EP0837901A1 - Nanocomposites de fluoropolymere - Google Patents

Nanocomposites de fluoropolymere

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Publication number
EP0837901A1
EP0837901A1 EP96924341A EP96924341A EP0837901A1 EP 0837901 A1 EP0837901 A1 EP 0837901A1 EP 96924341 A EP96924341 A EP 96924341A EP 96924341 A EP96924341 A EP 96924341A EP 0837901 A1 EP0837901 A1 EP 0837901A1
Authority
EP
European Patent Office
Prior art keywords
fluoropolymer
inorganic oxide
integer
group
phase
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.)
Withdrawn
Application number
EP96924341A
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German (de)
English (en)
Inventor
Michael Joseph Michalczyk
Kenneth George Sharp
Charles Winfield Stewart
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Priority claimed from US08/663,821 external-priority patent/US5726247A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0837901A1 publication Critical patent/EP0837901A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • C04B41/4838—Halogenated polymers
    • C04B41/4842—Fluorine-containing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C2240/00—Specified values or numerical ranges of parameters; Relations between them
    • F16C2240/40—Linear dimensions, e.g. length, radius, thickness, gap
    • F16C2240/60—Thickness, e.g. thickness of coatings
    • F16C2240/64—Thickness, e.g. thickness of coatings in the nanometer range

Definitions

  • FLUOROPOLYMER NANOCOMPOSITES FIELP OF THE INVENTIO This invention concerns a fluoropolymer composition having a nanodimensional inorganic component and a linear or branched fluoropolymer component.
  • Typical inorganic fillers can be either particulate or fibrous and can be derived from a variety of materials, including naturally occurring minerals and glass. In most cases, the inorganic filler is discontinuous and can be separated from the polymer matrix by simple mechanical processes or by extraction of the polymer component therefrom.
  • polysilicate or other inorganic oxide networks and particles can be generated from molecular precursors through room temperature hydrolytic and condensation sol-gel reactions. Such reactions generally require cosolvents for the reactants water and the molecular precursor compound, such as a tetraalkoxysilane, and are catalyzed by either acid or base.
  • a particularly interesting and potentially useful construct would involve a three-dimensional poly ⁇ silicate or other inorganic oxide network dispersed throughout a polymer matrix and thus altering polymer properties leading to improvements, such as enhancing durability and adhesion.
  • Certain properties of polymers could be improved, and new properties imparted to polymers by providing hybrid inorganic-organic polymer compositions comprising inorganic phases within polymeric phases.
  • U.S. Patent 5,252,654 describes a polymeric composite of an organic polymer and an inorganic glassy polymer and a process for making such composites which are useful as protective coatings and as nonlinear optical elements .
  • the ' 654 process requires substantial water solubility of the polymer component.
  • TEOS to polysilicate via the aqueous sol-gel process.
  • the microstructure of the resulting material exhibited agglomeration of PTFE in an inorganic matrix with the size of the agglomerates being on a 10- ⁇ m scale.
  • U.S. Patent 5,412,016 describes the formation of inorganic/organic "hybrid" materials using strong carboxylic acids, e.g., formic acid, which rapidly react with an inorganic network precursor to form inorganic networks without the need for either cosolvents or water as a reactant. No fluorine-bearing network precursors or fluorinated solvents are disclosed.
  • the only tractable solvents for highly fluorinated polymers are fluorinated solvents such as perfluoroaliphatic, polyfluoroaliphatic and perfluoroaromatic solvents which are non-solvents for reactants water, the molecular precursor compound, and acidic or basic catalysts generally used to promote inorganic network formation via conventional sol-gel chemistry.
  • the present invention provides chemistry to enable inorganic oxide precursors to polymerize in a fluorinated solvent medium and to then generate organic/inorganic "hybrid" nanocomposites in which the organic portion is a soluble fluoropolymer and the size of any particles with an inorganic phase is on a nanometer scale, i.e., less than about 75 nm.
  • a process of the present invention can work with these highly fluorinated solvent systems because water is not necessary as an initial reagent and a strong carboxylic acid, such as trifluoroacetic (TFA) , which is readily soluble in the fluorinated solvents of interest, can promote the reaction of inorganic oxide precursors without additional catalysts.
  • a strong carboxylic acid such as trifluoroacetic (TFA)
  • TFA trifluoroacetic
  • the nanocomposite of the present invention is an improvement over unmodified fluoropolymers and prior attempts to incorporate an inorganic phase within fluoropolymers in that it has been found hereunder that certain fluoropolymers when incorporated with an inorganic oxide phase generated from fluorine-bearing inorganic oxide precursors yield a nanocomposite having higher abrasion resistance and displaying better adhesion to oxide surfaces than that of the fluoropolymer by itself.
  • the inorganic oxide phase of the nanocomposites of the present invention either has no discernible particle (s) or substantially all particle (s) having a particle size of less than about 75 nm.
  • the present invention provides a fluoropolymer nanocomposite comprising (a) a fluoropolymer phase comprising at least one fluoropolymer; and (b) a partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase and said inorganic oxide phase either exhibiting no particles or substantially all particles present in the inorganic oxide phase having a particle size of less than about 75 nm; the fluoropolymer and the inorganic oxide precursor being soluble in a fluorinated solvent.
  • the present invention also provides a process for the preparation of a fluoropolymer nanocomposite comprising (a) a fluoropolymer phase comprising at least one fluoropolymer; and (b) a partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase and exhibiting no particles or substantially all particles having a particle size of less than about 75 nm; comprising: (a) contacting at least one fluoropolymer soluble in a fluorinated solvent with at least one inorganic oxide precursor soluble in the fluorinated solvent and an optional gelling agent in the presence of the fluorinated solvent to form a solution; (b) allowing the inorganic oxide precursor to partially or fully cross-link to form an inorganic oxide phase dispersed within a fluoropolymer phase; and
  • the present invention further provides a coating composition, comprising a fluoropolymer nanocomposite, said fluoropolymer nanocomposite comprising, a fluoropolymer phase comprising at least one fluoropolymer, and at least one partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase, said inorganic oxide phase exhibiting either no particles or substantially all particles present in the inorganic oxide phase having a particle size of less than about 75 nm, the fluoropolymer and the inorganic oxide precursor being soluble in a fluorinated solvent.
  • the present invention also provides a coated substrate wherein the coating comprises a fluoropolymer nanocomposite, said fluoropolymer nanocomposite comprising, a fluoropolymer phase comprising at least one fluoropolymer, and at least one partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase, said inorganic oxide phase exhibiting either no particles or substantially all particles present in the inorganic oxide phase having a particle size of less than about 75 nm, the fluoropolymer and the inorganic oxide precursor being soluble in a fluorinated solvent.
  • a fluoropolymer nanocomposite comprising, a fluoropolymer phase comprising at least one fluoropolymer, and at least one partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase
  • the present invention also provides a coated substrate wherein the coating is a multilayer coating comprising: a primer, a top coat, and optionally one or more intermediate coats between the primer and the topcoat, wherein the topcoat is a fluoropolymer and the primer is a coating comprising, a fluoropolymer nanocomposite, said fluroropolymer nanocomposite comprising, a fluoropolymer phase comprising at least one fluoropolymer, and at least one partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase, said inorganic oxide phase exhibiting either no particles or substantially all particles present in the inorganic oxide phase having a particle size of less than about 75 nm, the fluoropolymer and the inorganic oxide precursor being soluble in a fluorinated solvent.
  • the coating is a multilayer coating comprising: a primer, a top coat, and optional
  • the present invention further provides an anti- reflective coating for an optoelectronic display device, comprising the fluoropolymer nanocomposite described above; an interlayer dielectric coating having improved dimensional stability and improved bonding to metal top coats after thermal cycling, comprising the fluoropolymer nanocomposite described above; an article of cookware comprising a metal substrate coated with a scratch-resistant, non-stick coating system wherein said coating system comprises a primer applied to a metal substrate and a topcoat adhered to said primer, said primer comprising the fluoropolymer nanocomposite described above; and an article of cookware comprising a metal substrate coated with a scratch-resistant, non-stick coating system wherein said coating system comprises a primer applied to a metal substrate and a topcoat adhered to said primer, said primer comprising a fluoropolymer nanocomposite as described above.
  • Fig. 1 is a graph comparing the x-ray scattering intensity of a fluoropolymer nanocomposite of the present invention (depicted by squares) comprising a copolymer of tetrafluoroethylene and 2,2- bis (trifluoromethyl) -4, 5-difluoro-1, 3-dioxole, namely "TEFLON" AF, in hexafluorobenzene and an inorganic network derived from ⁇ i(OCH 2 CF 3 ) 4 (FES) with a composition (depicted by circles) comprising
  • Fig. 2 is a graph showing the x-ray scattering intensity of a composition comprising fumed silica (OX-50), "TEFLON” AF and hexafluorobenzene for determination of particle size distribution.
  • Fig. 3 is a transmission electron microscopy micrograph showing particles of the inorganic oxide phase of a fluoropolymer nanocomposite of the present invention prepared using Si (OCH 2 C 3 F 7 ) 4 (FBS) and "TEFLON” AF dissolved in perfluoro (butyl THF) (FC-75) .
  • Fig. 4 is a transmission electron microscopy micrograph showing silica particles of a composition prepared using "TEFLON” AF and OX-50 fumed silica.
