EP 0244838B1 EP 87106528 A EP87106528 A EP 87106528A EP 87106528 A EP87106528 A EP 87106528A EP 0244838 B1 EP0244838 B1 EP 0244838B1
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EP
European Patent Office
Prior art keywords
perfluoropolyether
viscosity
grease
cst
fluid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87106528A
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English (en)
French (fr)
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EP0244838A1 (de
Inventor
Giovanni Zanini
Mario Alfieri
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay Specialty Polymers Italy SpA
Original Assignee
Ausimont SpA
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Publication date
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Priority to AT87106528T priority Critical patent/ATE78864T1/de
Publication of EP0244838A1 publication Critical patent/EP0244838A1/de
Application granted granted Critical
Publication of EP0244838B1 publication Critical patent/EP0244838B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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
    • C10M119/00—Lubricating compositions characterised by the thickener being a macromolecular compound
    • C10M119/22—Lubricating compositions characterised by the thickener 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06—Perfluorinated compounds
    • 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
    • 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
    • C10M2213/02—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen and halogen 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
    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/02—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen and halogen only
    • C10M2213/023—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen and halogen only 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]
    • 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

Definitions

  • the present invention relates to the use of fluid linear perfluoropolyethers having a very high kinematic viscosity, comprised within the range of from 8,000 mm2/s (cSt) to 40,000 mm2/s (cSt) at 20°C, and preferably of at least 10,000 mm2/s (cSt), as lubricating oils, and as the basic components of perfluorinated lubricating greases.
  • EP-A-95825 discloses lubricating greases based on polytetrafluoroethylene and certain perfluoropolyethers which may have a linear or branched structure. In the former case the viscosity of the polyether ranges from 40 to 6000 mm2/s.
  • EP-A-89820 describes a process for the preparation of perfluoropolyethers of high viscosity but without linear structure.
  • US-A-4 438 006 is directed to lubricant compositions which contain perfluoropolyethers having a viscosity at 38°C of from about 15 to about 1000 mm2/s.
  • the present invention provides a process for lubricating under "mixed" lubrication conditions, characterized in that a perfluoropolyether of the neutral type, having a linear structure composed of a sequence of one or more of the following oxyperfluoroalkylene units: -CF2CF2O-, CF2O-, -CF2CF2CF2O-, and having a kinematic viscosity of from 8000 to 40000 mm2/s (cSt) at 20°C is used as lubricant.
  • a perfluoropolyether of the neutral type having a linear structure composed of a sequence of one or more of the following oxyperfluoroalkylene units: -CF2CF2O-, CF2O-, -CF2CF2CF2O-, and having a kinematic viscosity of from 8000 to 40000 mm2/s (cSt) at 20°C is used as lubricant.
  • a perfluorinated lubricating grease based on polytetrafluoroethylene (PTFE) and a perfluoropolyether as defined above, said grease containing from 60% to 90% by weight of oil, based on the total weight of the grease.
  • PTFE polytetrafluoroethylene
  • the chain end groups are of perfluorinated, neutral type.
  • the products of the invention can be advantageously used as lubricants for high temperatures.
  • the perfluoropolyethers used according to the present invention show a surprising and unexpected improvement as relates to the wear rate under "mixed" lubrication conditions, as compared to the up to date commonly used perfluoropolyethers, having a much lower viscosity. This improvement cannot be simply explained by taking into account the difference in viscosity; it could be thought as being in some way connected with the molecular structure of the product.
  • the equipment used for measuring the wear rate essentially comprises a a pin-on-rig system, consisting of a carbon steel (c 15) pin resting, for a surface area of 12 mm2, on the cylindrical surface, revolving at a rate of 350 rpm, of a specimen of the same material, having an average surface roughness of 0.15 ⁇ m (microns), and a diameter of 45 mm.
  • the pin is loaded with a weight of 15 kg.
  • the specimens and the pins are cleaned in 1,1,2-trichloro-2,2,1-trifluoroethane, let dry and weighed.
  • the specimen is assembled on the equipment in such a way that it can dip inside a tray containing the lubricating oil. After 1,000 revolutions, the specimen is drawn from the equipment, is cleaned in 1,1,2-trichloro-2,2,1-trifluoroethane, let dry and weighed again, and is then assembled again on the equipment. The measurement is repeated after 10,000 rpm.
  • Test Time Minutes Z 1600 ⁇ W/L (g/m) Z 25 ⁇ W/L (g/m) Z 03 ⁇ W/L (g/m) 3 0.1x10 ⁇ 5 3x10 ⁇ 5 3.1x10 ⁇ 5 30 1x10 ⁇ 5 2x10 ⁇ 5 2.5x10 ⁇ 5 Z 1600 Perfluoropolyether belonging to Class (1), a commercial product Fomblin (R) Z by Montedison, having a kinematic viscosity of 16,000 mm2/s (cSt) at 20°C. Z 25 Ditto, with a viscosity of 250 mm2/s (cSt) Z 03 Ditto, with a viscosity of 30 mm2/s (cSt).
  • the perfluoropolyethers used according to the invention are particularly fit for the formulation of perfluorinated greases endowed with enhanced characteristics as compared to analogous products manufactured from lower-viscosity perfluoropolyether oils. Because of the vary low value of high-temperature oil separation which was observed (even at a much higher oil percentage in the grease than in the products of the prior art), the grease according to the present invention is particularly suitable for high temperature uses.
  • a very meaningful characterizing property of the grease according to the invention is the low static friction coefficient (measured as the starting resistent torque).
  • the method of preparation of the greases according to the invention is similar to the method reported in EP-A-95 825, with the difference that, because of the high viscosity of the perfluoropolyether, the kneading and the following homogenizing have to be performed under high temperature conditions (70°C).
  • the oil used is Fomblin (R) Z 1600, an above-mentioned product, having a kinematic viscosity of 16,000 mm2/s (cSt) at 20°C.
  • the thickening agent is a granular PTFE (average particle diameter 4-5 ⁇ m; m.w. 40,000), used in an amount of 25.9% by weight, relative to the grease.
  • a perfluorinated grease was prepared by using the same PTFE type, and Fomblin (R) Z 25 oil, having a viscosity of 250 mm2/s (cSt).
  • the formulation comprised 68.5% by weight of Fomblin (R) Z 25 and 31.5% by weight of PTFE.
  • the rheological characterization of the grease was carried out by means of measurements of its dynamic viscosity by using the plate/cone system mounted on a Rotovisco HAAKE 12 system, with M150 head (PKII/0.3°).
  • the first type of measurements was carried out at 25°C with increasing ⁇ (flow gradient) values (20; 40; 80 sec ⁇ 1), with the viscosity of the grease being measured at start-up, and after 15 minutes. At each measurement, the used grease was replaced by fresh grease.
  • the limited range of signal oscillation is indicative of a better constancy of lubricating performance.
  • a second type of measurement was carried out under constant ⁇ conditions of 40 sec ⁇ 1, at temperatures of 25°C; 50°C; 100°C.
  • the endurance of the lubricating grease, at 100°C, is exceptionally good, whilst, under the same conditions, a grease formulated with a lower-viscosity oil (Fomblin (R) Z 25) shows a trend to unhomogeneousness.
  • the welding load was higher than 700 kg (device measurement limit).

