WO1998008906A1 - Composition de reseaux polymeres a semi-interpenetration comprenant un fluoropolymere et une resine epoxy - Google Patents

Composition de reseaux polymeres a semi-interpenetration comprenant un fluoropolymere et une resine epoxy Download PDF

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Publication number
WO1998008906A1
WO1998008906A1 PCT/US1997/013561 US9713561W WO9808906A1 WO 1998008906 A1 WO1998008906 A1 WO 1998008906A1 US 9713561 W US9713561 W US 9713561W WO 9808906 A1 WO9808906 A1 WO 9808906A1
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Prior art keywords
fluoropolymer
epoxy resin
semi
composition according
poly
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PCT/US1997/013561
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English (en)
Inventor
Mario A. Perez
William D. Coggio
Douglas S. Parker
Michael C. Palazzotto
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Minnesota Mining And Manufacturing Company
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Priority to EP97936354A priority Critical patent/EP0920482A1/fr
Priority to AU39043/97A priority patent/AU3904397A/en
Priority to JP10511654A priority patent/JP2000516983A/ja
Publication of WO1998008906A1 publication Critical patent/WO1998008906A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks

Definitions

  • This invention relates to semi-interpenetrating polymer networks (semi- IPNs) of thermoplastic resins and thermosetting resins prepared by polymerization of a thermosetting resin (i.e., an epoxy resin) in the presence of a fully prepolymerized thermoplastic fluoropolymer.
  • the invention also provides a method of preparing semi-IPNs that feature 100% solids processing and latent- or post- curing of the epoxy resin, and uses for the semi-IPNs produced by the method
  • Blending a small amount of elastomeric or thermoplastic material into a hardenable thermosetting resin in order to toughen (i.e., increase the ductility of) the thermoset is a common practice in industry.
  • Elastomeric or thermoplastic toughening agents include natural rubbers, polyolefins, and vinyl copolymers such as poly(styrene-co-butadiene)
  • the toughening agent is blended in a ratio of from about 1 :20 to about 1 :4 with a curable thermosetting resin such that the thermoplastic component becomes the dispersed phase in a thermosetting resin providing the continuous phase. See, for example, U.S. Patent Nos 4,861 ,647 and 5,008, 135.
  • Solvent-based blends of fluoropolymers and thermosetting resins have been described in U.S. Patent Nos. 3,784,506 and 4,179,542 as useful for coatings on metal substrates for corrosion protection. These coatings are prepared by ball milling or high-shear mixing of solid resins and a dispersing solvent, followed by application of the dispersion to the metal substrate, typically by spray coating, followed by baking at temperatures up to 250° C. Coating of a 100% solids semi- IPN is not described.
  • the photoinitiated cationic polymerization of epoxides is known
  • Organic aryl sulfonium and aryl iodonium salts are recognized as suitable photoinitiators, i e , compounds which, after irradiation with light, release protons which initiate, e.g., epoxide polymerization.
  • certain complex metal-arene organometallic salts have been described as photoinitiators for cationic polymerizations. In these cases, the cationically polymerizable components are monomers.
  • this invention provides a curable composition
  • a curable composition comprising a) a curable epoxy resin, b) an effective amount of a curative for the curable epoxy resin, c) a fully prepolymerized uncrosslinked fluoropolymer, and d) optionally, a polyolefin or a polyamide, wherein said composition is free of solvent.
  • the epoxy component is present in a range of more than zero and up to 75 weight percent, more preferably more than zero up to 70 weight percent, even more preferably more than zero up to 40 weight percent, and most preferably 0.5 to 15 weight percent
  • the fluoropolymer is present in a range of 25 to less than 100 weight percent, more preferably 30 to less than 100 weight percent, even more preferably 60 to less than 100 weight percent, and most preferably 85 to 95.5 weight percent, based on the total composition.
  • the composition preferably is free of curatives which physically integrate fluorine into the backbone of the cured epoxy.
  • the present invention describes a semi-interpenetrating polymer network comprising a thermally and/or photochemically cured epoxy resin and a fully pre-polymerized fluoropolymer.