  • Fig. 3 is a transmission electron microscopy micrograph showing particles of the inorganic oxide phase of a fluoropolymer nanocomposite of the present invention prepared using Si (OCH 2 C 3 F 7 ) 4 (FBS) and "TEFLON” AF dissolved in perfluoro (butyl THF) (FC-75) .
  • Fig. 4 is a transmission electron microscopy micrograph showing silica particles of a composition prepared using "TEFLON” AF
  • FIG. 5 is a graph showing the results of an extrusion of an abrasive polyethylene through stainless steel capillary dies coated with a fluoropolymer nanocomposite of the present invention (circles) (Example 27) , an uncoated control (squares) (Control A: Example 26) , fluoropolymer applied as a top coat over the fluoropolymer nanocomposite (triangle)
  • the fluoro polymer nanocomposite is prepared using a copolymer of tetrafluoroethylene (TFE) and 2, 2-bis (trifluoromethyl) - 4,5-difluoro-l,3-dioxole, (i.e., "TEFLON” AF 1601) and (C 3 F 7 CH 2 0) 3 SiCH 2 CH 2 (CF 2 ) 6 CH 2 CH 2 Si(OCH 2 C 3 F 7 ) 3 .
  • TFE tetrafluoroethylene
  • 2-bis (trifluoromethyl) - 4,5-difluoro-l,3-dioxole i.e., "TEFLON” AF 1601
  • C 3 F 7 CH 2 0 3 SiCH 2 CH 2 (CF 2 ) 6 CH 2 CH 2 Si(OCH 2 C 3 F 7 ) 3 .
  • the topcoat is a copolymer of TFE and hexafluoro- propylene (HFP) (i.e., "TEFLON” T9050, a "TEFLON” FEP copolymer) which has a melting point of 260°C and contains 15% HFP.
  • HFP hexafluoro- propylene
  • the fluoropolymer nanocomposites of the present invention comprise at least one partially or fully cross-linked inorganic oxide phase dispersed in a fluoropolymer phase, the inorganic oxide phase exhibiting no discernible particles or if any particles are present (i.e., discernible) substantially all of said particles have a particle size of less than about 75 nm.
  • the fluoropolymer nanocomposites of the present invention comprise wet gels and dried material.
  • wet gel is meant that there is a fluorinated solvent surrounding the fluoropolymer and inorganic oxide phases. Upon drying of the wet gel, solvent, volatile by-products and residual reactants can be removed to yield a dried fluoropolymer nanocomposite. Drying may also promote further network bonding, e.g., condensation reaction, within the inorganic oxide phase. Nanocomposite as used herein excludes polymer blends, block co-polymers and conventional inorganic filled polymers.
  • inorganic oxide phase refers to the material resulting from the condensation of the molecular inorganic oxide precursor which becomes partially or fully cross-linked and is dispersed within the fluoropolymer phase.
  • the inorganic oxide phase can be a continuous network without discernible particles or if particles are present substantially all of said particles have particle (s) a size less than about
  • Particle size is the diameter of (equivalent) spheres.
  • X-ray scattering or transmission electron microscopy techniques can be used to determine whether the inorganic oxide phase exhibits any particles or not, and can be used to determine the particle size of any particles that are discernible. Failure to detect particles with these techniques is consistent with the inorganic oxide phase exhibiting no particles.
  • the inorganic oxide phase has either no discernible particles or if particles exist substantially all of the particles have a particle size of less than about 50 nm. Both types of inorganic oxide phase (no particles and particles ⁇ 75 nm) are prepared from at least one inorganic oxide precursor.
  • atoms from the inorganic oxide precursors bond to form a partially or fully cross- linked system.
  • partially crosslinked is meant that some of the bonds of the inorganic oxide phase may not be part of the skeleton of the inorganic oxide phase, e.g., some may have nonbridging groups such as -OH or -OR, wherein R are fluoroalkoxy groups, as defined above, attached to them. Essentially none of the bonds of the inorganic oxide phase are covalently bound to the fluoropolymer of the nanocomposite unless specifically provided for and enabled by the chemistry.
  • the inorganic oxide phase can be continuous forming a semi-interpenetrating network with the fluoropolymer wherein the inorganic oxide phase is dispersed substantially uniformly throughout the fluoropolymer phase and particles are not discernible via x-ray scattering or transmission electron microscopy techniques, or the inorganic oxide phase can be discontinuous and form a heterogeneous mixture of extremely small particles within the fluoropolymer phase, wherein substantially all of said particles have a particle size of less than about 75 nm.
  • substantially all is meant that for fluoro ⁇ polymer nanocomposites in which the inorganic phase is present primarily as particles, at least 90%, preferably at least 95%, of those particles having a particle size of less than about 75 nm.
  • si-interpenetrating network is used herein to mean a polymer composition wherein a linear or branched organic polymer and a partially or fully cross-linked inorganic network have been combined to form a nanocomposite with essentially no covalent bonding between the organic polymer and the inorganic polymer.
  • Preferred inorganic oxide phases comprise silica, titania, alumina, and zirconia.
  • the most preferred inorganic oxide phase comprises silica.
  • inorganic oxide precursors Compounds of aluminum, boron, germanium, silicon, tin, titanium and zirconium can be useful as inorganic oxide precursors in the present invention.
  • the inorganic oxide precursor of the present invention must be soluble in a fluorinated solvent.
  • the inorganic oxide precursor will necessarily contain fluorinated groups .
  • prepared from at least one inorganic oxide precursor is meant that at least one inorganic oxide precursor will be used in the preparation of the inorganic phase along with other reactants as needed or desired.
  • the inorganic oxide precursor can comprise compounds having the formula (R f C a H 2a 0) n MR 4 _ n , wherein M is Ge, Si or Sn, or (R f C a H 2a O) n M 1 R 4 _ n (HOR) ⁇ _. ⁇ , wherein M 1 is Ti or Zr and q 1 is 0 or 1; a is 1 to 10; and n is 2, 3 or 4, and R f and R are as defined in Formula I.
  • the inorganic oxide precursor can also comprise a compound having the formula (R f C a H 2a O) n ⁇ M'R 3 _ n , wherein: M 1 is Al or B; n' is 1, 2, or 3; and a, R f and R are as defined in Formula I.
  • M is Si, Al, Ti or Zr
  • D is a chelating ligand, optionally fluorinated
  • en is a silicon, aluminum, titanium or zirconium coordination number, being in each case an integer
  • Chelating compounds suitable for use in the present invention are chemicals containing chelating ligands capable of bonding to silicon, aluminum, titanium or zirconium through two or more oxygen atoms.
  • Illustrative of compounds containing bidentate chelating ligands are those which are derived from 1,1,1,5,5, 5-hexafluoro-2, 4-pentanedione.
  • Illustrative of compounds containing tridentate chelating ligands is triethanolamine.
  • Representative examples are Si(CF 3 C(0)CHC(0)CF 3 ) 2 (OCH 2 Rf)2 Ti(OCH 2 R f ) 4 , Al (OCH 2 R f ) 3 and A1(CF 3 C(0)CHC(0)CF 3 ) (OCH 2 )R f ) .
  • Linear and branched fluoroalcohols can be used in the preparation of compounds useful in the present invention; however, linear fluoroalcohols are preferred.
  • various fluorine-bearing silanes are used as the inorganic oxide precursors in the formation of the inorganic oxide phase.
  • the silanes can be substituted, for example, with polyfluoroalkoxy groups or fluoroalkyl groups .
  • the silanes can be di-, tri- and tetrafunctional molecules, dioxolanes, or "stars", compounds having multiple arms terminating in di- and trifluoroalkoxy functionality.
  • the inorganic oxide precursor can also be a fluorinated oligomeric compound such as a polysilicate.
