WO2014174324A1 - Deposition of anhydride layers - Google Patents

Deposition of anhydride layers Download PDF

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Publication number
WO2014174324A1
WO2014174324A1 PCT/GB2014/051315 GB2014051315W WO2014174324A1 WO 2014174324 A1 WO2014174324 A1 WO 2014174324A1 GB 2014051315 W GB2014051315 W GB 2014051315W WO 2014174324 A1 WO2014174324 A1 WO 2014174324A1
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WIPO (PCT)
Prior art keywords
compound
substrate
formula
anhydride
coating
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Application number
PCT/GB2014/051315
Other languages
French (fr)
Inventor
Jas Pal Singh Badyal
Wayne Christopher Edward Schofield
Thomas J. Wood
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Surface Innovations Limited
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Publication date
Application filed by Surface Innovations Limited filed Critical Surface Innovations Limited
Publication of WO2014174324A1 publication Critical patent/WO2014174324A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/52—Polymerisation initiated by wave energy or particle radiation by electric discharge, e.g. voltolisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F122/00—Homopolymers 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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/04—Anhydrides, e.g. cyclic anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F122/00—Homopolymers 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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/04—Anhydrides, e.g. cyclic anhydrides
    • C08F122/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/54—Polymerisation initiated by wave energy or particle radiation by X-rays or electrons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and 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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/04—Anhydrides, e.g. cyclic anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and 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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/04—Anhydrides, e.g. cyclic anhydrides
    • C08F22/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/08—Anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0026—Activation or excitation of reactive gases outside the coating chamber
    • C23C14/0031—Bombardment of substrates by reactive ion beams
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/08—Organic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/213—Perfluoroalkyl carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/63—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing sulfur in the main chain, e.g. polysulfones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/667—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to the production of coatings that contain anhydride functional groups using precursors as described in Formula I, said method comprising excited deposition of compounds such as (trifluoromethyl)maleic anhydride to form layers.
  • Such layers can be subject to subsequent hydrolysis or derivatisation with other functional groups.
  • Formula I Anhydride precursor where X and or Y are sulphur, phosphorus, or carbon atoms with additional linkage(s) to one or more atoms or chemical groups, or alternatively X and Y form part of a cyclic structure.
  • An anhydride surface or layer offers a chemically versatile substrate that allows subsequent modification by the application of widely used solution-based chemistries including, but not limited to hydrolysis, aminolysis, imidization, esterification and acylation.
  • Suitable monomers are broadly characterised as possessing an anhydride functionality as shown in general formula (I).
  • the applicants have found that such monomers can either be used alone or be used in conjunction with other monomers for co-deposition (other monomers can include substituent groups such as partially or wholly substituted fluoroalkyls, unsaturated functional groups such as alkene, acrylate and methacrylate, but not limited to these).
  • the resulting films in comparison with the prior art, exhibit superior mechanical stability, biocompatibility, acidity, and proton conductivity.
  • a method for applying anhydride containing coatings to a substrate comprising subjecting said substrate to an excitation medium in the presence of a compound of formula (I) either alone or in conjunction with other compounds.
  • X and Y can be carbon, phosphorus, or sulphur and bonded to one or more other atoms or groups such as optionally substituted straight or branched hydrocarbyl chain(s) or group(s), or form part of a cyclic structure.
  • hydrocarbyl includes alkyl, alkenyl, alkynyl, aryl and aralkyl groups.
  • aryl refers to aromatic cyclic groups such as phenyl or naphthyl, in particular phenyl.
  • alkyl refers to straight or branched chains of carbon atoms, suitably of from 1 to 20 carbon atoms in length.
  • alkenyl and alkynyl refer to straight or branched unsaturated chains suitably having from 2 to 20 carbon atoms. These groups may have one or more multiple bonds.
  • alkenyl groups include allenyl and dienyl.
  • Suitable optional substituents for hydrocarbyl groups and alkylene/aryl groups are electron- withdrawing groups such as halo groups such as fluoro, chloro, bromo and iodo, or haloalkyl groups such as perhaloalkyl group.
  • Particularly preferred halo substituents include but are not limited to fluoro such as trifluoromethyl or perfluorooctyl.
  • Other suitable substituents are electron donating groups including but are not limited to alkyl, phenyl, alkenyl.
  • Particularly preferred compounds of Formula I are those where X and Y form part of an optionally substituted heterocyclic ring of from 4 to 7 and preferably 5-6 atoms.
  • Particular examples include maleic anhydride and itaconic anhydride, and such compounds which contain substituent groups or atoms which pull or draw electrons away from the anhydride group such as the trifluoromethyl group present in (trifluoromethyl)maleic anhydride.
  • optional substituents are a highly polymerisable group such as acrylate-like group (e.g. acrylate, methacrylate).
  • the invention provides a method with high deposition rates and good mechanical integrity.
  • the method also provides a coating with high proton conductivity.
  • a proton conductor is an electrolyte, typically a solid electrolyte, in which H + ions are the primary charge carriers.
  • Proton conductors are an essential part of many fuel cells. Precise conditions under which the excited deposition of the compound of Formula I takes place in an effective manner will vary depending upon factors such as the nature of the monomer, the substrate, the size and architecture of the excitation deposition chamber etc. and will be determined using routine methods and/or the techniques illustrated hereinafter. In general however, deposition is suitably effected using vapours or atomised droplets of compounds of Formula I at atmospheric and sub-atmospheric pressures suitably from 0.01 to 999 mbar.
  • the excitation medium can include continuous wave or pulsed electrical discharges, thermal chemical vapour deposition, initiated chemical vapour deposition (iCVD), photodeposition, e-beam curing, ion- beam curing, target sputtering.
  • the method of precursor(s) introduction can include but not limited to vapour, sputtering, injected liquid spray, and slurries.
  • inorganic-polymer and metal- polymer composite layers can be prepared by the use of injecting slurries of inorganic or metal compounds mixed with compounds of Formula I into the excitation medium.
  • the deposition regime is varied during the course of coating deposition so as to enable the production of gradated coatings.