Landscapes

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

Claims (4)

  1. Verfahren zur Schmierung unter "gemischten" Schmierungsbedingungen, dadurch gekennzeichnet, daß ein Perfluorpolyether vom neutralen Typ mit einer linearen Struktur aus einer Sequenz von einer oder mehreren der folgenden Oxyperfluoralkylen-Einheiten:



            -CF₂CF₂O-, -CF₂O-, -CF₂CF₂CF₂O-,



    und mit einer kinematischen Viskosität von 8000 bis 40 000 mm²/s (cSt) bei 20°C als Schmiermittel verwendet wird.
  2. Verfahren nach Anspruch 1, worin die kinematische Viskosität des Perfluorpolyethers mindestens 10 000 mm²/s (cSt) beträgt.
  3. Verfahren nach Anspruch 1, worin der Perfluorpolyether die Struktur:



            R'fO(CF₂CF₂O)m(CF₂O)nRf



    aufweist, worin Rf und R'f, gleich oder verschieden voneinander, -CF₃ oder -C₂F₅ sind, wobei die Perfluoroxyalkylen-Einheiten statistisch entlang der Kette verteilt sind, und m und n ganze Zahlen sind, derart, daß die Viskosität des Perfluorpolyethers im angegebenen Bereich liegt.
  4. Perfluoriertes Schmierfett auf der Basis von Polytetrafluorethylen und eines Perfluorpolyethers nach irgendeinem der Ansprüche 1 bis 3, welches Fett 60 bis 90 Gewichtsprozent Öl enthält, bezogen auf das Gesamtgewicht des Fetts.
EP87106528A 1986-05-06 1987-05-06 Verwendung eines flüssigen Perfluorpolyethers mit sehr hoher Viskosität als Schmiermittel Expired - Lifetime EP0244838B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87106528T ATE78864T1 (de) 1986-05-06 1987-05-06 Verwendung eines fluessigen perfluorpolyethers mit sehr hoher viskositaet als schmiermittel.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT20322/86A IT1189486B (it) 1986-05-06 1986-05-06 Impiego di un perfluoropolietere fluido ad altissima viscosita' come lubrificante
IT2032286 1986-05-06