  • the inorganic oxide precursor is selected from the group consisting of a compound of formula I, II, IIA, III, IIIA, IV, V, VA and VI as described below:
  • R f has up to about 18 carbon atoms and is selected from the group consisting of:
  • R is selected from the group consisting of: hydrogen, C x to about C 8 alkyl, C a H 2a R f , C ⁇ to about C 8 alkoxy, C-*_ to about C 10 carboxy, C to about C 10 fluorocarboxy, C 2 to about Cg alkenyl, C 2 to about C 8 alkynyl, C 6 H 5 aryl, and aralkyl; t is 1, 2, 3 or 4; and a is an integer from 1 to about 10; II: a compound having the formula:
  • X is at least one organic link selected from the group consisting of:
  • 1,4-C 6 H 10 (Y) 2 ;
  • 1,2,4-C 6 H 9 (Y) 3 ; 1.2,3-CgH c ,(Y) 3 ; 1,3,5-C 6 H 9 (Y) 3 ;
  • 1,2,3,4-C 6 H 8 (Y) 4 ;
  • R f has up to about 18 carbon atoms and is selected from the group consisting of: (a) ' C x to about C 18 perfluoroalkyl;
  • R 1 is C x to about C 8 alkyl or aryl
  • R 2 to R 9 are each independently hydrogen, C**_ to about C 8 alkyl, or aryl, provided that at least one of R 4 to R 7 is hydrogen
  • m is 0, 1 or 2
  • k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero
  • a is an integer from 1 to about 10
  • b is an integer from 1 to about 10
  • c is 1, 2 or 3
  • n is an integer greater than or equal to 2
  • IIA a compound having the formula: X(R 10 Si(OC a H 2a R f ) 2 ) n (IIA) wherein:
  • X is at least one organic link selected from the group consisting of: (a) R l m SiY 4 _ m ; (b) ring structures IIAb(i) IIAb(ii) IIAb(iii)
  • R f has up to about 18 carbon atoms and is selected from the group consisting of:
  • R 1 is C-
  • R 2 to R 9 are each independently hydrogen, C-j_ to about C 8 alkyl, or aryl, provided that at least one of R 4 to R 7 is hydrogen;
  • R 10 is C x to about C 8 alkyl or C a H 2a R f ; m is 0, 1 or 2; k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero; a is an integer from 1 to about 10; b is an integer from 1 to about 10; c is 1, 2 or 3; and n is an integer greater than or equal to 2; III: a compound having the formula:
  • R 13 is C x to about C 8 alkyl, C x to about C l0 carboxy, C to about C 10 fluorocarboxy, halogen or C a H 2a R f ;
  • R f has up to about 18 carbon atoms and is selected from the group consisting of:
  • each R optionally substituted with one or more hydrogen; a is an integer from 1 to about 10; v is an even integer from 2 to about 14; and
  • Y is -(CR 2 R 3 ) k CR R 5 CR 6 R 7 (CR 8 R 9 ) h -
  • R 1 is C x to about C 8 alkyl or aryl
  • R 2 to R 9 are each independently hydrogen, C to about C 8 alkyl, or aryl, provided that at least one of R 4 to R 7 is hydrogen
  • k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero
  • IIIA a compound having the formula:
  • R 10 is C- L to about C 8 alkyl or C a H 2a R f ;
  • R f has up to about 18 carbon atoms and is selected from the group consisting of:
  • each R f optionally substituted with one or more hydrogen; a is an integer from 1 to about 10; v is an even integer from 2 to about 14; and
  • Y is -(CR 2 R 3 ) k CR 4 R 5 CR 6 R 7 (CR 8 R 9 ) n -
  • R 13 is C x to about C 8 alkyl, C to about C 10 carboxy, C-*_ to about C 10 fluorocarboxy, halogen or C a H 2a R f ;
  • R 1 is x to about C 8 alkyl or aryl
  • R 2 to R 9 are each independently hydrogen, C-*_ to about C 8 alkyl, or aryl, provided that at least one of R 4 to R 7 is hydrogen; and k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero;
  • R f has up to about 18 carbon atoms and is selected from the group consisting of:
  • halogen selected from the group consisting of chlorine, bromine and iodine
  • C 1 to about C 8 alkoxy (i) C to about C 8 fluoroalkoxy; and (j) C to about C 10 carboxy or fluorocarboxy; and each of Q and T independently is selected from the group consisting of (k) halogen selected from the group consisting of chlorine, bromine and iodine;
  • V a dioxolane having the formula:
  • R 13 is C to about C 8 alkyl, C x to about C 10 carboxy, C x to about C 10 fluorocarboxy, halogen or C a H a R f ;
  • R f has up to about 18 carbon atoms and is selected from the group consisting of:
  • R 11 and R 12 are each independently selected from C x to C 3 fluoroalkyl or fluorine; a is an integer from 1 to about 10; and Y is -(CR 2 R 3 ) k CR R 5 CR 6 R 7 (CR 8 R 9 ) h - R 2 to R 9 are each independently hydrogen,
  • VA a dioxolane having the formula:
  • R 10 is C to about C 8 alkyl or C a H 2a R f ;
  • R f has up to about 18 carbon atoms and is selected from the group consisting of:
  • R 11 and R 12 are each independently selected from C x to C 3 fluoroalkyl or fluorine; a is an integer from 1 to about 10; and Y is -(CR 2 R 3 ) k CR R 5 CR 6 R 7 (CR 8 R 9 ) h - R 13 is C to about C 8 alkyl, C to about C 10 carboxy, C to about C 10 fluorocarboxy, halogen or C a H 2a R f ; R 2 to R 9 are each independently hydrogen,
  • y is an integer from 2 to about 10;
  • R f has up to about 18 carbon atoms and is selected from the group consisting of (a) C x to about C 18 perfluoroalkyl; (b) -[CF 2 CF(CF 3 )0] r -CF 2 -CF 2 -CF 3 , wherein r is an integer of at least 1;
  • fluorinated oligomeric compounds are polysilicates selected from the group consisting of a compound of formula VII, VIII and IX as described below:
  • z is a number from about 0.5 to about 3.0; a is an integer from 1 to about 10; and R f has up to about 18 carbon atoms and is selected from the group consisting of:
  • Ar is a divalent aromatic radical
  • R f has up to about 18 carbon atoms and is selected from the group consisting of:
  • each R f optionally substituted with one or more hydrogen.
  • the R f group can be a fluoroalkyl or perfluoroalkyl group, which can be either normal or branched, and has up to about 18 carbon atoms, preferably one to eight carbon atoms, especially preferred one to three carbon atoms .
  • Normal perfluoroalkyl groups include, for example, trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorodecyl, perfluorododecyl, and perfluoro- octadecyl.
  • Fluorosilanes of formulas I-VI where R f has more than eighteen carbon atoms are considered less practical to synthesize, although such fluorosilanes would be perfectly suitable in all applications contemplated for this class of compounds.
  • a typical suitable branched fl ' uoroalkyl group is -CH 2 -C(CF 3 ) 2 -CF 2 -CF 2 -CF 3 .
  • the R f groups also can be certain perfluoro- (alkyleneoxy) alkyl) radicals . These include perfluoro- (methylene (polymethyleneoxy)methyl) radicals (c) and perfluoro ( (polyisopropyleneoxy)propyl) radicals (b) .
  • Each R f can be optionally substituted with one or more hydrogen provided that the inorganic oxide precursor remains soluble in a fluorinated solvent. Thus, it may not be possible for every fluorine of the R f group to be replaced with hydrogen.
  • R f is preferably a C x to about C 8 perfluoroalkyl group; most preferably, CF 3 or C 3 F 7 .
  • R is preferably a lower alkyl of 1 to about 6 carbon atoms or a lower alkoxy group of 1 to about 6 carbon atoms; most preferably methyl, ethyl, methoxy or ethoxy.
  • n is 3 or 4, and a is preferably 1 or 2.
  • the alkenyl group is vinyl or allyl.
  • the preferred aralkyl is benzyl and the preferred aryl is phenyl.
  • X is preferably (a) R 1 m SiY 4 _ m or (c) R x m Si (OSi (CH 3 ) 2 Y) 4 _ m .
  • the most preferred organic link X is where m is 0, k is 0 or 1 , h is 0 or 1, and all of R 2 to R 9 are hydrogen.
  • R f is preferably CF 3 , C 2 F 5 or n-C 3 F 7 .
  • Z is preferably CH 3 ; the preferred aralkyl being benzyl and the preferred aryl being phenyl.
  • n is preferably 2-6; most preferably 2, 3, or 4.
  • a is preferably 1 or 2, most preferably 1.
  • OR 13 is preferably a fluoroalkoxy group; most preferably -OCH 2 CF 3 , -OCH 2 C 2 F 5 or -OCH 2 C 3 F 7 .
  • R 2 to R 9 are preferably hydrogen, and v is preferably 4, 6, 8 or 10.
  • Representative examples of compounds of formula III comprise (C 3 F 7 CH 2 0) 3 Si (CH 2 ) 2 (CF 2 ) 6 (CH 2 ) 2 Si (OCH 2 C 3 F 7 ) 3 , (CF 2 ) 6 ( (CH 2 ) 2 Si(OCH 2 CF 3 ) 3 ) 2 , and (CF 2 ) 6 ( (CH 2 ) 2 Si (OCH 2 CH 3 ) 3 ) 2 .
  • R 10 is preferably C to C 3 alkyl; most preferably methyl.
  • R 10 is preferably C 6 F 13 ' n-C 8 F 17 and n-C 10 F 21 .
  • Ar in formula IV, VI and IX above can be any divalent aromatic radical, as this term is understood in the art, including those comprising six-, ten-, and fourteen-carbon aromatic rings, including, for example, radicals remaining when two ring hydrogen atoms are removed from an aromatic compounds such as benzene, napthalene, toluene, xylene, and anthracene, or from a five-membered or six-membered heterocyclic ring containing oxygen or nitrogen atoms such as, for example, furan, pyrrole, and pyridine.
  • Biphenyl and triphenyl groups are also included within the definition of Ar.
  • Ar is preferably phenyl.
  • Preferred alkoxy groups of W, Q and T are methoxy and ethoxy groups .
  • Preferred fluoroalkoxy groups of W, Q and T are -CH 2 CF 3 , -CH 2 C 2 F 5 and -CH 2 C 3 F 7 .
  • W, Q and T may also comprise other groups attached through hydrolyzable bonds such as carboxylates and oximes .
  • Suitable compounds of formula IV comprise C 8 F 17 C 6 H 4 Si (OCH 3 ) 3 ; C 10 F 21 C 6 H 4 Si (OCH 3 ) 3 ;
  • R f is preferably CF 3 , C 2 F 5 or C 3 F 7 .
  • Suitable compounds of formula V comprise
  • Synthesis of compounds of formula I can be afforded by alkoxylation of chlorosilanes or by alcohol exchange reactions .
  • Compounds of formula I are thus prepared by contacting a molar excess of fluoroalcohol having the formula R f C a H 2a OH, wherein R f and a are defined as above, with SiCl 4 , Si(OR 1 ) 4 , R 1 SiCl 3 , R 1 Si(OR 1 ) 3 or R 1 2 SiCl 2 , wherein R 1 is C x to about C 8 alkyl, to form the corresponding fluoroalkoxysilanes .