  • a high average-power excitation regime may be used at the start of sample treatment to yield a highly cross-linked, insoluble sub-surface coating that adheres well to the substrate.
  • a low average-power excitation regime may then be adopted for conclusion of the treatment cycle, yielding a surface layer displaying high levels of retained anhydride functionality on top of said well-adhered sub-surface.
  • Such a regime would be expected to improve overall coating durability and adhesion, without sacrificing any of the desired surface properties (i.e. reactive surface anhydride functionality).
  • Suitable plasmas for use in the method of the invention include non-equilibrium plasmas such as those generated by audio-frequencies, radiofrequencies (RF) or microwave frequencies.
  • the plasma is generated by a hollow cathode device.
  • the pulsed plasma is produced by direct current (DC).
  • the plasma may operate at low, sub-atmospheric or atmospheric pressures, as well as introduction of the reactant mixture downstream (remote plasma) as are known in the art.
  • the monomer(s) may be introduced into the plasma as a vapour or an atomised spray of liquid droplets (WO03101621 and WO03097245, Surface Innovations Limited).
  • the monomer may be introduced into the pulsed plasma deposition apparatus continuously or in a pulsed manner by way of, for example, a gas pulsing valve.
  • the substrate to which the anhydride bearing coating is applied will preferentially be located substantially inside the plasma during coating deposition.
  • the substrate may alternatively be located outside of the plasma, thus avoiding excessive damage to the substrate or growing coating.
  • the monomer will typically be directly excited within the plasma discharge.
  • "remote" plasma deposition methods may be used as are known in the art. In said methods the monomer enters the deposition apparatus substantially "downstream" of the pulsed plasma, thus reducing the potentially harmful effects of bombardment by short-lived, high-energy species such as ions.
  • the feed into the excitation medium chamber or apparatus may comprise the monomeric compound alone, in the absence of other compounds or in admixture with other compounds or for example an inert gas.
  • Deposition of anhydride compound alone may be achieved as illustrated hereinafter, by first evacuating the reactor vessel as far as possible, and then purging the reactor vessel with the anhydride compound for a period sufficient to ensure that the vessel is substantially free of other gases.
  • the temperature in the deposition chamber is suitably high enough to allow sufficient monomer in gaseous phase to enter the chamber. This will depend upon the monomer and conveniently ambient temperature will be employed. However, elevated temperatures for example from 25 to 250 °C may be required in some cases.
  • materials additional to the anhydride coating precursor are introduced into the excitation deposition apparatus.
  • the additional materials may be introduced into the coating deposition apparatus continuously or in a pulsed manner by way of, for example, a gas pulsing valve.
  • Additional materials may also be introduced into the coating deposition apparatus by but not limited to sputtering, evaporation, atomization, spraying, or ablation.
  • Said additive materials may be but not limited to inert species and act as buffers without any of their atomic structure being incorporated into the growing anhydride coating layer
  • a buffer of this type may be necessary to maintain a required process pressure.
  • the inert buffer may be required to sustain the excitation medium.
  • APGD atmospheric pressure glow discharge
  • the additive materials possess the capability to modify and/or be incorporated into the coating forming material and/or the resultant deposited coating.
  • Suitable examples include but not limited to other reactive gases such as halogens, oxygen, and ammonia.
  • the additive materials may be other monomers.
  • the resultant coatings comprise copolymers as are known and described in the art for the relevant excitation medium.
  • Suitable monomers for use within the method of the invention include organic (e.g. perfluorostyrene), inorganic, organo-silicon and organo-metallic precursors.
  • Particular additional monomers include organic monomers and in particular hydrocarbon or halogenated hydrocarbon monomers.
  • suitable additional organic monomers contain from 1-10, in particular 3-10 carbon atoms, that are in the form of alkyl, alkenyl or alkynyl or aryl groups or combinations of these, and in particular are halogenated and suitably perhalogenated.
  • the additional monomer may be a perfluorinated Ci-io alkane, for instance perfluorohexane, or a perfluorinated aryl compound such as perfluorostyryl.
  • the invention further provides a substrate having an anhydride containing coating thereon, obtained by a process as described above.
  • substrate can include any solid, particulate, permeable and/or porous substrate or finished article, consisting of any materials (or combination of materials) as are known in the art.
  • materials include, but are not limited to, woven or non-woven fibres, natural fibres, synthetic fibres, metal, glass, ceramics, semiconductors, cellulosic materials, paper, wood, or polymers such as polytetrafluoroethylene, polyethylene or polystyrene.
  • the surface comprises a support material, such as a polymeric material or glass.
  • a support material such as a polymeric material or glass.
  • examples include such substrates as are utilised in bio-technological fields (such as but not limited to genomics, proteomics, glycomics, wound healing, and tissue culture), fuel cells, packaging, and aerospace (Forch, R. et al., Plasma Processes and Polymers 2005, 2, 351).
  • the substrate having an anhydride functionalised coating obtained by a process as described above, is a porous media for use in applications that involve fluid transfer, filtration, and/or chemical separation phenomena.
  • purification, wicking, and emanation / venting applications abound in industries that include aerospace and defence; chemical processing; environmental control; power generation; oil and gas; air and water; food and beverage; healthcare and pharmaceuticals.
  • the anhydride functionalised surface is a sintered porous polymer media used for separating or extracting molecules of interest from mixtures. Such items are often utilised in the pharmaceutical, biomedical, food, and healthcare industries.
  • the substrate is coated continuously by means of a reel-to-reel apparatus. In one embodiment the substrate is moved past and through a coating apparatus acting in accordance with this invention.
  • the excitation deposition of the invention is therefore a solventless method for functionalising solid surfaces with anhydride groups and layers at fast deposition rates.
  • thick deposited layers can be used alone or ground into powders for use as stand alone anhydride containing materials exhibiting properties such as but not limited to high water uptake, acidity, biocompatibility (Sasai, Y. et al., J. Photopolym. Sci. Technol. 2009, 22, 477; Schiller, S. M. et al., Macromolecular Chemistry and Physics 2010, 211, 222) heat resistance (Roberts, R. D. et al., Journal of Cellular Plastics 2007, 43, 135), corrosion inhibition (AU 2010-100175), lubricity and adhesion.