  • the present invention describes a method of preparing a semi-IPN comprising the steps of (a) in the absence of a solvent, intimately mixing a fully prepolymerized fluoropolymer optionally in combination with one or both of a polyolefin and a polyamide, both of which preferably are uncrosslinked, in the presence of a photochemically- or thermally-curable epoxy resin, and at least one photo curing agent or high-temperature stable thermal curing agent for the epoxy resin, (b) optionally, applying the solvent-free mixture to a substrate, and (c) at any subsequent time after mixing, activating the curing agent or photocatalyst by supplying sufficient thermal and/or photo energy to the mixture
  • dehydrofluorination of the fluoropolymer prior to combining with an epoxy monomer, optionally in the presence of a polyolefin or a polyamide provides a semi-IPN having increased adhesion to a substrate
  • a solvent-free curable composition comprising a curable thermosetting resin, i.e., an epoxy resin and a curative therefor, and a fully pre-polymerized fluoroelastomer, optionally in the presence of a polyolefin or polyamide, wherein the curable epoxy resin preferably is not exposed to curing conditions, i.e., irradiation by light, preferably UV light, or temperatures greater than about 170° C, in the presence of a suitable oniu salt photoinitiator such as Ar 3 SSbF 6 (wherein "Ar” refers to an aromatic species such as, for instance, phenyl), or a fluorene amine as curing agent until the composition is formed in place, molded, coated, or otherwise prepared in a useful format.
  • a curable thermosetting resin i.e., an epoxy resin and a curative therefor
  • a fully pre-polymerized fluoroelastomer optionally in the presence of a polyole
  • the fluoropolymer-epoxy semi-IPNs are useful as protective coatings, adhesives, and in multilayer assemblies. More particularly, the semi-IPNs of the invention are useful as structural adhesives for metals, plastics, glass or ceramics, as free-standing hot melt adhesives, or as a protective coatings In a preferred embodiment, the fluoropolymer-epoxy semi-IPN can be coated on a flexible substrate to produce an adhesive tape In an additional preferred embodiment, the fluoropolymer-epoxy semi-IPN can be coated on a polymeric tank or vessel, preferably comprising a polyolefin, more preferably comprising polypropylene, used for storage or transporting hydrocarbon fuels such as gasoline, wherein the semi- IPN of the invention can be an intermediate (or "tie") coating that acts as a binding agent between the polymeric vessel and a subsequent fluoropolymer (e.g., poly(tetrafluoroethylene) (PTFE)) protective coating.
  • PTFE
  • backbone means the main polymer chain and not including pendent or end groups
  • cationic organo etallic salt means a salt, the cationic portion of which contains at least one carbon atom of an organic group bonded to a metal atom ("Basic Inorganic Chemistry", F A Cotton, G Wilkinson, Wiley, New York, 1976, p 497), preferably the metal atom is a transition metal atom,
  • group means a chemical species that allows for substitution or which may be substituted by conventional substituents which do not interfere with the desired product, e.g , substituents can be alkoxy, phenyl, halo (F, Cl, Br, I), cyano, mtro, etc ,
  • si-interpenetrating polymer network means a polymer network of two or more polymers wherein at least one polymer is crosslinked and at least one polymer is uncrosslinked
  • fluoroelastomer means a fluorinated polymer having properties of natural or synthetic rubber in that it stretches under tension, has a high tensile strength, retracts rapidly, and recovers its original dimensions fully, and can also exhibit plasticity such that when deformed to the limit, it fails
  • fluoropolymer or fluorocarbon polymer means a polymer prepared from at least one monomer in which at least half of the hydrogen atoms directly attached to carbon atoms have been replaced by fluorine atoms,
  • dehydrofluo ⁇ nation means removal of HF from a fluorocarbon unit of a polymer to produce an unsaturated unit in the polymer
  • curative means removal of HF from a fluorocarbon unit of a polymer to produce an unsaturated unit in the polymer
  • curative means removal of HF from a fluorocarbon unit of a polymer to produce an unsaturated unit in the polymer
  • curative means removal of HF from a fluorocarbon unit of a polymer to produce an unsaturated unit in the polymer
  • Semi-IPNs of the present invention have advantageous properties in that the fluoropolymer component can contribute to electrical properties, chemical resistance, and low usage temperature, and the epoxy monomer component contributes to stability, formulation flexibility, and post-curability of the composition
  • the present invention provides a curable composition
  • a curable composition comprising a) a curable epoxy resin, b) an effective amount of a curative for the curable epoxy resin, and c) a fully prepolymerized uncrosslinked fluoropolymer, and optionally a polyolefin or polyamide
  • blending of the components takes place at a temperature that is below the thermal activation temperature of the catalyst, i e 170° C or higher, preferably in the range of 170 to 400° C, more preferably in the range of 200 to 400° C
  • Useful fluoropolymers can be prepared by methods known in the art and are also commercially available, for example from Dyneon LLC, St Paul, MN, under the trade names THVTM 200, THV 230, THV 500, THV 530, FluorelTM (HFP/VDF), Fluorel- 11TM (TFE/PP/VDF), and Kel-FTM 800, fluoroelastomer, from Elf Atochem North America Inc. (Philadelphia, PA), under the trade names KynarTM 740, 2800, 9301, from Kureha Chemical Co under the trade name KFTM polymer, From Daikin America, Ine (New York, NY), under the trade name
  • NeofluronTM VDF from Central Glass (Tokyo, Japan) under the trade name Cefral SoftTM G-150, and from Asahi Glass Co , Ltd (Tokyo, Japan), under the trade name AFLASTM 200.