  • the fluoroalcohol is typically added dropwise to the silane compound or alcohol compound, with an optional acid or base catalyst for Si(OR 1 ) 4 or R 1 Si(OR 1 ) 3 which is being stirred, over a period of time ranging from 30 min to about 4 hours .
  • the reaction temperature is in the range of about -15°C to about 10°C, preferably, about 0°C and is eventually raised to room temperature (25°C) .
  • the fluoroalcohol reacts to replace all of the chlorine atoms of the silicon chloride, or 1, 2, 3 or all of the alkoxy groups of the silicon alkoxide compound with fluorinated alkoxy groups, with liberation of hydrogen chloride or alcohol.
  • the fluoroalkoxysilane product may be recovered in purified state by removal of solvent and residual alcohol followed by distillation of the crude reaction product. Hydrogen chloride by-product is normally removed by purging the reaction mixture with dry inert gas, such as argon.
  • Mixtures comprising compounds of Formula I, II, IIA, III, IIIA, IV, V, VA or VI and a compound such as an inorganic oxide precursor not normally soluble in or capable of gelation by itself in the fluorinated solvent, e.g., (R f C a H 2a O) t .Si _ t . , where R is alkoxy and t' is 0, 1 or 2, can be used in the present process as long as the mixtures are soluble in the fluorinated solvent.
  • the at least one inorganic oxide precursor can comprise a mixture of inorganic oxide precursors, each precursor being soluble or insoluble in the fluorinated solvent provided the mixture is soluble in the fluorinated solvent.
  • Such a mixture can be prepared, for example, from tetraethoxysilane and heptafluorobutanol to yield a mixture of formula I silanes, i.e., (C 3 F 7 CH 2 0) t Si (OCH 2 CH 3 ) 4 _ t , or from tetraethoxysilane and C 8 F 17 C 6 H 4 Si (OCH 3 ) 3 to yield a mixture of silanes from formula I and formula IV.
  • This is generally not feasible in an aliphatic fluorinated solvent; however, hexafluorobenzene can be an effective solvent.
  • Synthesis of the compounds of formula II and IIA are afforded from hydrosilylation reactions, i.e., an addition reaction between a compound containing a Si-H group with a compound containing aliphatic unsaturation, such as an alkene, in the presence of a catalyst or free radical initiator.
  • Either precursor segment can contain the vinyl or other unsaturated group capable of Si-H addition.
  • Equations denoted A or B above are chosen depending upon the commercial availability of the starting reagents .
  • Specific sources of reactants are listed hereinafter just prior to the Examples.
  • a transition metal catalyst such as platinum, or a free radical initiatior is employed in an effective amount.
  • suitable free radical initators include "VAZO" azo compounds available from E. I. du Pont de Nemours and Company, Wilmington, DE.
  • reaction time is typically from about 4 hours to about 24 hours.
  • solvent is not required in these reactions .
  • Suitable solvents which may be employed are those capable of dissolving the reactants, such as toluene, and which do not interfere with the reaction or generate desirable by-products.
  • the desired product can be isolated by any means known to those skilled in the art. Preferably the desired product is isolated by removal of volatiles under reduced pressure.
  • Synthesis of the compounds of formula III and IIIA can also be realized by insertion of unsaturated trifluoroalkoxy-silanes or trihalosilanes into the C-I bond of I(CF 2 ) V I, followed by reduction of the C-I to C-H using standard organic reduction reagents as shown in Equation 11B.
  • suitable reagents are zinc metal, tri-n-butyl tin hydride or samarium iodide.
  • Synthesis of compounds of formula VI are prepared by methods known in the art for hydrocarbon silanes (see, Kirk-Othmer, Encyclopedia of Chemical Technology, third edition, vol. 20, and Mehrota, R. C, Pure Appl. Chem., 13, 111; 1966) .
  • the preferred method is by reacting the corresponding perfluoroalkyl trichloro- silane with the proper alcohol, such as methanol, ethanol, or 1, 1, 1-trifluoroethanol, for example, according to the following equation: F(CF 2 ) 0 CH 2 CH 2 SiCl 3 + 3 HOCH 3 ⁇ F(CF 2 ) 0 CH 2 CH 2 Si(OCH 3 ) 3 + 3 HCl where o is 6-18.
  • the fluorinated trichlorosilane starting materials for the above reaction can be prepared by one of several recognized procedures; for example, see McBee, E. T., J. Am. Chem. Soc, 79, 2329 (1957); Adv. Organomet. Chem., 17, 407 (1970); U.S. Patent 3,012,006; U.S. Patent 4,089,882, or U.S. Patent 4,549,003.
  • F (CF 2 ) 6 CH 2 CH 2 Si (OCH 2 CH 3 ) 3 is commercially available from PCR Incorporated, P.O. Box 1466, Gainesville, FL 32602 (catalog #12303-4) .
  • the compounds of formula VII are prepared by dissolving a fluorine-bearing silane, such as one having the formula Si(OCH 2 R f ) 4 , wherein R f is as defined in formula VII, or mixed silanes, such as
  • IPA isopropyl alcohol
  • a soluble source of fluoride ion, such as CsF is added to the solution along with less than a 1.5:1 molar excess of water.
  • the solution is maintained, with optional heating, until the water has substantially consumed.
  • the by-product alcohols and any unreacted water are then removed from the system by, for instance, distillation.
  • the remaining material is an oligomeric silicate with sufficient residual fluorine-bearing groups to be soluble in fluorinated solvents.
  • polysilicates of formula VII can be made by combining a fluorine-bearing silane such as Si (OCH 2 C 3 F 7 ) 4 (FBS) with a stoichiometric deficiency (i.e., ⁇ 2:1) for trifluoroacetic acid (TFA) or other strong fluorocarboxylic acid.
  • FBS fluorine-bearing silane
  • TFA trifluoroacetic acid
  • the solution will generally be heated so as to promote extensive reaction between the silane and acid. Reaction by-products (ester, alcohol and any unreacted acid) are then removed, for example, by distillation.
  • Preparation of the oligomeric compounds of formulas VIII and IX can proceed in like fashion using compounds of formula IV and VI. In the altnerative process using a strong fluorocarboxylic acid, heating is optional.
  • Formulas VII, VIII and IX are idealized formulas which correspond to ' 100% crosslinking of the SiOH group; however, there can be residual uncrosslinked SiOH groups during preparation.
  • z is the molar ratio of water or other gelling agent to silane and ranges from about 0.5 to about 3.0-.
  • R f is preferably CF 3 , C 2 F 5 or C 3 F 7 for formula VII and C 6 F 13 , n-C 8 F 17 and n-C 10 F 21 for formulas VIII and IX.
  • fluoropolymer phase is meant at least one fluoropolymer, wherein fluoropolymer refers to a partially fluorinated or perfluorinated organic polymer or a copolymer generated from at least one partially fluorinated or perfluorinated monomer.
  • the fluoro ⁇ polymer can be linear or branched but not substantially crosslinked.
  • the fluoropolymer used in the present invention must be substantially soluble in one or more fluorinated solvents.
  • the fluoropolymer can comprise hydrogen, oxygen and/or chlorine substituents provided the luoropolymer remains substantially soluble in a fluorinated solvent.
  • Fluoropolymers useful in the present invention comprise polytetrafluoroethylene (PTFE) , and copolymers derived from tetrafluoroethylene (TFE) and other fluoromonomers such as hexafluoro- propylene (HFP) ; perfluoromethylvinylether; perfluoro- ethylvinylether; perfluoro (2,3 dimethyl dioxole) ; and hexafluoropropylene oxide.
  • PTFE polytetrafluoroethylene
  • TFE tetrafluoroethylene
  • HFP hexafluoro- propylene
  • perfluoromethylvinylether perfluoro- ethylvinylether
  • perfluoro (2,3 dimethyl dioxole) perfluoro (2,3 dimethyl dioxole
  • hexafluoropropylene oxide hexafluoropropylene oxide
  • the most preferred fluoropolymers are the copolymers derived from TFE and HFP; TFE and 2, 2-bis (trifluoromethyl) -4, 5-difluoro-1,3- dioxole; and TFE and a perfluoroalkylvinylether.
  • fluorinated solvent which solvent can be either poly- fluorinated or perfluorinated; preferably perfluorinated.
  • Perfluoroaliphatic e.g., perfluoro- (butyl THF)
  • polyfluoroaliphatic e.g., C 3 F 7 OCHFCF 3
  • perfluoroaromatic e.g., hexafluorobenzene
  • Preferred solvents comprise perfluoro (butyl THF), also known as "FLUORINERT" FC-75;
  • FLUORINERT FC-40, a mixture of perfluorotrialkylamines containing mostly perfluoro (di (n-butyl)methylamine; perfluorophen- anthrene, e.g., "FLUTEC” PP-11; C 3 F 7 OCHFCF 3 , e.g.,
  • fluoropolymer and inorganic oxide precursor selected for the preparation of a particular fluoropolymer nanocomposite must be soluble in or miscible with a common fluorinated solvent system.
  • the present invention further provides a process for preparing the fluoropolymer nanocomposite described above.