  • the anhydride group may be further derivatised, or complexed with additional reagents as required.
  • additional reagents such as an amine terminated oligonucleotide strand or protein.
  • the derivatisation reaction may be effected in the gaseous phase where the reagents allow, or in a solvent such as water or an organic solvent.
  • solvents include alcohols (such as methanol), and tetrahydrofuran.
  • the derivatisation may hence result in the immobilisation of reagents on said surface. If derivatisation is spatially addressed, as is known in the art, this results in chemical patterning of the surface.
  • deposited anhydride containing layers include but not limited to lubricity, adhesion (Winther-Jensen, B. et al., Science 2008, 321, 671), heat resistance, biological cell growth, and the capture of compounds, gases, biomolecules and biospecies.
  • Super-acid layers, proton conduction fuel cell components can be prepared by hydrolysis of the deposited anhydride containing layers to yield acid groups.
  • any feature disclosed herein may be replaced by an alternative feature serving the same or a similar purpose.
  • anhydride monomers maleic anhydride, itaconic anhydride and (trifluoromethyl)maleic anhydride
  • plasma polymerization the resulting films are characterized by XPS, FTIR, and impedance spectroscopy (for proton conductivity).
  • the reactor had been scrubbed with cream cleaner, rinsed in acetone and dried in an oven. A continuous wave air plasma was run to ensure the reactor was completely clean.
  • a substrate was placed into the middle of the chamber above the heated holder. Using the heater a monomer pressure of 0.45 mbar for maleic anhydride, and 0.3 mbar for itaconic anhydride was used. 20 W continuous wave bursts lasting 10 ms, followed by an off- period set at 20 ms were used for pulsed plasma deposition.
  • the rf generator was switched off and the monomer allowed to continue through the system for a further 5 min.
  • the chamber was evacuated to base pressure to remove all the monomer vapour and then exposed to atmospheric pressure.
  • perfluorohexane was also loaded into a glass tube and subjected to several freeze-pump-thaw cycles to removed dissolved gases and introduced through a separate leak valve at 0.15 mbar vapour pressure.
  • Plasmachemical polymer film thickness measurements were carried out using an NKD-6000 spectrophotometer (Aquila Instruments Ltd.). Transmittance and reflectance curves within the 350- 1000 nm wavelength range were fitted to a Cauchy model for dielectric materials using a modified Levenburg-Marquardt method. For films with thickness greater than 5 ⁇ , the silicon wafer was snapped after immersion in liquid nitrogen and the cross section viewed and measured under an optical microscope.
  • Sessile drop contact angle measurements were carried out at 20 °C with a video capture apparatus (A.S.T. Products VCA-2500XE).
  • Fourier transform infrared (FTIR) analyses of the plasmachemically deposited films were carried out using an infrared spectrometer (Perkin-Elmer Spectrum One) equipped with a liquid nitrogen cooled mercury cadmium telluride (MCT) detector. All spectra were averaged over 256 scans at a resolution of 4 cm "1 .
  • Attenuated total reflection (ATR) measurements were taken using a single bounce diamond tip accessory (Graseby Specac Golden Gate).
  • Reflection-absorption (RAIRS) measurements utilized a variable angle accessory (Graseby Specac) fitted with a KRS-5 polarizer (to remove the s-polarized component) and set at 66°.
  • a VG Escalab spectrometer equipped with an unmonochromatized Mg K X-ray source (1253.6 eV) and a concentric hemispherical analyzer were used for X-ray photoelectron spectroscopy (XPS) characterization of the plasmachemical films. Elemental compositions were calculated using sensitivity (multiplication) factors derived from chemical standards, C(ls):0(ls):F(ls) 1.00:0.40:0.27.
  • Impedance measurements were carried out on membranes deposited on a glass substrate with two gold electrodes 16 mm long, separated by a distance of 7 mm.
  • the impedance was measured using an HP 4192A LF impedance analyser in the frequency range from 10 Hz to 13 MHz.
  • Impedance plots took the form of a high frequency impedance arc and a 45° line at lower frequencies. This is a typical response for electrolytes, whose bulk resistance is responsible for the high frequency arc, and the low frequency line is due to diffusion of charged particles (Mikhailenko, S. D et al, Solid State Ionics 2008, 179, 619.).
  • the bulk resistance of the membrane was extracted from fitting the high frequency arc.
  • the formula o l/R s A, where ⁇ is the membrane conductivity, R s is the bulk resistance, I is the length of the electrodes, and A is the cross-sectional area of the film.
  • FTIR spectra for the plasmachemically deposited maleic anhydride films are shown in Figure 1.
  • FTIR spectra for the plasmachemically deposited itaconic anhydride films are shown in Figure 2.
  • FTIR spectra for plasmachemically deposited maleic anhydride with the introduction of a 0.15 mbar perfluorohexane vapour can be seen in Figure 4.
  • the perfluorohexane monomer shows intense v(CF x ) bands in the region 1350-1100 cm “1 . These can be seen as a broad, strong band in the pulse plasma perfluorohexane spectrum.
  • C(ls) XPS spectra for pulsed plasma perfluorohexane are shown in Figure 5.
  • the C:0:F elemental compositions are shown in Table 1.
  • O to F gives the percentage monomer constituents of the film as 72% maleic anhydride to 28% perfluorohexane.
  • Table 1 XPS Atomic Percentages for Pulsed Plasma Perfluorohexane with and without mixing with
  • Table 2 shows the proton conductivities and stabilities of the different plasma polymer films.
  • (Trifluoromethyl)maleic anhydride is the most stable film and its contact angle is hydrophobic.
  • (Trifluoromethyl)maleic anhydride's high conductivity is enhanced by the electron withdrawing effect of the trifluoromethyl group, which makes the acid stronger. Stronger acid means more free protons in the film (when hydrated) to give higher proton conductivity.