  • the fully polymerized fluoropolymer is a terpolymer of tetrafluoroethylene, hexafluoropropylene, and vinylidenefluoride (hereinafter designated THV, available from Dyneon LLC, St Paul, MN) Most preferably, THV 200 (42 mole percent TFE, 20 mole percent HFP, 30 mole percent VDF) is used
  • THV 200 42 mole percent TFE, 20 mole percent HFP, 30 mole percent VDF
  • the terpolymer backbone comprises units arising from the following monomers source unit
  • TFE tetrafluoroethylene
  • VDF vinylidine fluoride
  • fluoropolymers that can be useful in the present invention include in general, homopolymers and copolymers prepared from the group comprising tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropene, vinylidene fluoride, perfluoroalkyl vinyl ethers such as perfluoropropyl vinyl ether, and trifluoroethylene.
  • Specific polymers include, but are not limited to, poly(ethylene-co-chlorotrifluoroethylene) (ECTFE), poly(tetrafluoroethylene) (PTFE), poly(tetrafluoroethylene-co- hexafluoropropylene) (FEP), poly(ethylene-co-tetrafluoroethylene) (ETFE), poly(ethylene-co-tetrafluoroethylene-co-hexafluoropropylene) (EFEP), poly(vinylidene fluoride) (PVDF), and poly(chlorotrifluoroethylene) (PCTFE).
  • ECTFE poly(ethylene-co-chlorotrifluoroethylene)
  • PTFE poly(tetrafluoroethylene)
  • FEP poly(tetrafluoroethylene-co- hexafluoropropylene)
  • EEP poly(ethylene-co-tetrafluoroethylene)
  • EEP poly(ethylene-co-tetrafluoroethylene-co-hex
  • dehydrofluorination of the fluoropolymer prior to combining with an epoxy monomer, and optionally a polyolefin or polyamide provides a semi-IPN having increased adhesion to a substrate.
  • Dehydrofluorination of a fluoropolymer incorporated in a semi-IPN of the invention can provide desirable adhesive properties toward substrates
  • the mole percent of dehydrofluorination present in the fluoropolymer can be in the range of 0.01 to 20, preferably 0.01 to 5.0, more preferably 0.02 to 2.0 mole percent, more preferably 0.2 to 1.15 mole percent.
  • the fluoropolymer can be dehydrofluorinated by any method that will provide sufficient carbon-carbon unsaturation of the fluoropolymer to create increased bond strength between the fluoropolymer and a substrate.
  • the dehydrofluorination process will not introduce into the fluoropolymer a significant amount of grafted substituents.
  • a significant amount it is meant, for instance, an amount greater than about 2 mole percent, based on the number of interpolymerized monomeric units comprising the dehydrofluorinated fluoropolymer.
  • fewer than about 1 mole percent adhesion-promoting groups are grafted onto the fluorinated polymer during dehydrofluorination, e g , fewer than about 0.5, preferably 0.2, or most preferably 0 1 mole percent, based on the total number of interpolymerized polymeric units comprising the dehydrofluorinated fluoropolymer.
  • the introduction of less than a significant amount of grafted substituents onto the fluoropolymer will preferably not alter by a measurable amount the physical or mechanical properties of the fluoropolymer
  • dehydrofluorination of bulk fluoropolymer can be accomplished by solvent-based methods wherein a fluoropolymer is dissolved in a solution of organic solvent. A basic reagent is added to the solution to cause dehydrofluorination, optionally in the presence of a phase transfer catalyst Typical solvents include tetrahydrofuran, methyl isobutyl ketone, methyl ethyl ketone, acetone, n,n-dimethyl formamide, dimethylacetamide, etc. See, for example, U S Patent Nos.