  • the fluoropolymer nanocomposite can be prepared by contacting at least one fluoropolymer soluble in a fluorinated solvent with at least one inorganic oxide precursor soluble in the fluorinated solvent and an optional gelling agent in the presence of the fluorinated solvent. Mixtures of inorganic oxide precursors where some are soluble in the fluorinated solvent and others are not can be used provided the mixture is soluble in the fluorinated solvent. This can be accomplished in a variety of ways.
  • the fluoropolymer nanocomposite can be prepared by dissolving at least one fluoropolymer, as described above, in a first fluorinated solvent to form a first solution.
  • At least one inorganic oxide precursor, as described above can then be dissolved in a second fluorinated solvent, which solvent can be and is preferably the same as the first solvent, to form a second solution. If the second solvent is different from the first solvent, the second solution must be soluble in or miscible with the first solution.
  • the first solution is then contacted, for example by mixing, with the second solution.
  • the optional gelling agent can be added either to the first solution, to the second solution, or to the contacted first and second solutions .
  • the gelling agent must be soluble in or miscible with the first solution unless the gelling agent is added to the second solution prior to contact with the first solution.
  • Polysilicates developed from the above described fluorine-bearing silanes prior to contact with the dissolved fluoropolymer are also efficacious.
  • a gelling agent such as trifluoroacetic acid which is soluble in a fluorinated solvent, is optional.
  • treatment of a polysilicate with water vapor at an elevated temperature after film deposition is also efficacious.
  • a gelling agent such as formic acid in tetrahydrofuran (THF) may be used.
  • C 8 F 17 C 6 H 4 Si (OCH 3 ) 3 can be converted into a polysilicate by reaction of formic acid in THF or methylene chloride and then added to the dissolved fluoropolymer to form the nanocomposite of the present invention.
  • the inorganic oxide phase is formed within the fluoropolymer phase by allowing the inorganic oxide precursor to partially or fully cross-link.
  • the resultant fluoropolymer nanocomposite is optionally isolated from residual liquid, byproducts, and unreacted starting materials, usually by drying.
  • the inorganic oxide precursor can be dissolved in the first solution comprising the fluoropolymer and then contacted with the gelling agent.
  • the gelling agent is preferably a strong organic carboxylic acid, such as trifluoroacetic acid (TFA) , perfluoropropionic acid, or trifluoromethanesulfonic acid.
  • the gelling agent can also be a fluoride ion source, such as guanidium fluoride or CsF.
  • the gelling agent must be soluble in a fluorinated solvent unless the gelling agent is used to prereact the inorganic oxide precursor prior to contact with the dissolved fluoropolymer.
  • a weight percent ratio of fluoropolymer to inorganic oxide precursor ranging from 1 to 99 is possible.
  • a 60 to 90 fluoropolymer to inorganic oxide precursor weight ratio is used.
  • a 80% to 90% fluoropolymer to inorganic oxide precursor weight percent ratio is used.
  • the mixture After contacting the fluoropolymer solution with the inorganic oxide precursor solution or the prereacted inorganic oxide precursor, the mixture is maintained at a temperature within the range of about 0°C to about 100°C at ambient pressure.
  • Gel time varies with the fluoropolymer, amount of gelling agent, fluorinated solvent, inorganic oxide precursor, and temperature selected.
  • the fluoropolymer nanocomposite of the present invention can be isolated via removal of liquid byproducts and unreacted starting materials, such as solvent, generally by evaporation to yield a monolith glass, gel, film or coating. Drying can be at atmospheric pressure and at a temperature of from about 20°C to about 225°C. Vacuum up to 10 -5 torr or exposure to water vapor at elevated temperatures may also be employed.
  • Particles of an inorganic oxide phase resulting from the solution-grown processes of the present invention are substantially smaller than those resulting from simple dispersion of particulate inorganics or from a combination of an aqueous-based sol-gel and a fluoropolymer dispersion.
  • the fluoro ⁇ polymer nanocomposites of the present invention can comprise continuous inorganic networks which are interpenetrated by linear or branched fluoropolymers.
  • the inorganic oxide phase in the nanocomposites of the present invention can alternatively comprise a particles substantially all of which have a particle size such that when a small angle x-ray procedure described herein is applied to a sample of the nanocomposite, a particle diameter less than about 75 nm is indicated for substantially all of the particles of the inorganic oxide phase.
  • SAXS Small Angle X-ray Scattering
  • a wet gel was used.
  • Particle size can be determined by SAXS, according to the following technique:
  • the SAXS data should be acquired on a high-resolution instrument such as the one originally designed by Bonse and Hart, Zeit . fur
  • the machine can also be fitted with an optional accessory system and the appropriate signal detectors for scanning transmission electron microscopy (STEM) and for reflection scanning electron microscopy (SEM) , in order to be able to access the additional information, e.g., atomic number or Z-contrast, available from the different modes of operation.
  • the CM12 is also equipped with the Link/Oxford Instruments lo-Z (inc F, C, N, O) capable LZ-5 windowless energy dispersive x- ray spectrometer (EDX/EDS) and the associated eXL analysis system (Oxford Instruments, Bucks HP12 3SE, England) . Analyses are possible in TEM and more selectively in the STEM mode of operation. Samples are prepared directly onto carbon filmed 200 mesh copper grid TEM sample supports by dipping them in the suspension and subsequently drying.
  • the high resolution images can be recorded in TEM at primary magnifications of, for example, 35,000x and 100,000x, and be printed with a further enlargement of 3x for final print magnifications of 105,000x and 300,000x, respectively.
  • the electron beam dose can be restricted with careful manipulation of the experiment, by a 50 urn condenser aperture and a small spot size (#5) defocused to fill the field of view.
  • a low light level TV camera is used for focusing, and the photographic exposure times on Kodak 163 film can be 5 to 10 seconds.
  • STEM can be done on the same instrument and samples .
  • Figure 3 shows the TEM photograph of a fluoropolymer nanocomposite coating prepared from FBS with "TEFLON" AF which indicates uniform, spherical particles ranging from 10 to 15 nm. Analyses of the particles confirmed the presence of the elements Si, C, 0 and F. Other continuous inorganic oxide networks may also be present but not images.
  • the present invention can be compared to the composition prepared from fumed silica (OX-50) with "TEFLON" AF as shown in the TEM photograph in Figure 4 which indicates aggregates of large silica particles of the size 100 nm or greater.
  • the fluoropolymer nanocomposites of the present invention are useful as protective coatings, displaying improved adhesion to substrate surfaces while maintaining low surface energy of the unmodified polymer.
  • Durable, adherent coatings on substrates, such as glass, metal, and ceramic incorporate fluoropolymer surface features such as non-sticking, non-soiling, high lubricity and low chemical reactivity.
  • An example is coating metal molds, e.g., for the manufacture of golf balls.
  • the fluoropolymer nanocomposites of the present invention can function both as primers for fluoropolymer overcoats and stand alone coatings. Both systems have shown improved adhesion to glass and abrasion resistance and are stable to oxidation at 300°C in air.
  • the standalone fluoropolymer nanocomposite coatings of the present invention are useful for coating articles requiring anti-fouling, durability, anti-reflective, low dielectric constant, abrasion resistant, chemical resistant, lubricity, release, anti-soiling, anti-staining or reduced surface energy characteristics.
  • These articles can be made of glass; ceramic; amorphous (such as poly(methylmethacrylate) ) or crystalline (such as nylon, polyester film, e.g., "MYLAR” polyester film, or polyimide film, e.g., "KAPTON” polyimide film) plastic; rubber such as silicone rubber or nitrile rubber; elastomer such as copolymers of hexafluoropropylene and vinylidene fluoride, e.g., "VITON” elastomer, copolymers of ethylene and methyl aerylate, e.g., "VAMAC” elastomer or copolymers derived from TFE and PFVME plus optional cure site monomers, such as "KALREZ” or "CHEMRAZ” or ethylene/propylene/hexadiene rubber (EPDM) ; wood; or metal such as stainless steel, copper or brass.
  • amorphous such as poly(methylmethacrylate)
  • crystalline such
  • the standalone coatings can be used to coat a variety of articles, such as lined reactor vessels, heat exchangers, shower doors, shower heads, lenses, head lamps, mirrors, auto windshields, optoelectronic display devices such as cathode ray tubes (TV screens, rear projection screens, radar screens and computer monitors) and flat panel displays (liquid crystal displays, light emitting diodes, electroluminescent panels, plasma display panels and vacuum fluorescent displays) , circuit boards, cable, wire, interlayer dielectrics for electronic devices, automotive surfaces, statuary, architectural buildings and panels, the interior of tubing, oven and microwave glass, laboratory glassware, vials for pharmaceuticals, o- rings, gaskets and stainless steel for preserving appearance.
  • articles such as lined reactor vessels, heat exchangers, shower doors, shower heads, lenses, head lamps, mirrors, auto windshields, optoelectronic display devices such as cathode ray tubes (TV screens, rear projection screens, radar screens and computer monitors) and flat panel displays (liquid crystal displays, light emitting diodes,
  • Multilayer coatings wherein a primer coat comprises the fluoropolymer nanocomposite of the present invention can also be used to coat the articles named above.
  • the multilayer coatings of the present invention wherein a primer coat comprises the fluoropolymer nanocomposite of the present invention are useful for coating articles requiring, for example, abrasion resistant or scratch resistant, anti-reflective, anti- fouling, chemical resistant, release, lubricity, anti- soiling, anti-staining, low dielectric constant or reduced surface energy characteristics .