  • Table 2 Proton conductivities at 293 K and Stability in Water of Plasma Polymer Films
  • Pulsed Plasma Layer conductivity / contact angle / ° stability Deposition mS/cm Rate / nm min "1 maleic anhydride 90 ⁇ 10 25 ⁇ 1 some cracking 5 ⁇ 1 maleic anhydride and 80 ⁇ 10 81 ⁇ 1 no cracking 130 ⁇ 20 perfluorohexane

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Abstract

A method for applying anhydride containing coatings to a substrate, said method comprising subjecting said substrate to an excitation medium in the presence of a compound of formula (I) where X and or Y are sulphur, phosphorus, or carbon atoms with additional linkage(s) to one or more atoms or chemical groups, which are selected from hydrogen or optionally substituted hydrocarbyl group; or alternatively X and Y together with the oxygen atom to which they are attached form part of an optionally substituted heterocyclic ring, either alone or in conjunction with other compounds, provided that when the compound of formula (I) is maleic anhydride, it is co-administered with a further monomer or gas.

Description

Deposition of Anhydride Layers
The present invention relates to the production of coatings that contain anhydride functional groups using precursors as described in Formula I, said method comprising excited deposition of compounds such as (trifluoromethyl)maleic anhydride to form layers. Such layers can be subject to subsequent hydrolysis or derivatisation with other functional groups.
Figure imgf000002_0001
Formula I: Anhydride precursor where X and or Y are sulphur, phosphorus, or carbon atoms with additional linkage(s) to one or more atoms or chemical groups, or alternatively X and Y form part of a cyclic structure.
The surface functionalisation of solid and porous objects is a topic of considerable technological importance, since it offers a cost effective means of improving substrate performance without affecting the overall bulk properties.
An anhydride surface or layer offers a chemically versatile substrate that allows subsequent modification by the application of widely used solution-based chemistries including, but not limited to hydrolysis, aminolysis, imidization, esterification and acylation.
Existing methods of depositing anhydride containing layers include plasma enhanced chemical vapour deposition, plasma polymerization, radiation grafting, spraying, solvent casting. These approaches suffer from drawbacks such as lack of mechanical stability and dissolution (Roucoules, V. et al., Langmuir 2007, 23, 13136; Drews, J. et al., Proceedings of 2 h Riso International Symposium on Materials Science: Interface Design of Polymer Matrix Composites - Mechanics, Chemistry, Modelling and Manufacturing 2008, 165; Drews, J. et al., J. Vac. Sci. Technol. A 2007, 25, 1108).
To achieve absence of mechanical instability and faster deposition rates, we hence propose that a methodology combining excitation deposition techniques and the selection of suitable monomer structures must be utilised. Suitable monomers are broadly characterised as possessing an anhydride functionality as shown in general formula (I). The applicants have found that such monomers can either be used alone or be used in conjunction with other monomers for co-deposition (other monomers can include substituent groups such as partially or wholly substituted fluoroalkyls, unsaturated functional groups such as alkene, acrylate and methacrylate, but not limited to these). The resulting films, in comparison with the prior art, exhibit superior mechanical stability, biocompatibility, acidity, and proton conductivity.
According to the present invention there is provided a method for applying anhydride containing coatings to a substrate, said method comprising subjecting said substrate to an excitation medium in the presence of a compound of formula (I) either alone or in conjunction with other compounds.
For Formula I, X and Y can be carbon, phosphorus, or sulphur and bonded to one or more other atoms or groups such as optionally substituted straight or branched hydrocarbyl chain(s) or group(s), or form part of a cyclic structure.
As used herein, the term "hydrocarbyl" includes alkyl, alkenyl, alkynyl, aryl and aralkyl groups. The term "aryl" refers to aromatic cyclic groups such as phenyl or naphthyl, in particular phenyl. The term "alkyl" refers to straight or branched chains of carbon atoms, suitably of from 1 to 20 carbon atoms in length. The terms "alkenyl" and "alkynyl" refer to straight or branched unsaturated chains suitably having from 2 to 20 carbon atoms. These groups may have one or more multiple bonds. Thus examples of alkenyl groups include allenyl and dienyl.
Suitable optional substituents for hydrocarbyl groups and alkylene/aryl groups are electron- withdrawing groups such as halo groups such as fluoro, chloro, bromo and iodo, or haloalkyl groups such as perhaloalkyl group. Particularly preferred halo substituents include but are not limited to fluoro such as trifluoromethyl or perfluorooctyl. Other suitable substituents are electron donating groups including but are not limited to alkyl, phenyl, alkenyl. Particularly preferred compounds of Formula I, are those where X and Y form part of an optionally substituted heterocyclic ring of from 4 to 7 and preferably 5-6 atoms. Particular examples include maleic anhydride and itaconic anhydride, and such compounds which contain substituent groups or atoms which pull or draw electrons away from the anhydride group such as the trifluoromethyl group present in (trifluoromethyl)maleic anhydride.
In another embodiment of the invention, optional substituents are a highly polymerisable group such as acrylate-like group (e.g. acrylate, methacrylate).
The invention provides a method with high deposition rates and good mechanical integrity. The method also provides a coating with high proton conductivity. A proton conductor is an electrolyte, typically a solid electrolyte, in which H+ ions are the primary charge carriers. Proton conductors are an essential part of many fuel cells. Precise conditions under which the excited deposition of the compound of Formula I takes place in an effective manner will vary depending upon factors such as the nature of the monomer, the substrate, the size and architecture of the excitation deposition chamber etc. and will be determined using routine methods and/or the techniques illustrated hereinafter. In general however, deposition is suitably effected using vapours or atomised droplets of compounds of Formula I at atmospheric and sub-atmospheric pressures suitably from 0.01 to 999 mbar.
The excitation medium can include continuous wave or pulsed electrical discharges, thermal chemical vapour deposition, initiated chemical vapour deposition (iCVD), photodeposition, e-beam curing, ion- beam curing, target sputtering. The method of precursor(s) introduction can include but not limited to vapour, sputtering, injected liquid spray, and slurries. For example, inorganic-polymer and metal- polymer composite layers can be prepared by the use of injecting slurries of inorganic or metal compounds mixed with compounds of Formula I into the excitation medium.