  • dehydrofluorination can be accomplished in a two phase solvent method wherein fluoropolymer is dissolved in an organic solvent, and this solvent phase is mixed with an aqueous phase containing an alkali metal hydroxide and a phase transfer catalyst.
  • Useful catalysts are known in the fluoropolymer art and include, for example, tetrabutylammonium bromide (TBAB), tetraalkyl phosphonium halides, alkylarylphosphonium halides, alkyl ammonium halides, and alkyl phosphonium halides. See U.S. Patent No. 4,742,126.
  • fluoropolymers can be dehydrofluorinated by dry, bulk dehydrofluorination methods referred to in the art as "reactive extrusion methods.”
  • dehydrofluorination is achieved by a dry basic process using, e.g., an extruder or a bowl mixer.
  • Dehydrofluorination of fluoropolymer within an aqueous fluoropolymer emulsion can be also accomplished under relatively mild conditions in a basic, aqueous medium containing substantially no organic solvent, preferably in a 100 percent aqueous medium that contains no organic solvent, and optionally in the presence of a suitable emulsifying surfactant.
  • a basic compound can be added to a fluoropolymer emulsion that contains a fluoropolymer having a structural segment according to formula (1):
  • X and X' are each independently either hydrogen or an electron- withdrawing group.
  • the hydrogen atom is sufficiently acidic to result in dehydrofluorination of the fluoropolymer upon the addition of a base compound to the fluoropolymer emulsion.
  • Suitable basic compounds include ethylamine, hydroxides such as potassium hydroxide (KOH), ammonium hydroxide (NH-OH), sodium hydroxide (NaOH), lithium hydroxide (LiOH); carbonates such as potassium carbonate (K 2 CO 3 ), sodium carbonate (NasCO 3 ), etc.
  • KOH potassium hydroxide
  • NH-OH ammonium hydroxide
  • NaOH sodium hydroxide
  • LiOH lithium hydroxide
  • carbonates such as potassium carbonate (K 2 CO 3 ), sodium carbonate (NasCO 3 ), etc.
  • the basic compound is added to the emulsion in an amount that does not disrupt the stability of the emulsion, and therefore does not cause coagulation of the fluoropolymer.
  • coagulation refers to the condition of fluoropolymer precipitation out of the emulsion.
  • the aqueous dehydrofluorination reaction conditions i.e., reaction time and temperature
  • the emulsifying surfactant within the fluoropolymer emulsion can be one of various emulsifying surfactant known in the fluoropolymer emulsion art These include, for example, anionic surfactants such as fatty acid soaps (sodium or potassium stearate, laurate, palmitate), sulfates and sulfonates (sodium lauryl sulfate and sodium dodecylbenzene sulfonate), nonionic surfactants such as poly(ethylene oxide), poly(vinyl alcohol) and hydroxyethyl cellulose, and fluorinated surfactants including perfluorinated carboxylic acids.
  • anionic surfactants such as fatty acid soaps (sodium or potassium stearate, laurate, palmitate), sulfates and sulfonates (sodium lauryl sulfate and sodium dodecylbenzene sulfonate), nonionic surfactants such
  • emulsifying surfactants can be used alone or in combinations of two or more emulsifying surfactants, and can be present in any effective amount, i.e., an amount that will result in an emulsion. (See, e.g., George Odian, Principles of Polymerization, 3332-3 (2nd ed., 1981.))
  • the above-described dehydrofluorination methods relate to the dehydrofluorination of bulk fluoropolymer (e.g., fluoropolymer granules), or fluoropolymer emulsions.
  • the amount of dehydrofluorination of the fluoropolymer can preferably be in the range from about 0.01 mole percent to 20 mole percent, based on the number of interpolymerized monomeric units used to prepare the dehydrofluorinated fluoropolymer, with the range from about 0.02 mole percent to about 2.0 mole percent being particularly preferred.
  • Two embodiments using a dehydrofluorinated polymer include the following 1. Cure of an epoxy monomer in the presence of a dehydrofluorinated polymer provides a semi-IPN with some chemical binding between the epoxy and fluoropolymer chains.