  • These articles can be made of glass, ceramic, amorphous or crystalline plastic, rubber, elastomer, wood or metal such as stainless steel, copper or brass.
  • the multilayer coatings can be used to coat bearings, metal containers, ducts, valves, wire, metal foil, boilers, pipes, ship bottoms, oven liners, iron soleplates, metal cookware such as frypans and rice cookers, snow shovels and plows, chutes, conveyors, dies, tools such as saws, files and drills, hoppers and other industrial containers and molds.
  • the standalone coatings of the present invention can also be used to coat these same articles.
  • Coating the substrate via dip, flow or spray coating methods can be provided by contacting the substrate with the fluoropolymer/inorganic oxide precursor solution prior to gelation, with subsequent drying and optional heating up to about 350°C.
  • the coating solution can be heated at a temperature ranging from about room temperature to about the boiling point of the solvent, or to 100°C prior to coating. Coating thicknesses range from about lOOA to about l ⁇ . Dip coating from solutions comprising the fluoropolymer, the inorganic oxide precursor and gelling agent in a fluorinated solvent onto glass slides, followed by an optional overcoat comprising same or another fluoropolymer, can give optically transparent films .
  • these slides After curing at temperatures ranging from about 25°C to about 320°C, these slides show low surface energies as measured by advancing hexadecane contact angles of greater than 50°.
  • the films generally show good adhesion surviving 30 min in boiling water followed by a tape pull.
  • TEFLON 2,2- bis (trifluoromethyl) -4, 5-difluoro-1, 3-dioxole
  • Adhesion is generally measured herein using the standard ASTM test method D3359. The method covers procedures for assessing the adhesion of coating films to metallic substrates by applying and removing pressure-sensitive tape over cuts made in the film. As is shown in the Examples and Fig. 5, fluoropolymer nanocomposites of the present invention display improved abrasive resistance. After coating an extrusion die with a primer solution of a fluoropolymer nanocomposite of the present invention followed by a top coat of a fluoropolymer and extruding abrasive material through the die, an improvement in the performance and the durability of the fluoropolymer top coat is shown.
  • Preferred fluoropolymer topcoats comprise copolymers derived from tetrafluoroethylene (TFE), such as TFE and bis 2, 2- (trifluoromethyl) -4, 5- difluoro-1, 3-dioxole; TFE and hexafluoropropylene; and TFE and a perfluoroalkylvinylether.
  • TFE tetrafluoroethylene
  • TFE and bis 2, 2- (trifluoromethyl) -4, 5- difluoro-1, 3-dioxole such as TFE and bis 2, 2- (trifluoromethyl) -4, 5- difluoro-1, 3-dioxole
  • TFE and hexafluoropropylene TFE and a perfluoroalkylvinylether.
  • EXAMPLES All reactions with air-sensitive materials were carried out in a Vacuum Atmospheres Co. dry box or under nitrogen. In the examples that follow, all commercial reagents ' were
  • Tetrachlorosilane, trichlorosilane, vinyltrichloro- silane, allyltrichlorosilane 1, 3, 5, 7-tetramethyl- cyclotetrasilane, tetrakis (dimethylsiloxy) -silane, 1, 1, 3, 3-tetramethyldisiloxane, and pentamethylcyclo- pentasiloxane and trifluoroacetic acid were purchased from Aldrich Chemical Co., Milwaukee, WI, United Techologies Inc., Bristol, PA or PCR Inc., Gainesille, FL.
  • Platinum divinylsiloxane complex (3-3.5% Pt concentration in xylene, Huls PC072) was obtained from Huls America Inc. and diluted 5:1; by volume (toluene, Pt complex) prior to use. Toluene was reagent grade and purified by distillation from calcium hydride prior to use.
  • Tetraallylsilane was snythesized by a modification of a published procedure (J. Organomet. Chem., 84 (1975), pg 199-229) .
  • FBS tetra (heptafluorobutoxy) silane, Si (OCH 2 C 3 F 7 ) 4
  • FBS-PDD bis (tri (heptafluorobutoxy) silylethyl) -2, 2- bis (trifluoromethyl) -4, 5-difluoro-1, 3-dioxolane
  • FBS-Star 16 (C 3 F 7 CH 2 0) 3 SiCH 2 CH 2 (CF 2 ) 6 CH 2 CH 2 Si (OCH 2 C 3 F 7 ) 3
  • FC-75 perfluoro (butyl THF)
  • FES tetra (tri luoroethoxy) silane, Si (OCH 2 CF 3 ) 4
  • FOES F(CF 2 ) 6 CH 2 CH 2 Si (OCH 2 CH 3 ) 3
  • FStar 3 Si [OSiMe 2 CH 2 CH 2 Si (OCH 2 C 3 F 7 ) 3 ] 4
  • PMMA poly(methylmethacrylate)
  • TEOS Si (OCH 2 CH 3 ) 4 , tetraethoxysilane
  • TFA trifluoroacetic acid, CF 3 COOH
  • Adhesion promotion in "TEFLON" AF in HFB 0.123 g of "TEFLON” AF 1600 was dissolved in 12.019 g hexafluorobenzene (HFB) .
  • a second solution of tetra (trifluoroethoxy) silane (FES) (0.065 g) and HFB (3.004 g) was prepared.
  • a portion of the FES solution 2.006 g was added to a portion of the "TEFLON” AF 1600 solution (1.997 g) while it was being magnetically stirred. After the silane/"TEFLON" AF solution had stirred for 3 min.
  • the advancing contact angle was 60 2 , higher than that for pol tetra ⁇ fluoroethylene) of 45 s .
  • the sample was then subjected to boiling water for 10 min, and the contact angle remeasured after drying.
  • the advancing angle for hexadecane was 53 s .
  • Example 5 A coating was made as in Example 3 except that pure "TEFLON” AF 1600 in FC-75 (2%) was used. After heating to 120 2 C for 18 min and cooling, the coating was completely removed by the adhesive tape.
  • EXAMPLE 5 A coating was made as in Example 3 except that pure "TEFLON” AF 1600 in FC-75 (2%) was used. After heating to 120 2 C for 18 min and cooling, the coating was completely removed by the adhesive tape.
  • the transparent, air-dried coating was heated to 150 2 C for 15 min, cooled and subjected to an adhesive tape test (cross hatched) and submersion in boiling water for 10 min.
  • the coating was nearly unaffected by the tape pull and suffered some detachment from the substrate after the immersion in the water.
  • a coating was made as in Example 5 except that pure "KALREZ” in FC-75 (2%) was used.
  • the dried coating was easily completely removed from the substrate with tape (no cross hatching) or by 30 sec. immersion in boiling water.
  • EXAMPLE 7 Adhesion promotion of "KALREZ” with FES 135 mg FES and 73 mg TFA were added to 13.33 g HFB. The clear solution was added to 6.73 g of a 1% solution of "KALREZ” in HFB. The combined solution was heated to 35 2 C until it completely clarified. A dip coating on glass was made 44 hours later at a withdrawal rate of 92 mm/min. The film was heated to 200 2 C for 60 min., then submersed in boiling water for 10 min. The film was intact and showed a hexadecane contact angle of 43 2 .
  • Adhesion promotion of "TEFLON” AF using FBS-PDD/HFBS/"TEFLON” AF primer in FC-75 A mixture of 1:1 molar FBS-PDD and HFBS (24 mg) and 3.5 mg of TFA were added to 1.25 g of a 6% "TEFLON” AF 1601S stock solution diluted in 13.75 g of FC-75. This resulted in a solution consisting of 0.5% "TEFLON” AF 1601S and 0.1% silanes. The solution was allowed to stand for 72 hours. This solution was used to dip coat glass microscope slides at a withdrawal rate of 14.6 mm/min. After the first coat, all slides were dried at 150 2 C for 30 min. A second coat of solution was applied and dried under the same conditions. The final coating was from a 0.5%
  • TEFLON AF 1600 solution in FC-75.
  • the slides were then heated to 150 2 C for 30 min followed by 225 S C for 30 min. After cooling, the sample was analyzed for surface energy by measuring the contact angle of the low energy fluid hexadecane on the surface, using the sessile drop method. The advancing contact angle was 66 2 , higher than that for poly(tetrafluoroethylene) which is 45 2 .
  • the sample was then subjected to boiling water for 30 min, and the contact angle remeasured after drying.
  • the advancing angle for hexadecane was 62 2 .
  • the samples were subjected to an adhesive tape test (not cross hatched) . The coating was unaffected by the tape pull. Similar slides containing no "TEFLON" AF topcoat gave advancing contact angles of 70 2 . After boiling for 30 min, the advancing angle was 58 2 .
  • FBS-PDD/HFBS in FC-75 as described above.
  • Some slides contained an additional top coat of 0.5% "TEFLON" AF 1600. After cooling, the samples were analyzed by contact angle measurements. The advancing hexadecane contact angle for all slides, with or without a
  • Adhesion promotion of "TEFLON” AF using FBS-PDD/HFBS/"TEFLON” AF primer in HFB A solution consisting of 0.014 g of FBS-PDD, 4 mg of TFA, 0.062 g of "TEFLON” AF 1601 in 12.34 g of hexafluorobenzene was prepared and allowed to stand for 1 hr. Glass microscope slides were dip coated first using this solution, heated, dip coated again with 0.5% "TEFLON” AF 1601 solution and heated as described in the previous example. After cooling, the samples were analyzed by contact angle measurements. The advancing contact angle for hexadecane was 66°. After boiling the sample for 30 min, the advancing angle was 59°. The coating was unaffected by the tape pull.