In one embodiment of the invention the deposition regime is varied during the course of coating deposition so as to enable the production of gradated coatings. For example, a high average-power excitation regime may be used at the start of sample treatment to yield a highly cross-linked, insoluble sub-surface coating that adheres well to the substrate. A low average-power excitation regime may then be adopted for conclusion of the treatment cycle, yielding a surface layer displaying high levels of retained anhydride functionality on top of said well-adhered sub-surface. Such a regime would be expected to improve overall coating durability and adhesion, without sacrificing any of the desired surface properties (i.e. reactive surface anhydride functionality).
Suitable plasmas for use in the method of the invention include non-equilibrium plasmas such as those generated by audio-frequencies, radiofrequencies (RF) or microwave frequencies. In another embodiment the plasma is generated by a hollow cathode device. In yet another embodiment, the pulsed plasma is produced by direct current (DC).
The plasma may operate at low, sub-atmospheric or atmospheric pressures, as well as introduction of the reactant mixture downstream (remote plasma) as are known in the art. The monomer(s) may be introduced into the plasma as a vapour or an atomised spray of liquid droplets (WO03101621 and WO03097245, Surface Innovations Limited). The monomer may be introduced into the pulsed plasma deposition apparatus continuously or in a pulsed manner by way of, for example, a gas pulsing valve.
The substrate to which the anhydride bearing coating is applied will preferentially be located substantially inside the plasma during coating deposition. However, the substrate may alternatively be located outside of the plasma, thus avoiding excessive damage to the substrate or growing coating.
The monomer will typically be directly excited within the plasma discharge. However, "remote" plasma deposition methods may be used as are known in the art. In said methods the monomer enters the deposition apparatus substantially "downstream" of the pulsed plasma, thus reducing the potentially harmful effects of bombardment by short-lived, high-energy species such as ions.
The feed into the excitation medium chamber or apparatus may comprise the monomeric compound alone, in the absence of other compounds or in admixture with other compounds or for example an inert gas. Deposition of anhydride compound alone may be achieved as illustrated hereinafter, by first evacuating the reactor vessel as far as possible, and then purging the reactor vessel with the anhydride compound for a period sufficient to ensure that the vessel is substantially free of other gases. The temperature in the deposition chamber is suitably high enough to allow sufficient monomer in gaseous phase to enter the chamber. This will depend upon the monomer and conveniently ambient temperature will be employed. However, elevated temperatures for example from 25 to 250 °C may be required in some cases.
In alternative embodiments of the invention, materials additional to the anhydride coating precursor are introduced into the excitation deposition apparatus. The additional materials may be introduced into the coating deposition apparatus continuously or in a pulsed manner by way of, for example, a gas pulsing valve. Additional materials may also be introduced into the coating deposition apparatus by but not limited to sputtering, evaporation, atomization, spraying, or ablation.
Said additive materials may be but not limited to inert species and act as buffers without any of their atomic structure being incorporated into the growing anhydride coating layer
(suitable examples include the noble gases). A buffer of this type may be necessary to maintain a required process pressure. Alternatively the inert buffer may be required to sustain the excitation medium. For example, the operation of atmospheric pressure glow discharge (APGD) plasmas often requires large quantities of helium. This helium diluent maintains the plasma by means of a Penning Ionisation mechanism without becoming incorporated within the deposited coating. The use of an inert species as the additive material results in a copolymer coating that contains anhydride functionality.
In other embodiments of the invention, the additive materials possess the capability to modify and/or be incorporated into the coating forming material and/or the resultant deposited coating. Suitable examples include but not limited to other reactive gases such as halogens, oxygen, and ammonia.
In alternative embodiments of the invention, the additive materials may be other monomers. The resultant coatings comprise copolymers as are known and described in the art for the relevant excitation medium. Suitable monomers for use within the method of the invention include organic (e.g. perfluorostyrene), inorganic, organo-silicon and organo-metallic precursors.
Particular additional monomers include organic monomers and in particular hydrocarbon or halogenated hydrocarbon monomers. For instance, suitable additional organic monomers contain from 1-10, in particular 3-10 carbon atoms, that are in the form of alkyl, alkenyl or alkynyl or aryl groups or combinations of these, and in particular are halogenated and suitably perhalogenated. In particular the additional monomer may be a perfluorinated Ci-io alkane, for instance perfluorohexane, or a perfluorinated aryl compound such as perfluorostyryl.
The invention further provides a substrate having an anhydride containing coating thereon, obtained by a process as described above. Such substrate can include any solid, particulate, permeable and/or porous substrate or finished article, consisting of any materials (or combination of materials) as are known in the art. Examples of materials include, but are not limited to, woven or non-woven fibres, natural fibres, synthetic fibres, metal, glass, ceramics, semiconductors, cellulosic materials, paper, wood, or polymers such as polytetrafluoroethylene, polyethylene or polystyrene.
In a particular embodiment, the surface comprises a support material, such as a polymeric material or glass. Examples include such substrates as are utilised in bio-technological fields (such as but not limited to genomics, proteomics, glycomics, wound healing, and tissue culture), fuel cells, packaging, and aerospace (Forch, R. et al., Plasma Processes and Polymers 2005, 2, 351).
In another particular embodiment the substrate having an anhydride functionalised coating, obtained by a process as described above, is a porous media for use in applications that involve fluid transfer, filtration, and/or chemical separation phenomena. Examples of such purification, wicking, and emanation / venting applications abound in industries that include aerospace and defence; chemical processing; environmental control; power generation; oil and gas; air and water; food and beverage; healthcare and pharmaceuticals. Hence, in a further embodiment of an article or substrate produced by the method of the invention, the anhydride functionalised surface is a sintered porous polymer media used for separating or extracting molecules of interest from mixtures. Such items are often utilised in the pharmaceutical, biomedical, food, and healthcare industries.
In one embodiment of the invention the substrate is coated continuously by means of a reel-to-reel apparatus. In one embodiment the substrate is moved past and through a coating apparatus acting in accordance with this invention.