Publications (2)

Publication Number Publication Date
EP0244838A1 EP0244838A1 (de) 1987-11-11
EP0244838B1 true EP0244838B1 (de) 1992-07-29

Family

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Family Applications (1)

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EP87106528A Expired - Lifetime EP0244838B1 (de) 1986-05-06 1987-05-06 Verwendung eines flüssigen Perfluorpolyethers mit sehr hoher Viskosität als Schmiermittel

Country Status (6)

Country Link
EP (1) EP0244838B1 (de)
JP (1) JPS6322896A (de)
AT (1) ATE78864T1 (de)
CA (1) CA1285549C (de)
DE (1) DE3780695D1 (de)
IT (1) IT1189486B (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1329586C (en) * 1988-05-06 1994-05-17 Takashi Tohzuka Fluorine-containing grease and its preparation
US5171899A (en) * 1988-05-17 1992-12-15 Daikin Industries Ltd. Process for production of 1,1,1-trifluoro-2,2-dichloroethane
IT1237887B (it) * 1989-12-12 1993-06-18 Ausimont Spa Lubrificanti perfluoropolieterei aventi proprieta' antiusura
WO1995013341A1 (fr) * 1993-11-12 1995-05-18 Aktsionernoe Obschestvo Zakrytogo Tipa 'amtek' Compose de modification antifriction
JP3816118B2 (ja) * 1993-12-01 2006-08-30 アウシモント、ソチエタ、ペル、アツィオーニ 改良された特性を有する、水素添加された鉱物性または合成グリース
JP3875108B2 (ja) * 2002-01-15 2007-01-31 Ｎｏｋクリューバー株式会社 低トルクグリース組成物
DE102011055683A1 (de) 2011-11-24 2013-05-29 Götz von Foerster Synthetisches Schmiermittel zur Verwendung als Synovialflüssigkeitsersatz
CN110760361B (zh) * 2019-09-24 2022-07-26 中国石油化工股份有限公司 一种全氟聚醚型的润滑脂及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4523039A (en) * 1980-04-11 1985-06-11 The University Of Texas Method for forming perfluorocarbon ethers

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242218A (en) * 1961-03-29 1966-03-22 Du Pont Process for preparing fluorocarbon polyethers
US3665041A (en) * 1967-04-04 1972-05-23 Montedison Spa Perfluorinated polyethers and process for their preparation
US4438006A (en) * 1981-06-29 1984-03-20 The United States Of America As Represented By The Secretary Of The Air Force Perfluorinated aliphatic polyalkylether lubricant with an additive composed of an aromatic phosphine substituted with perfluoroalkylether groups
IT1150705B (it) * 1982-03-19 1986-12-17 Montedison Spa Processo di inserimento di perfluoroolefine su perfluoropolieteri e prodotti relativi
IT1152230B (it) * 1982-05-31 1986-12-31 Montedison Spa Procedimento per la preparazione di grassi lubrificanti a base di politetrafluoroetilene e perfluoropolieteri
US4438007A (en) * 1982-09-14 1984-03-20 The United States Of America As Represented By The Secretary Of The Air Force Perfluorinated aliphatic polyalkylether lubricant with an additive composed of an aromatic phosphine substituted with perfluoroalkylether groups
EP0148482B1 (de) * 1983-12-26 1992-03-25 Daikin Industries, Limited Verfahren zur Herstellung von Halogen enthaltenden Polyäthern
JPS61113694A (ja) * 1984-11-07 1986-05-31 Daikin Ind Ltd 含フツ素グリ−ス組成物

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4523039A (en) * 1980-04-11 1985-06-11 The University Of Texas Method for forming perfluorocarbon ethers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Lubricants" by D. Klamann (Verlag Chemie 1984) p.38-42 *

Also Published As

Publication number Publication date
IT1189486B (it) 1988-02-04
IT8620322A0 (it) 1986-05-06
CA1285549C (en) 1991-07-02
ATE78864T1 (de) 1992-08-15
DE3780695D1 (de) 1992-09-03
IT8620322A1 (it) 1987-11-06
EP0244838A1 (de) 1987-11-11
JPS6322896A (ja) 1988-01-30

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