  • Cure of an epoxy in the presence of a blend of dehydrofluorinated polymer and functionalized (i.e., acidified, e.g., maleated) polyolefin provides a semi-IPN with some chemical binding between the epoxy and fluoropolymer chains and between epoxy and polyolefin chains.
  • Epoxy resins useful in the invention preferably comprise compounds which comprise one or more 1,2-, 1,3- and 1,4-cyclic ethers, which also may be known as 1,2-, 1,3- and 1,4-epoxides.
  • the 1,2-cyclic ethers are preferred
  • Such compounds can be saturated or unsaturated, aliphatic, alicyclic, aromatic or heterocyclic, or can comprise combinations thereof
  • Compounds that contain more than one epoxy group i.e., polyepoxides
  • Monoepoxy monomers useful in the present invention include 3 -hydroxy- 1,2-propylene oxide, oxacyclobutane, cyclohexene oxide, indene oxide, styrene oxide, butyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, n-butylphenol glycidyl ether, vinylcyclohexane monoxide, octylene oxide, alpha-pinene oxide, limonene oxide, and 3- pentadecylphenyl glycidyl ether
  • Aromatic polyepoxides i.e., compounds containing at least one aromatic ring structure, e.g., a benzene ring, and more than one epoxy group
  • polyglycidyl ethers of polyhydric phenols such as Bisphenol A-type resins and their derivatives, epoxy cresol-novolac resins, Bisphenol-F resins and their derivatives, and epoxy phenol-novolac resins
  • glycidyl esters of aromatic carboxylic acids e.g., phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, trimellitic anhydride trigylcidyl ester, and pyromellitic acid tetraglycidyl ester, and mixtures thereof
  • Preferred aromatic polyepoxides are the polyglycidyl ethers of polyhydric phenols, such as the EPONTM series of diglycidyl ethers of Bisphenol-
  • Representative aliphatic polyepoxides include l,4-bis(2,3- epoxypropoxy)butane, polyglycidyl ethers of aliphatic polyols such as glycerol, polypropylene glycol, 1 ,4-butanediol, and the like, and the diglycidyl ester of linoleic dimer acid.
  • monohydroxy- and polyhydroxy-alcohols may be added to the curable compositions of the invention, as chain-extenders for the epoxy resin
  • Suitable examples of alcohols include but are not limited to methanol, ethanol, 1 -propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, pentaerythritol, 1,2-propanediol, ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 ,4-cyclohexane dimethanol, 1,4-cyclohexanediol and glycerol
  • compounds containing hydroxyl groups particularly compounds containing from about 2 to 50 hydroxyl groups and above all, compounds having a weight average molecular weight of from about 50 to 25,000, preferably from about 50 to 2,000, for example
  • Low molecular weight compounds containing at least two reactive hydroxyl groups (molecular weight from about 50 to 400) suitable for use in accordance with the present invention are compounds preferably containing hydroxyl groups and generally containing from about 2 to 8, preferably from about 2 to 4 reactive hydroxyl groups It is also possible to use mixtures of different compounds containing at least two hydroxyl groups and having a molecular weight in the range of from about 50 to 400 Examples of such compounds are ethylene glycol, 1,2- and 1,3 -propylene glycol, 1,4- and 2, 3-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1 ,4-cyclohexane dimethanol, 1,4- cyclohexanediol, trimethylolpropane, 1 ,4-bis- hydroxymethyl cyclohexane, 2-methyl-l,3-propanedio
  • polyols suitable for the purposes of the present invention are the mixtures of hydroxy aldehydes and hydroxy ketones (“formose”) or the polyhydric alcohols obtained therefrom by reduction (“formitol”) which are formed in the autocondensation of formaldehyde hydrate in the presence of metal compounds as catalysts and compounds capable of enediol formation as co-catalysts (see, for example, German Offenlegungsschrift Nos. 2,639,084, 2,714,084, 2,714,104, 2,721,186, 2,738,154 and 2,738,512).
  • polyfunctional alcohols such as carbowaxes, poly(ethylene glycol), poly(ethylene glycol methyl ether), poly(ethylene glycol) tetrahydrofiirfuryl ether, poly(propylene glycol) may also be used in the compositions of the present invention.
  • Mixtures of THV and epoxies within the present invention can define a miscibility window having a composition range that allows for the manufacture of semi-IPNs. No depression in the crystallization onset of THV 200 was observed upon the incorporation of an epoxy monomer Crystalline point depression in combination with melting point depression was indicative of thermodynamic partial miscibility.