The excitation deposition of the invention is therefore a solventless method for functionalising solid surfaces with anhydride groups and layers at fast deposition rates. Alternatively thick deposited layers can be used alone or ground into powders for use as stand alone anhydride containing materials exhibiting properties such as but not limited to high water uptake, acidity, biocompatibility (Sasai, Y. et al., J. Photopolym. Sci. Technol. 2009, 22, 477; Schiller, S. M. et al., Macromolecular Chemistry and Physics 2010, 211, 222) heat resistance (Roberts, R. D. et al., Journal of Cellular Plastics 2007, 43, 135), corrosion inhibition (AU 2010-100175), lubricity and adhesion.
Once the anhydride functional coating has been deposited, the anhydride group may be further derivatised, or complexed with additional reagents as required. In particular, it may be reacted with an amine such as an amine terminated oligonucleotide strand or protein. The derivatisation reaction may be effected in the gaseous phase where the reagents allow, or in a solvent such as water or an organic solvent. .Examples of such solvents include alcohols (such as methanol), and tetrahydrofuran.
The derivatisation may hence result in the immobilisation of reagents on said surface. If derivatisation is spatially addressed, as is known in the art, this results in chemical patterning of the surface.
Other applications for the deposited anhydride containing layers include but not limited to lubricity, adhesion (Winther-Jensen, B. et al., Science 2008, 321, 671), heat resistance, biological cell growth, and the capture of compounds, gases, biomolecules and biospecies. Super-acid layers, proton conduction fuel cell components can be prepared by hydrolysis of the deposited anhydride containing layers to yield acid groups.
Preferred features of all aspects of the invention may be as described above in connection with the first aspect.
Throughout the description and claims of this specification, the words "comprise" and "contain" and variations of the words, for example "comprising" and "comprises", mean "including but not limited to", and do not exclude other moieties, additives, components, integers or steps. Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.
Other features of the present invention will become apparent from the following example. Generally speaking the invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims and drawings). Thus features, integers, characteristics, compounds, chemical moieties or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith.
Moreover unless stated otherwise, any feature disclosed herein may be replaced by an alternative feature serving the same or a similar purpose.
The invention will now be particularly described by way of examples with reference to the accompanying drawings in which:
Figure 1: FTIR spectra of (a) maleic anhydride monomer, (b) pulsed plasma polymer (time on= 20μ5, time off = 1200 με, peak power = 5 W), (c) pulsed plasma polymer (time on = 10 ms, time off = 20 ms, peak power = 20 W, heated monomer). * corresponds to the polymerizable double bond.
Figure 2: FTIR spectra of (a) itaconic anhydride monomer, (b) pulsed plasma polymer (time on= 20 με, time off = 1200 με, peak power = 5 W), (c) pulsed plasma polymer (time on = 10 ms, time off = 20 ms, peak power = 20 W, heated monomer). * corresponds to the polymerizable double bond.
Figure 3: FTIR spectra of (a) (trifluoromethyl)maleic anhydride monomer, (b) pulsed plasma polymer (time on= 20 με, time off = 1200 με, peak power = 5 W). * corresponds to the polymerizable double bond.
Figure 4: FTIR spectra of (a) perfluorohexane monomer, (b) pulsed plasma perfluorohexane (time on = 10 ms, time off = 20 ms, peak power = 20 W), (c) pulsed plasma perfluorohexane with maleic anhydride (same pulsing conditions).
Figure 5: C(ls) XPS peak fits for (a) pulsed plasma perfluorohexane film, (b) pulsed plasma perfluorohexane and maleic anhydride. -Examples
Here various anhydride monomers (maleic anhydride, itaconic anhydride and (trifluoromethyl)maleic anhydride) are deposited using plasma polymerization, the resulting films are characterized by XPS, FTIR, and impedance spectroscopy (for proton conductivity).
Briquettes of maleic anhydride (Aldrich, 99% purity) or itaconic anhydride (Fluka, 97% purity) were ground into a fine powder and loaded into a heated holder. Plasma polymerization experiments were carried out in an electrodeless cylindrical glass reactor surrounded by a copper coil, enclosed in a Faraday cage. The chamber was pumped down using a rotary pump attached to a liquid nitrogen cold trap; a Pirani gauge was used to monitor system pressure. The output impedance of a 13.56 MHz radio frequency (rf) power supply was matched to the partially ionized gas load. During plasmachemical deposition, a signal generator controlled the rf generator and an oscilloscope was used to observe the pulse shape. Before deposition the reactor had been scrubbed with cream cleaner, rinsed in acetone and dried in an oven. A continuous wave air plasma was run to ensure the reactor was completely clean. Next, a substrate was placed into the middle of the chamber above the heated holder. Using the heater a monomer pressure of 0.45 mbar for maleic anhydride, and 0.3 mbar for itaconic anhydride was used. 20 W continuous wave bursts lasting 10 ms, followed by an off- period set at 20 ms were used for pulsed plasma deposition. Upon completion, the rf generator was switched off and the monomer allowed to continue through the system for a further 5 min. Finally, the chamber was evacuated to base pressure to remove all the monomer vapour and then exposed to atmospheric pressure.
In the case of (trifluoromethyl)maleic anhydride, the monomer was loaded into a glass tube and subjected to several freeze-pump-thaw cycles to remove dissolved gases.
For copolymerizations, perfluorohexane was also loaded into a glass tube and subjected to several freeze-pump-thaw cycles to removed dissolved gases and introduced through a separate leak valve at 0.15 mbar vapour pressure.
Plasmachemical polymer film thickness measurements were carried out using an NKD-6000 spectrophotometer (Aquila Instruments Ltd.). Transmittance and reflectance curves within the 350- 1000 nm wavelength range were fitted to a Cauchy model for dielectric materials using a modified Levenburg-Marquardt method. For films with thickness greater than 5 μιτι, the silicon wafer was snapped after immersion in liquid nitrogen and the cross section viewed and measured under an optical microscope.
