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
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
  • C10M105/70—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen as ring hetero atom
• • 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
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
  • C10M105/54—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen 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
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
  • C10M105/58—Amines, e.g. polyalkylene polyamines, quaternary amines
  • C10M105/60—Amines, e.g. polyalkylene polyamines, quaternary amines having amino groups bound to an acyclic or cycloaliphatic carbon atom
  • C10M105/62—Amines, e.g. polyalkylene polyamines, quaternary amines having amino groups bound to an acyclic or cycloaliphatic carbon atom containing hydroxy groups
• • 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
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
  • C10M105/68—Amides; Imides
• • 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
  • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
  • C10M2211/042—Alcohols; Ethers; Aldehydes; Ketones
  • C10M2211/0425—Alcohols; Ethers; Aldehydes; Ketones 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
  • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
  • C10M2211/06—Perfluorinated compounds
  • C10M2211/063—Perfluorinated compounds used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
  • C10M2215/0425—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/08—Amides
  • C10M2215/0806—Amides used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/10—Amides of carbonic or haloformic acids
  • C10M2215/102—Ureas; Semicarbazides; Allophanates
  • C10M2215/1023—Ureas; Semicarbazides; Allophanates used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/2203—Heterocyclic nitrogen compounds 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31678—Of metal
  • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]