  • Partial miscibility means that only over a narrow range of conditions, that is composition/temperature/pressure, was a homogeneous solution observed
  • the area of the crystallization exotherms and melting endotherms decreased with increasing epoxy content for the THV/epoxy semi-IPN, as was shown by differential scanning measurements taken between room temperature and 200°C This demonstrated that the crystalline content of the fluoropolymer, which was relatively low ( ⁇ 20%), was being adversely affected by the presence of the epoxy monomer. It is believed that most of the epoxy monomer was taken up by (swelled) the amorphous component of the THV
  • Catalysts for curing the epoxy of the present invention can be activated by either thermal means or photochemical means Preferred catalysts are thermally activated.
  • Known photocatalysts are of two general types onium salts and cationic organometallic salts, and both are useful in the invention
  • Onium salt photoinitiators for cationic polymerizations include iodonium and sulfonium complex salts Useful aromatic iodonium complex salts are of the general formula. wherein
  • Ar 1 and Ar 2 are the same or different and are aromatic groups having from 4 to about 20 carbon atoms, and are selected from the group consisting of phenyl, thienyl, furanyl, and pyrazolyl groups;
  • Z is selected from the group consisting of oxygen, sulfur, a carbon-carbon bond
  • R is an aryl group (having from 6 to about 20 carbon atoms, such as phenyl) or acyl group (having from 2 to about 20 carbon atoms, such as acetyl, or benzoyl), and
  • Ri and R 2 are selected from the group consisting of hydrogen, alkyl groups having from 1 to about 4 carbon atoms, and alkenyl groups having from 2 to about 4 carbon atoms; m is zero or 1 ; and
  • X has the formula DQdonating, wherein D is a metal from Groups IB to VIII or a metalloid from Groups IIIA to VA of the Periodic Chart of the Elements (Chemical Abstracts version), Q is a halogen atom, and n is an integer having a value of from 1 to 6.
  • the metals are copper, zinc, titanium, vanadium, chromium, magnesium, manganese, iron, cobalt, or nickel and the metalloids preferably are boron, aluminum, antimony, tin, arsenic and phosphorous
  • the halogen, Q is chlorine or fluorine.
  • suitable anions are BF 4 " , PF ( .
  • the anions are BF 4 " , PF 6 “ , SbF 6 “ , AsF 6 “ , SbF 5 OH “ , and SbCl 6 “ .
  • the anions are SbF 6 " , AsF 6 " , and SbF 5 OH "
  • the A ⁇ and Ar 2 aromatic groups may optionally have one or more fused benzo rings (e.g., naphthyl, benzothienyl, dibenzothienyl, benzofiiranyl, dibenzofiiranyl, etc.).
  • the aromatic groups may also be substituted, if desired, by one or more non-basic groups if they are essentially non-reactive with epoxide and hydroxyl functionalities.
  • aromatic iodonium complex salts are described more fully in U S Patent No. 4,256,828, incorporated herein by reference.
  • the preferred aromatic iodonium complex salts are (Ar) 2 I PF ⁇ and (Ar) 2 I SbF ⁇ .
  • aromatic iodonium complex salts useful in the invention are photosensitive only in the ultraviolet region of the spectrum. However, they can be sensitized to the near ultraviolet and the visible range of the spectrum by sensitizers for known photolyzable organic halogen compounds.
  • Illustrative sensitizers include aromatic amines and colored aromatic polycyclic hydrocarbons, as described in U S Patent No. 4,250,053, incorporated herein by reference.
  • Aromatic sulfonium complex salt initiators suitable for use in the invention are of the general formula
  • R 3 , R t and R ? can be the same or different, provided that at least one of the groups is aromatic.
  • These groups can be selected from the group consisting of aromatic groups having from 4 to about 20 carbon atoms (e.g., substituted and unsubstituted phenyl, thienyl, and furanyl) and alkyl groups having from 1 to about 20 carbon atoms.
  • alkyl includes substituted alkyl groups (e.g., substituents such as halogen, hydroxy, alkoxy, and aryl).
  • R 3 , R 4 and R 5 are each aromatic; and
  • Z, m and X are all as defined above with regard to the iodonium complex salts.
  • R 3 , R_, or R5 is an aromatic group, it may optionally have one or more fused benzo rings (e.g., naphthyl, benzothienyl, dibenzothienyl, benzofiiranyl. dibenzofuranyl, etc.).