Sessile drop contact angle measurements were carried out at 20 °C with a video capture apparatus (A.S.T. Products VCA-2500XE). Fourier transform infrared (FTIR) analyses of the plasmachemically deposited films were carried out using an infrared spectrometer (Perkin-Elmer Spectrum One) equipped with a liquid nitrogen cooled mercury cadmium telluride (MCT) detector. All spectra were averaged over 256 scans at a resolution of 4 cm"1. Attenuated total reflection (ATR) measurements were taken using a single bounce diamond tip accessory (Graseby Specac Golden Gate). Reflection-absorption (RAIRS) measurements utilized a variable angle accessory (Graseby Specac) fitted with a KRS-5 polarizer (to remove the s-polarized component) and set at 66°.
A VG Escalab spectrometer equipped with an unmonochromatized Mg K X-ray source (1253.6 eV) and a concentric hemispherical analyzer were used for X-ray photoelectron spectroscopy (XPS) characterization of the plasmachemical films. Elemental compositions were calculated using sensitivity (multiplication) factors derived from chemical standards, C(ls):0(ls):F(ls) 1.00:0.40:0.27.
Impedance measurements were carried out on membranes deposited on a glass substrate with two gold electrodes 16 mm long, separated by a distance of 7 mm. The impedance was measured using an HP 4192A LF impedance analyser in the frequency range from 10 Hz to 13 MHz. Impedance plots took the form of a high frequency impedance arc and a 45° line at lower frequencies. This is a typical response for electrolytes, whose bulk resistance is responsible for the high frequency arc, and the low frequency line is due to diffusion of charged particles (Mikhailenko, S. D et al, Solid State Ionics 2008, 179, 619.). The bulk resistance of the membrane was extracted from fitting the high frequency arc. The formula o=l/RsA, where σ is the membrane conductivity, Rs is the bulk resistance, I is the length of the electrodes, and A is the cross-sectional area of the film.
FTIR spectra for the plasmachemically deposited maleic anhydride films are shown in Figure 1. For the maleic anhydride monomer, the following bands can be assigned: v(C-H) at 3131 cm"1, va(C=0) at 1861 cm"1, vs(C=0) at 1799 cm"1, and v(C=C) at 1592 cm"1 ( Ryan, M. E. et al, Chem. Mater. 1996, 8, 37). In the pulsed plasma polymers, the v(C-H) and v(C=C) bands have disappeared indicating a polymerization at the double bond of maleic anhydride. In the heated deposition, the va(C=0) and vs(C=0) peaks are retained (although slightly shifted due to conformational changes) which indicates retention of the anhydride group within the deposited coating.
FTIR spectra for the plasmachemically deposited itaconic anhydride films are shown in Figure 2. The itaconic anhydride monomer absorbance bands v(C-H) at 3128 cm"1, va(C=0) at 1842 cm"1, vs(C=0) at 1765 cm"1, and v(C=C) at 1668 cm"1 can be assigned. In the pulsed plasma polymers the v(C-H) and v(C=C) bands have disappeared (as with maleic anhydride) indicating loss of carbon-carbon double bond and thus polymerization. For both plasma polymers the anhydride ring has been largely preserved (there is no significant shift in the va(C=0) and vs(C=0) bands). FTIR spectra for the plasmachemically deposited (trifluoromethyl)maleic anhydride film are shown in Figure 3. For the (trifluoromethyl)maleic anhydride monomer, the va(C=0) at 1848 cm"1, vs(C=0) at 1779 cm"1, and v(C=C) at 1666 cm"1 can be assigned. The pulsed plasma polymer has lost the v(C=C) band at 1666 cm"1 indicating polymerization has taken place. The vs(C=0) peak is much wider in the pulsed polymer, which indicates that small amounts of the anhydride rings have opened up to become carboxylic acids.
FTIR spectra for plasmachemically deposited maleic anhydride with the introduction of a 0.15 mbar perfluorohexane vapour can be seen in Figure 4. The perfluorohexane monomer shows intense v(CFx) bands in the region 1350-1100 cm"1. These can be seen as a broad, strong band in the pulse plasma perfluorohexane spectrum. When maleic anhydride is introduced, then the vs(C=0) band at 1784 cm"1 can be clearly seen.
C(ls) XPS spectra for pulsed plasma perfluorohexane are shown in Figure 5. The C:0:F elemental compositions are shown in Table 1. For the pulsed plasma perfluorohexane and maleic anhydride film, a ratio of O to F gives the percentage monomer constituents of the film as 72% maleic anhydride to 28% perfluorohexane.
Table 1: XPS Atomic Percentages for Pulsed Plasma Perfluorohexane with and without mixing with
Maleic Anhydride
Figure imgf000011_0001
Table 2 shows the proton conductivities and stabilities of the different plasma polymer films. (Trifluoromethyl)maleic anhydride is the most stable film and its contact angle is hydrophobic. (Trifluoromethyl)maleic anhydride's high conductivity is enhanced by the electron withdrawing effect of the trifluoromethyl group, which makes the acid stronger. Stronger acid means more free protons in the film (when hydrated) to give higher proton conductivity. Table 2: Proton conductivities at 293 K and Stability in Water of Plasma Polymer Films
Pulsed Plasma Layer conductivity / contact angle / ° stability Deposition mS/cm Rate / nm min"1 maleic anhydride 90±10 25±1 some cracking 5 ± 1 maleic anhydride and 80±10 81±1 no cracking 130 ± 20 perfluorohexane
itaconic anhydride 110±10 35±1 lots of cracking 20 ± 6 itaconic anhydride and 120±10 80±10 little cracking 29 ± 8 perfluorohexane
(trifluoromethyl)maleic 170±10 91±1 no cracking 45 ± 5 anhydride
Nafion Reference 100 - -

Claims

Claims
1. A method for applying anhydride containing coatings to a substrate, said method comprising subjecting said substrate to an excitation medium in the presence of a compound of formula (I)
Figure imgf000013_0001
(I) where X and or Y are sulphur, phosphorus, or carbon atoms with additional linkage(s) to one or more atoms or chemical groups, which are selected from hydrogen or optionally substituted hydrocarbyl group; or alternatively X and Y together with the oxygen atom to which they are attached form part of an optionally substituted heterocyclic ring, either alone or in conjunction with other compounds, provided that when the compound of formula (I) is maleic anhydride, it is co-administered with a further monomer or gas.