Definitions

• the present invention relates to a new ultra-thin hydrophobic and oleophobic layer formed by self-assembly on a solid substrate surface of catechol foot compounds, a process for preparing this ultra-thin layer and the use thereof as a barrier film.
• antimigration film or antimouillage film which will be called "epilame” in the rest of the exposition by analogy with the watchmaking world.
• the proper functioning of a mechanical movement depends inter alia on its lubrication.
• the durability of the lubricant depends in particular on its maintenance in the operating zone: however, a drop of lubricant spreads rapidly over a clean part.
• the deposition of an epilame layer generally in the form of a hydrophobic and oleophobic invisible molecular layer, avoids the spreading of the lubricant and its components.
• the spreading of a liquid depends on the interaction forces between the liquid, the surface and the surrounding air (cf. JC Berg, “Wettability", Marcel Dekker, New York, 1993 and AW Adamson, “Physical Chemistry of Surfaces", Wiley ).
• the parameter that characterizes the interaction forces between a liquid and the air is the surface tension, ⁇ LV .
• a surface energy ⁇ SV between a solid and the surrounding air and a parameter ⁇ LS between the solid and the liquid is similarly defined.
• Young's equation also shows that if the surface tension of the liquid is lower than the surface energy, the contact angle is zero and the liquid wets the surface. This is what happens with a lubricant deposited on a clean metal surface: in fact, a lubricant has a surface tension of 35-40 mN / m, whereas a current metal surface has a higher surface energy.
• the coating of the components on the substrate is carried out by soaking it in a solution of perfluorinated solvent loaded with polymer.
• the solvent used is generally tetradecafluorohexane (C 6 F 14 ) which, once volatilized, is a greenhouse gas since it remains stable for 3200 years in the air and has a greenhouse potential of 7'400 equiv. . CO 2 .
• the object of the invention is to propose compounds which can be used as epilame and which can be attached to a solid substrate surface without the use of environmentally toxic fluorinated solvents.
• the invention indeed proposes a novel ultra-thin hydrophobic and oleophobic layer formed by self-assembly on a solid substrate surface of catechol foot compounds, and a process for preparing this ultra-thin layer which uses a non-fluorinated solvent which is environmentally friendly.
• the environment for example a mixture of water and 2-propanol.
• This ultra-thin layer is firmly attached to the solid substrate surface.
• This ultra-thin layer has satisfactory properties for use as an epilame, in particular a contact angle in advance with water and a spreading of a drop, quite comparable to that of the layer obtained from the product. Fixodrop FK-BS reference product.
• the invention thus makes an important contribution to the ecological preparation of epilames.
• the group A serves in particular to allow the attachment of the compounds to the solid substrate surface through the catechol group and the solubilization of the amphiphilic molecule A-B in the dipping solution.
• Group B gives the ultra-thin layer its hydrophobic and oleophobic properties.
• group B is a linear aliphatic group perfluorinated in its terminal part, for example of formula (CH 2 ) n - (CF 2 ) m CF 3 wherein n is 1 to 5, especially 1 to 3, and m is 4 to 11, especially 5 to 9.
• Interesting groups A are those selected from one of the following groups:
• a particularly preferred compound is N- (3,4-dihydroxyphenethyl) -4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11- heptadécafluoroundécanamide (SuSoS2).
• the compounds of formulas A-B can be obtained from known compounds using techniques and reactions well known to the organic chemist.
• N- (3,4-dihydroxyphenethyl) -4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecanamide may be obtained by reacting 2H, 2H, 3H, 3H-perfluoro-undecanoic acid-N-succinimidyl ester and 3-hydroxy-tyrosine hydrochloric acid in solution in DMF in the presence of N-methylmorpholine; 1- (3,4-dihydroxyphenethyl) -3-octadecylurea (SuSoS1) by reacting octadecylisocyanate and 3-hydroxy-tyramine hydrochloric acid in solution in DMF in the presence of N-methyl-morpholine.
• 3- (4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecanamido) -6,7-dihydroxy-1,1 dimethyl-1,2,3,4-tétrahydroquinolinium (SuSoS 3) can be prepared from ANACAT and 2H, 2H, 3H, 3H-perfluoro-undecanoic acid-N-succinimidyl by methods analogous to those described by Y.Bethuel. K. Gademann, J. Orch. Chem 2005, 70, 6258 .
• N- (3,4-dihydroxyphenethyl) -3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10,10-heptadecafluorodecan-1-aminium can also be prepared by methods analogous to those mentioned above, from 3-hydroxy-tyrosine hydrochloric acid and 1,1,1,2,2,3,3,4,4,5,5 , 6,6,7,7,8,8-heptadecafluoro-10-iododecane.
• N- (4,5-dihydroxy-2-nitrophenethyl) -4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecanamide (SuSoS6) can also be prepared by methods analogous to those mentioned above, from 4- (2-aminoethyl) -5-nitrobenzene-1,2-diol and 2H, 2H, 3H, 3H-perfluoro-undecanoic -acid-N-succinimidyl.
• the solid substrate on the surface of which the self-assembly is made can be any solid substrate involved in the operation of a mechanical movement, in particular consisting of a material chosen from gold, steel, steel aluminum, brass, cuproberyllium, titanium dioxide, ruby, sapphire, as well as other metal surfaces, such as iron, chromium, tantalum, yttrium, copper, platinum, nickel, and nickel-phosphorus, and of metal or ceramic oxides, such as zirconia, or niobia (niobium oxide), this list not being limiting.