  • the aromatic groups may also be substituted, if desired, by one or more non-basic groups if they are essentially non-reactive with epoxide and hydroxyl functionalities.
  • Triaryl-substituted salts such as triphenylsulfonium hexafluoroantimonate and p-(phenyl(thiophenyl)diphenylsulfonium hexafluoroantimonate are the preferred sulfonium salts.
  • Useful sulfonium salts are described more fully in U.S. Patent No. 5,256,828.
  • aromatic sulfonium complex salts useful in the invention are photosensitive only in the ultraviolet region of the spectrum. However, they can be sensitized to the near ultraviolet and the visible range of the spectrum by a select group of sensitizers such as described in U.S. Patent Nos 4,256,828 and 4,250,053
  • Suitable photoactivatable organometallic complex salts useful in the invention include those described in U.S. Patent Nos. 5,059,701, 5,191,101, and 5,252,694, each of which is incorporated herein by reference.
  • Such salts of organometallic cations have the general formula
  • M" 1 represents a metal atom selected from elements of periodic groups IVB, VB, VTB, VIIB and VIII, preferably Cr, Mo, W, Mn, Re, Fe, and Co
  • L 1 represents none, one, or two ligands contributing ⁇ -electrons that can be the same or different ligand selected from the group consisting of substituted and unsubstituted acyclic and cyclic unsaturated compounds and groups and substituted and unsubstituted carbocyclic aromatic and heterocyclic aromatic compounds, each capable of contributing two to twelve ⁇ -electrons to the valence shell of the metal atom M.
  • L 1 is selected from the group consisting of substituted and unsubstituted ⁇ 3 -allyl, ⁇ 5 -cyclopentadienyl, ⁇ 7 -cycloheptatrienyl compounds, and ⁇ 6 -aromatic compounds selected from the group consisting of ⁇ 6 -benzene and substituted ⁇ 6 -benzene compounds (e.g.
  • L 2 represents none or 1 to 3 ligands contributing an even number of ⁇ - electrons that can be the same or different ligand selected from the group consisting of carbon monoxide, nitrosonium, triphenyl phosphine, triphenyl stibine and derivatives of phosphorous, arsenic and antimony, with the proviso that the total electronic charge contributed to MTM by L l and L 2 results in a net residual positive charge of e to the complex; and e is an integer having a value of 1 or 2, the residual charge of the complex cation;
  • X is a halogen-containing complex anion, as described above
  • suitable salts of organometallic complex cations useful as photoactivatable catalysts in the present invention include:
  • Preferred salts of organometallic complex cations useful in the invention include one or more of the following: ( ⁇ -xylenes (mixed isomers))( ⁇ 5 - cyclopentadienyl)Fe +1 SbF 6 " , ( ⁇ 6 -xylenes (mixed isomers))( ⁇ 5 -cyclopentadienyl)Fe ⁇ PF 6 " , ( ⁇ 6 -o, p, or m-xylene)( ⁇ 5 -cyclopentadienyl)Fe +1 SbF 6 " , and ( ⁇ 6 -mesitylene)( ⁇ 5 - cyclopentadienyl)Fe +1 SbF 6 ' .
  • the organometallic salt initiators can be accompanied by an accelerator such as an oxalate ester of a tertiary alcohol.
  • the accelerator preferably comprises from 0.01 to 10 percent by weight, preferably from 0 1 to 4% by weight of the total polymerizable mixture (thermoplastic component, thermosetting co ponent and catalyst(s)), as described in U.S. Patent No 5,252,694, which is incorporated herein by reference.
  • Useful commercially available initiators include FX-512, an aromatic sulfonium complex salt (3M Company, St. Paul, MN), UVITM-6974, an aromatic sulfonium complex salt (Union Carbide Corp., Danbury, CT) and IRGACURETM 261, a cationic organometallic complex salt (Ciba Geigy Chemicals, Hawthorne, NY).
  • Photoinitiators useful in the invention can be present in an amount in the range of 0.01 to 10 weight percent, preferably 0 1 to 5, and most preferably 0 1 to 2 weight percent based on total curable resin composition
  • thermally-activated curing agents for epoxy resins e.g., compounds that effect curing and crosslinking of the epoxide by entering into a chemical reaction therewith
  • curing agents are thermally stable at temperatures at which mixing of the components takes place.