  • FBS-PDD/HFBS/"TEFLON" AF primer in "FREON” El A solution consisting of 0.018 g of FBS-PDD, 4.2 mg of TFA, 0.063 g of "TEFLON” AF 1601 in 12.60 g of C 3 F 7 CHFCF 3 (e.g., "FREON” El) was prepared and allowed to stand for 1 hr. Glass microscope slides were dip coated first using this solution, heated, dip coated again with 0.5% "TEFLON” AF 1601 solution and heated as described in the previous example. After cooling, the samples were analyzed by contact angle measurements. The advancing contact angle for hexadecane was 65°. After boiling for 30 min, the advancing angle was 62°. The coating was unaffected by the tape pull. EXAMPLE 13
  • FBS-PDD/HFB /"TEFLON" AF primer in perfluoro (methylcyclohexane)
  • EXAMPLE 14 Adhesion promotion of "TEFLON” AF using FBS-PDD/HFBS/"TEFLON” AF primer in perfluoro (n-ethylmorpholine)
  • a solution consisting of 0.020 g of FBS-PDD, 3 mg of TFA, 0.103 g of "TEFLON” AF 1601 in 20.016 g of perfluoro (n-ethylmorpholine) was prepared and allowed to stand for 1 hr. Glass microscope slides were dip coated using this solution as described in the previous examples. After cooling, the samples were analyzed by contact angle measurements . The advancing contact angle for hexadecane was 67°. After boiling for 30 min, the advancing angle was 63°. The coating was unaffected by the tape pull.
  • the advancing hexadecane contact angle for the single layer coating was 68°, and for the double layer coating was 69°. After boiling for 30 min, the advancing angle for the single layer was 31° and for the double layer coating was 39°. Both coatings were unaffected by the tape pull.
  • EXAMPLE 17 Adhesion promotion in "TEFLON” AF using FBS/"TEFLON” AF primer in FC-75. with or without “TEFLON” AF topcoat Si(OCH 2 C 3 F 7 ) 4 (FBS) (0.018 g) was added to 13.50 g of a 0.5% "TEFLON” AF 1601 stock solution in FC-75 and stirred. TFA (1.3 mg) was added, and the solution stirred for about one hr, then filtered before use to remove a slight precipitate. Glass microscope slides were dip coated using this solution as described in the previous example. After cooling, the samples were analyzed by contact angle measurements . The advancing hexadecane contact angle for the single layer coating was 65°, and for the double layer coating was 67°.
  • FBS-Star 16/FQES/"TEFLON" AF primer in FC-75 FBS-Star 16 (9 mg) , FOES (4 mg) , and TFA (5 mg) were added to 13.01 g of a 0.5% "TEFLON" AF 1601 stock solution in FC-75.
  • the solution was allowed to stand for 1 hr. Glass microscope slides were dip coated using this solution as described in the previous examples. After cooling, the samples were analyzed by contact angle measurements. The advancing contact angle for hexadecane was 67°. After boiling for
  • TEFLON AF 1601 stock solution in FC-75. The solution was allowed to sit overnight. Glass microscope slides were dip coated using this solution as described in the previous examples. After cooling, the samples were analyzed by contact angle measurements. The advancing contact angle for hexadecane was 67°. After boiling for 30 min, the advancing angle was 55°. The coating was unaffected by the tape pull.
  • FBS-PDD/HFBS/"TEFLON" AF Primer in FC-75 A 1:1 molar mixture of FBS-PDD and HFBS (19 mg) and TFA (3 mg) were added to 19.01 g of a 0.5% "TEFLON" AF 1601 stock solution in FC-75. The solution was allowed to stand for 1 hr. Cleaned poly (methylmethacr late) (PMMA) samples (1" x 2") were dip coated using this solution as described in the previous examples. After dip coating, the samples were air dried overnight. The samples were analyzed by contact angle measurements. The advancing contact angle for hexadecane was 68 s . After boiling for 30 min, the advancing angle was 64 s . The coating was unaffected by the tape pull.
  • PMMA poly (methylmethacr late)
  • TEFLON AF on tun ⁇ sten carbide capillary die using FBS-PDD/HFBS/"TEFLON” AF coatings
  • the inside surface of a cleaned tungsten carbide capillary die was coated with a solution comprising 1.0% “TEFLON” AF 1601 and 0.2% FBS-PDD/HFBS in FC-75 made similar to those described in Example 9
  • the coating was dried for 2 hr. at 250°C.
  • Linear low density polyethylene containing 2.5 wt. % silica filler was extruded through the coated capillary using an Instron capillary rheometer for a period of two hours at 220°C at a constant shear rate.
  • the time required to remove the coating was nearly 100 min as compared to 30 min observed for ' a capillary coated from a 1.0% solution of "TEFLON" AF 1601 in FC-75.
  • Control B Extrusion of abrasive polyethylene through stainless steel capillary die that has been coated with Teflon AF from solution The stainless steel capillary die of Control A was cleaned by heating to red heat with a propane torch. After cooling to room temperature, the inside surface of the capillary was coated with a 3% solution of
  • Teflon AF 1601 dissolved in "FLUORINERT" FC-75 Teflon AF 1601 dissolved in "FLUORINERT" FC-75.
  • the coating was dried for 2 hours at 250°C.
  • the linear low density polyethylene of Control A which contained 2.5 wt % of a silica filler, was extruded through the coated capillary for a period of two hours at 220°C and at a constant shear rate of 704 s -1 .
  • the shear stress required to extrude the polyethylene through the coated die was 0.30 MPa at the start of the extrusion.
  • the shear stress remained constant for a period of about 10 minutes and then increased to 0.50 MPa after a total of about 20 minutes.
  • the shear stress then remained constant at 0.50 MPa for the duration of the test.
  • the surface of the extrudate was smooth at the start of the extrusion but became rough after about 20 minutes.
  • This example shows that a coating of "TEFLON” AF on an extrusion die acts as a processing aid for the extrusion of linear low density polyethylene.
  • the "TEFLON” coating allows the polyethylene to be extruded at a lower extrusion pressure (lower shear stress) and results in an extrudate with better surface appearance.
  • the "TEFLON” coating is removed from the surface of the die by abrasion during the extrusion process.
  • the stainless steel capillary die of Control B was cleaned by heating to red heat with a propane torch. After cooling to room temperature, the inside surface of the capillary was coated with a solution of 1% "TEFLON” AF and 0.2%, (C 3 F 7 CH 2 0) 3 SiCH 2 CH 2 (CF 2 ) 6 CH 2 CH 2 Si(OCH 2 C 3 F 7 ) 3 dissolved in "FLUORINERT” FC-75. The coating was dried 2 hours at 250°C.
  • This primer coating was then top coated with a 3% solution of "TEFLON” AF 1601 dissolved in "FLUORINERT” FC-75. The top coat was dried for 2 hours at 250°C.
  • Control A which contained 2.5 wt % of a silica filler, was extruded through the coated capillary for a period of two hours at 220°C and at a constant shear rate of 704 s _1 .
  • the shear stress required to extrude the polyethylene was 0.22 MPa at the start of the extrusion.
  • the shear stress remained constant for a period of about 10 minutes and then increased to
  • EXAMPLE 27 Improved Performance and Durability of Fluoronano- composite Coatings on Stainless Steel Capillary Dies
  • the stainless steel capillary die of Example 26 was cleaned by heating to red heat with a propane torch. After cooling to room temperature, the inside surface of the capillary was coated with a solution consisting of 1.0% "TEFLON” AF 1601 and 0.2% of (C 3 F 7 CH 2 0) 3 SiCH 2 CH 2 (CF 2 ) 6 CH 2 CH 2 Si (OCH 2 C 3 F 7 ) 3 in "FLUORINERT" FC-75 as described in Example 18. The coating was dried for 2 hours at 250°C.
  • Example 26 The linear low density polyethylene of Example 26 (Control A) , which contained 2.5 wt.% of a silica filler, was extruded through the coated capillary for a period of 2 hours at 220°C and at a constant shear rate of 704 s" 1 .
  • the shear stress required to extrude the polyethylene was 0.32 MPa at the start of the extrusion.
  • the shear stress remained constant for the first 3 mins. and slowly decreased to 0.30 MPa. After 10 min. the shear stress slowly increased to 0.36 MPa after 20 min.
  • the fluoronanocomposite coating performed as a processing aid for the extrusion of low density polyethylene and showed improved abrasion resistance.
  • the improved performance by the fluoropolymer nanocomposite demonstrates that it can be useful in durable coatings in, for example, molds, ducts, and in cookware items such as fry pans .
  • TFE/HFP copoly ⁇ ne-r The stainless steel capillary die of Control A in Example 26 was cleaned by heating to red heat with a propane torch. After cooling to room temperature, the inside surface of the capillary was coated with a 3% dispersion of 85/15 wt ratio (TFE/HFP) copolymer in "FLUTEC" PP-11 solvent. The coating was dried for 2 hours at 300°C.
  • the linear low density polyethylene of Control A which contained 2.5 wt % of a silica filler, was extruded through the coated capillary for a period of two hours at 220°C and at a constant shear rate of 704 s "1 .