• the substrate may also be a substrate in one of these materials or another whose surface has been coated or coated, for example by a galvanic deposition of gold, gold-copper-cadmium and gold, nickel, rhodium, tin-nickel, or treated by anodizing, as in the case of parts made of aluminum alloy or titanium, or modified by a surface treatment such as oxidation, carburetion or nitriding.
• the thickness of the ultra-thin layer measured in ellipsometry is generally from 0.5 to 10 nm, preferably from 1 to 4 nm.
• the angle of contact in advance with the water is at least 100 °.
• the ultra-thin layer remains functional as epilame after two washes.
• the invention also relates to a mechanical part characterized in that it comprises an ultra-thin layer as defined above.
• the invention also relates to a method for preparing the ultra-thin layer defined above, characterized in that it comprises immersing the substrate in a solution of the compound of formula AB in water, or a mixture of water and protic solvent such as, for example, 2-propanol. This process does not use a fluorinated solvent and is therefore respectful of the environment.
• Octadecylisocyanate (668 mg, 2.26 mmol) was dripped into a solution of 3-hydroxy-tyramine hydrochloric acid (428 mg, 2.26 mmol) and N-methyl-morpholine (372 ⁇ l). ) in DMF (5 ml). The mixture was stirred under a nitrogen atmosphere for 6 hours. Water (50 ml) was added and the white precipitate formed was filtered and washed with water (10 ml) and acetone (10 ml). Recrystallization from acetone (160 ml) at -20 ° C gave 870 mg of white powder.
• SuSoS2 (0.052 mmol) 33 mg was dissolved in 35 ml of 2-propanol in a graduated 100 ml flask and shaken until completely dissolved. Ultrapure water was added to the mark and shaken vigorously, which increased the temperature of the solution. After returning the solution to room temperature, a few drops of water were added to adjust the volume to 100 ml. The solution was sonicated for 10 seconds to degas it and allow complete mixing of water and 2-propanol.
• the samples of gold, polished steel, aluminum, titanium oxide and ruby were cleaned in a UV / ozone chamber for 30 minutes and immersed overnight in the SuSoS1 or SuSoS2 solution.
• the samples were then immersed in 2-propanol for 10 seconds, rinsed with additional 2-propanol and dried with a stream of nitrogen.
• the surfaces were lightly polished with a wipe soaked in 2-propanol, rinsed with additional 2-propanol and dried with nitrogen flow.
• X-ray photoelectron spectroscopy (XPS) analysis shows that the SuSoS1 and SuSoS2 molecules are present on all surfaces by the detection of N and F elements (for the SuSoS2 molecule).
• Example 5 Comparison of ultra-thin layers formed by self-assembly of SuSoS2 and Fixodrop FK-BS on surfaces of gold, polished steel and ruby.
• An ultra-thin layer of SuSoS2 is coated with substrates of gold, polished steel and ruby as described in Example 3.
• the surface appearance is excellent for gold and ruby: layer is invisible and no mark is visible due to the deposit.
• Fixodrop FK-BS An ultra-thin layer of Fixodrop FK-BS is coated with gold, polished steel and ruby substrates as specified by the manufacturer by dipping the substrates in a solution of tetradecafluorohexane.
• the thickness of this layer measured by ellipsometry on gold is 0.66 ⁇ 0.01 nm for SuSoS2 and 1.70 ⁇ 0.04 nm for Fixodrop.
• the contact angles in advance with water, hexadecane, diodomethane and ethylene glycol were measured by dynamic contact angle measurement or direction finding according to a technique similar to that used in Example 4.
• SuSoS2 For gold, steel and ruby, the layer formed with SuSoS2 shows a dispersive character only, as expected for a molecule of this type.
• the surface energy seems to vary with the material, but is in any case below 20 mJ / m 2 .
• the weakest energy (and therefore a priori the best holding) is obtained for steel, followed by ruby and gold.
• the spreading of the lubricants on a surface is characterized by measuring the average diameter of a drop of typically 0.5 mm in diameter immediately after the drop has been deposited and after 20 minutes.
• the spread corresponds to the relative variation of the average diameter after 20 minutes.
• a good performance of a lubricant corresponds to a spread of 2% or less. Spreading greater than 10% is noticeable in the eye and is not acceptable.
• the oils used for the tests are a watch oil “941" (Moebius and Fils house, mixture of alkyl-aryl-monooleate and two C 10 -C 13 di-esters, viscosity of 110 cSt at 20 ° C, surface tension of 32.8 mN / m) and a test oil CESNIII (Swiss Laboratory for Watchmaking Research, silicone oil, surface tension of 23.1 mN / m, "Watchmaking Switzerland” No 43, 7.11.1974).
• the contact angle obtained on the ultra-thin layers made with the SuSoS2 molecule is greater than 100 °, the surface energy is less than 20 mJ m -2 , and the spread is less than 1%.
• the layers are resistant to ruby washes, but less well on gold and steel.
• the properties of the ultra-thin layer SuSoS2 are equivalent to those obtained with the commercial product Fixodrop.

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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)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Laminated Bodies (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Other Surface Treatments For Metallic Materials (AREA)

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• 2006
  • 2006-12-01 EP EP20060405505 patent/EP1927649A1/de not_active Withdrawn
• 2007
  • 2007-11-29 US US12/517,121 patent/US20100098926A1/en not_active Abandoned
  • 2007-11-29 WO PCT/CH2007/000603 patent/WO2008064512A1/fr active Application Filing
  • 2007-11-29 WO PCT/CH2007/000604 patent/WO2008064513A1/fr active Application Filing
  • 2007-11-29 EP EP07816286.4A patent/EP2102319B1/de not_active Not-in-force

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