2. A method according to claim 1 wherein the compound of formula (I) is a compound formula IA
Figure imgf000013_0002
(IA)
where Rl and R2 are selected from hydrocarbyl groups that carry an electron-withdrawing or electron donating substituent, or together form an optionally unsaturated 3-8 carbon chain that optionally carries at least one electron withdrawing or electron donating substituent.
3. A method according to claim 1 or claim 2 wherein the compound of formula (I) is a compound of formula (II)
Figure imgf000013_0003
(Π)
wherein the dotted bond is either a single or double bond, and R3 and R4 are selected from hydrogen or an electron-withdrawing group, provided at least one of said groups is an electron withdrawing group.
4. A method according to any one of claims 1 or 2 wherein an electron-withdrawing group R3 or R4 is selected from methylene or trifluoromethyl.
5. A method according to claim 3 wherein the compound of formula (II) is selected from maleic anhydride, itaconic anhydride or (trifluoromethyl)maleic anhydride.
6. A method according to any one of the preceding claims wherein the compound of formula (I) is administered with another compound that has the capability to modify and/or be incorporated into the coating forming material and/or the resultant deposited coating.
7. A method according to claim 6 wherein said another compound is inert.
8. A method according to claim 7, wherein the said another compound is not
incorporated within the anhydride coating.
9. A method according to claim 6 wherein the said another compound is selected from a reactive gas or a further monomer.
10. A method according to claim 9 wherein the said another compound is a further monomer which is an organic monomer.
11. A method according to claim 10 wherein the additional monomer is a perfluorinated Ci-io alkane a perfluorinated aryl compound.
12. A method according to any one of claims 6 to 11 wherein the said another compound is delivered in a pulsed manner.
13. A method according to any one of the preceding claims wherein the substrate is subjected to an excitation medium comprising a pulsed plasma in the presence of the compound of formula (I).
14. A method according to claim 13, wherein the plasma is pulsed according to a pulsing regime which changes in a controlled manner throughout the course of a single coating deposition.
15. A method according to any one of the preceding claims wherein the anhydride coating formed is subsequently modified by hydrolysis, aminolysis, esterifcation or acylation of the anhydride groups thereon.
16. A method according to any one of the preceding claims wherein the compound of formula I and/or the further monomer or gas are introduced into the excitation medium in the form of atomised liquid droplets.
17. A method according to any one of the preceding claims wherein at least one of a chamber containing the excitation medium, the substrate, compound of formula I and other compound is heated.
18. A method according to any one of the preceding claims, wherein the substrate is selected from the group comprising a solid, particulate, permeable and porous substrate.
19. A method according to any one of the preceding claims, wherein the substrate comprises a finished article selected from the group comprising a metal, semi-conductor, ceramic, woven or non- woven fibres, synthetic fibres, natural fibres, glass, paper wood, cellulosic material, powder or polymers, such as polytetrafluoroethylene, polythene or polystyrene.
20. A method according to any one of the preceding claims wherein application of the anhydride coating occurs at atmospheric pressure.
21. A substrate coated using a method according to any one of the preceding claims.
22. A substrate according to claim 21, wherein the coating has a proton conductivity equal or greater than 70 mS/cm.
23. A substrate according to claim 22, wherein the coating has a proton conductivity greater than lOOmS/cm.
24. A fuel cell comprising a substrate according to any one of claims 21 to 23.
25. Use of a coating obtained by subjecting a substrate to an excitation medium in the presence of a compound of formula (I)
Figure imgf000016_0001
(I) where X and or Y are sulphur, phosphorus, or carbon atoms with additional linkage(s) to one or more atoms or chemical groups, which are selected from hydrogen or optionally substituted hydrocarbyl group; or alternatively X and Y together with the oxygen atom to which they are attached form part of an optionally substituted heterocyclic ring, either alone or in conjunction with other compounds, as a proton conductor.
26. Use of a coating according to claim 22, wherein the excitation medium comprises continuous wave or pulsed electrical discharges, thermal chemical vapour deposition, initiated chemical vapour deposition (iCVD), photodeposition, e-beam curing, ion-beam curing, target sputtering.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3713874A (en) * 1967-03-14 1973-01-30 Gen Electric Photopolymerized polycarboxylic acid anhydride film coating and product,and method of forming
WO2003084682A1 (en) * 2002-04-10 2003-10-16 Dow Corning Ireland Limited Protective coating composition
US20100072642A1 (en) * 2006-08-25 2010-03-25 Sauflon Cl Limited Method of Coating a Contact Lens
US20100240827A1 (en) * 2005-03-16 2010-09-23 David Barwick Method for Producing a Grafted Polymer Coating and Substrates Formed in Accordance With the Method
WO2013113518A1 (en) * 2012-02-01 2013-08-08 Bioenergy Capital Ag Hydrophilizing plasma coating method

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Publication number Priority date Publication date Assignee Title
GB201112077D0 (en) * 2011-07-14 2011-08-31 Surface Innovations Ltd A method of producing a functionalised surface and surfaces made thereby

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3713874A (en) * 1967-03-14 1973-01-30 Gen Electric Photopolymerized polycarboxylic acid anhydride film coating and product,and method of forming
WO2003084682A1 (en) * 2002-04-10 2003-10-16 Dow Corning Ireland Limited Protective coating composition
US20100240827A1 (en) * 2005-03-16 2010-09-23 David Barwick Method for Producing a Grafted Polymer Coating and Substrates Formed in Accordance With the Method
US20100072642A1 (en) * 2006-08-25 2010-03-25 Sauflon Cl Limited Method of Coating a Contact Lens
WO2013113518A1 (en) * 2012-02-01 2013-08-08 Bioenergy Capital Ag Hydrophilizing plasma coating method

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