  • the shear stress required to extrude the polyethylene was 0.25 MPa at the start of the extrusion. The shear stress remained constant for a period of about 10 minutes and then increased to
  • TEFLON AF/FBS-Star 16 primer top coat of TFE/HFP copolymer
  • the stainless steel capillary die of Control C was cleaned by heating to red heat with a propane torch. After cooling to room temperature, the inside surface of the capillary was coated with a solution of 1% "TEFLON” AF and 0.2% silane coupling agent, (C 3 F 7 CH 2 0) 3 SiCH 2 CH 2 (CF 2 ) 6 CH 2 CH 2 Si (OCH 2 C 3 F 7 ) 3 dissolved in "FLUORINERT" FC-75. The coating was dried for 2 hours at 250°C.
  • This primer coating was then top coated with a 3% dispersion of a 85/15 wt ratio TFE/HFP copolymer (e.g., "TEFLON” FEP T9050) in "FLUTEC” PP-11 solvent.
  • the top coat was dried for 2 hours at 30°C.
  • the linear low density polyethylene of Control A which contained 2.5 wt % of a silica filler, was extruded through the coated capillary for a period of two hours at 220°C and at a constant shear rate of 704 s -1 .
  • the shear stress required to extrude the polyethylene was 0.20 MPa at the start of the extrusion.
  • the shear stress remained constant for a period of about 20 minutes and then slowly increased to 0.30 MPa after a total of two hours .
  • the surface of the extrudate was smooth throughout the test.
  • EXAMPLE 30 Improved Performance of Metal Topcoat Layers on a Fluoronanocomposite Interlayer Dielectric Coating Using FBS and a Copolymer of TFE and PDD
  • FBS fluoropolymer stock solution consisting of 6% of a TFE/PDD copolymer in FC-75 was prepared.
  • FBS 3.79 g
  • TFA 1.57 g
  • Three other solutions consisting of 59.71 g of the stock solution, 1.80 g FBS, 0.745 g TFA; 65.61 g of stock solution, 0.811 g FBS, 0.337 g TFA; and
  • the gold coating of the fluoropolymer control sample showed visible cracking after thermal cycling, while all the gold coatings of the fluoropolymer nanocomposite samples were intact, shiny and showed no cracking of the coating.
  • the samples from the 6% FBS and 0.6% FBS solutions were crosshatched subjected to a adhesive tape pull. The gold coatings were unaffected by a tape pull.
  • EXAMPLE 37 Low surface energy coating on crystalline Nylon 6,6 using HFBS/FBS-PDD and a copolymer of TFE and PDD
  • a bar of Nylon 6,6 (125 mm x 13 mm x 3 mm) was dipcoated using the solution described in Example 31. The sample was air dried for 1.5 hr, and analyzed by contact angle measurements. The hexadecane advancing contact angle for the coated Nylon was 60° while that of the uncoated Nylon was 6°.
  • EXAMPLE 38 Low surface energy coating on crystalline Nylon 6.6 using FBS and a copolymer of TFE and PDD
  • a bar of Nylon 6,6 (125 mm x 13 mm x 3 mm) was dipcoated using the ' solution described in Example 32. The sample was air dried for 1.5 hr, and analyzed by contact angle measurements . The hexadecane advancing contact angle for the coated Nylon was 65° while that of the uncoated Nylon was 6° .
  • EXAMPLE 39 Low surface energy coating on crystalline Nylon 6.6 using FBS and a copolymer of TFE and PDD
  • EXAMPLE 40 Low surface energy coating on copper using FBS and a copolymer of TFE and PDD
  • the slab of copper (3" x 1" x 1/8") cleaned as described in the previous example was dipcoated using the solution described in Example 32.
  • the coated metal was dried at 150°C for 30 min in air, and analyzed by contact angle measurements.
  • the hexadecane advancing contact angle for the coated copper was 55° while that of the uncoated copper was 5°.
  • EXAMPLE 41 Low surface energy coating on brass using HFBS/FBS-PDD and a copolymer of TFE and PDD
  • a slab of brass (3" x 1" x 1/8") was cleaned as described in Example 39.
  • the brass was next dipcoated using the solution described in Example 31.
  • the coated metal was dried at 150°C for 30 min in air, and analyzed by contact angle measurements .
  • the hexadecane advancing contact angle for the coated brass was 58° while that of the uncoated brass was 6°.
  • EXAMPLE 42 Low surface energy coating on brass using FBS and a copolymer of TFE and PDD A slab of brass (3" x 1" x 1/8") was cleaned as described previously. The brass was next dipcoated using the solution described in Example 32. The coated metal was dried at 150°C for 30 min in air, and analyzed by contact angle measurements. The hexadecane advancing contact angle for the coated brass was 46° while that of the uncoated brass was 6°.
  • EXAMPLE 43 Corrosion resistant coatings using HFBS/FBS-PDD and a copolymer of TFE and PDD on copper and brass Samples of copper and brass prepared as described in Examples 39 and 41 were soaked in a solution consisting of 3.5 wt. % NaCl dissolved in distilled water for 18 hr at room temperature. Upon removing samples from the solution, the uncoated areas were discolored and corroded while the coated area was not discolored and resembled the original metal prior to dip coating.
  • EXAMPLE 44 Corrosion resistant coatings using HFBS/FBS-PDD and a copolymer of TFE and PDD on copper and brass Samples of copper and brass prepared as described in Examples 39 and 41 were soaked in a solution consisting of 3.5 wt. % NaCl dissolved in distilled water for 18 hr at room temperature. Upon removing samples from the solution, the uncoated areas were discolored and corroded while the coated area was not discolored and
  • EXAMPLE 45 Low surface energy coating on silicone rubber using FBS and a copolymer of TFE and PDD A slab of silicone rubber (22.5 mm x 77 mm x 3 mm) was dipcoated using the solution described in Example 32. The sample was air dried for 1.5 hr, and analyzed by contact angle measurements . The hexadecane advancing contact angle for the coated silicone was 60° while that of the uncoated silicone was 25°.
  • EXAMPLE 47 Low surface energy coating on PMMA using FBS and a copolymer of TFE and PDD A slab of PMMA (22.5 mm x 77 mm x 3 mm) was dipcoated using the solution described in Example 32. The sample was air dried for 1.5 hr, and analyzed by contact angle measurements. The hexadecane advancing contact angle for the coated PMMA was 48° while that of the uncoated PMMA was 11°.
  • EXAMPLE 48 Low surface energy coating on "KAPTON” polyimide film using HFBS/FBS-PDD and a copolymer of TFE and PDD
  • a piece of "KAPTON” polyimide film (22.5 mm x 77 mm x .075 mm) was dipcoated using the solution described in Example 31.
  • the sample was air dried for 1.5 hr, and analyzed by contact angle measurements.
  • the hexadecane advancing contact angle for the contact angle for the coated "KAPTON” was 63° while that of the uncoated “KAPTON” was 4°.
  • EXAMPLE 49 Low surface energy coating on "KAPTON” polyimide film using FBS and a copolymer of TFE and PDD A piece of "KAPTON” polyimide film (22.5 mm x 77 mm x .075 mm) was dipcoated using the solution described in Example 32. The sample was air dried for 1.5 hr, and analyzed by contact angle measurements. The hexadecane advancing contact angle for the coated "KAPTON” was 53° while that of the uncoated “KAPTON” was 6° .
  • EXAMPLE 50 Low surface energy coating on "KAPTON” polyimide film using FBS and a copolymer of TFE and PDD
  • EXAMPLE 55 Low surface energy coating on "VITON” elastomer using PFPS and a copolymer of TFE and HFP A slab of "VITON” GF elastomer (1" x 3") was cleaned using CH C1 2 , dried and dipcoated using the solution in Example 52. The slab was dried at 100°C for 30 min., and analyzed by contact angle measurements. The hexadecane advancing contact angle for the coated "VITON” was 67°.
  • EXAMPLE 56 Low surface energy coating on "VITON” elastomer using PFPS and a copolymer of TFE and HFP A slab of "VITON” GF elastomer (1" x 3") was cleaned using CH C1 2 , dried and dipcoated using the solution in Example 52. The slab was dried at 100°C for 30 min., and analyzed by contact angle measurements. The hexadecane advancing contact angle for the coated "VITON” was 67°.
  • a slab of "VAMAC” (1" x 3") was cleaned using CH 2 C1 2 , dried and dipcoated using the solution in
  • Example 52 The slab was dried at 100°C for 30 min., and analyzed by contact angle measurements. The hexadecane advancing contact angle for the coated "VAMAC" was 60°. EXAMPLE 59

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Abstract

Cette invention concerne un nanocomposite de fluoropolymère comprenant une phase fluoropolymère et une phase oxyde inorganique en dispersion, cette dernière phase ne comportant pas de particules ou bien des particules qui présentent toutes une grosseur particulaire inférieure à environ 75 nm, qui peut être déterminée à l'aide de techniques de dispersion d'angle miniature aux rayons X et de microscopie électronique à transmission. Ces nanocomposites sont utiles comme revêtements protecteurs.
EP96924341A 1995-06-28 1996-06-27 Nanocomposites de fluoropolymere Withdrawn EP0837901A1 (fr)

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US57195P 1995-06-28 1995-06-28
US571 1995-06-28
US205495P 1995-08-09 1995-08-09
US08/663,821 US5726247A (en) 1996-06-14 1996-06-14 Fluoropolymer nanocomposites
US663821 1996-06-14
PCT/US1996/011193 WO1997001599A1 (fr) 1995-06-28 1996-06-27 Nanocomposites de fluoropolymere
US2054 1997-12-31

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