  • Suitable thermal curing agents include aliphatic and aromatic primary and secondary amines, e.g., di(4-aminophenyl)sulfone, di(4-aminophenyl)ether, and 2,2- bis-(4-aminophenylpropane; aliphatic and aromatic tertiary amines, e.g., dimethylaminopropylamine and pyridine; quaternary ammonium salts, particularly pyridinium salts such as N-methyl-4-picolinium hexafluorophosphate; fluorene diamines, such as those described in U S.
  • aliphatic and aromatic primary and secondary amines e.g., di(4-aminophenyl)sulfone, di(4-aminophenyl)ether, and 2,2- bis-(4-aminophenylpropane
  • aliphatic and aromatic tertiary amines e.g., dimethylamin
  • Patent No 4,684,678 incorporated herein by reference; boron trifluoride complexes such as BF 3 * Et 2 O and BF 3 »H 2 NC 2 H 5 OH, imidazoles, such as methylimidazole, hydrazines, such as adipohydrazine, and guanidines, such as tetramethylguanidine and dicyandiamide (cyanoguanidine, commonly known as DiCy).
  • boron trifluoride complexes such as BF 3 * Et 2 O and BF 3 »H 2 NC 2 H 5 OH
  • imidazoles such as methylimidazole
  • hydrazines such as adipohydrazine
  • guanidines such as tetramethylguanidine and dicyandiamide (cyanoguanidine, commonly known as DiCy).
  • these catalysts are particularly suited to use with the higher extrusion temperatures of, for example, fluoroelastomers, of 200°C or greater.
  • the compositions are stable in the extruder, i.e., they do not cure, eliminating problems that would be caused by crosslinking during this processing step. When finally cured, these compositions give surprisingly high overlap shear bond strengths.
  • cationic nitrogen centered salts are active in this temperature range.
  • a surprising result is the order of the exotherm temperatures for a series of these compounds when the anion is varied and the cation is held constant The exothem temperatures increase in the order PF 6 ' ⁇ AsF 6 " ⁇ SbF 6 " . This is surprising in that those skilled in the epoxy resin art would expect the order to be the reverse.
  • Classes of salts useful as thermal curatives include pyridinium, quinoliniun, benzoxazolium, benzothiazolium, indolenium, ammonium, and phosphonium salts Structures of salts that have been found to be particularly suitable as catalysts in the epoxy/ polypropylene compositions include'
  • R is an alkyl group or an aryl group
  • R is an alkyl group or an acyl group or an aryl group
  • R" is an alkyl group or an aryl group
  • R"' is an alkyl group or an aryl group
  • R and R together can form a ring structure of from 4 to 8 carbon ato s (R, R and R'" together can form a bi cyclic ring structure )
  • Alkyl groups can have 1 to 12 carbon atoms
  • aryl groups can be 1 to 3 fused rings (e.g , naphthalene) or joined rings (e.g., biphenyl) having up to 30 carbon atoms
  • Each cationic charge must be balanced by the appropriate number of anions, X " and wherein X ' can be as previously defined, preferably X " is BF " 4 , PF " 6 ,
  • X is PF " 6 wherein each R, R', R", R"' independently can be an alkyl, aryl, or alkaryl group having up to 20 carbon atoms, and X is as previously defined
  • Thermal curatives can be present in an amount such that the ratio of epoxy equivalents to thermal epoxy curative equivalents is in the range of 0 9 1 to 2 1 Photocuring can take place before the thermoplastic crystallizes or after crystallization takes place For most potential uses, curing of the film is not required until it is ready to be made into the final product Curing in-line can be desirable when molecular orientation of the thermoplastic needs to be preserved
  • Various adjuvants can also be added to the compositions of the invention to alter the physical characteristics of the cured semi-IPN Included among useful adjuvants are thixotropic agents such as fumed silica, pigments to enhance color tones such as ferric oxide, carbon black and titanium dioxide, fillers such as mica, silica, acicular wollastonite, calcium carbonate, magnesium sulfate and calcium sulfate; clays such as bentonite; glass beads and bubbles, reinforcing materials such as unidirectional woven and nonwoven webs of organic and inorganic fibers such
  • polyolefins preferably refers to fully pre-polymerized polymeric hydrocarbons bearing essentially no organic functional groups, prepared from homopolymerization and/or copolymerization of hydrocarbon olefinic monomers by cationic-, anionic-, or Ziegler-Natta-type polymerization processes
  • Homopolymeric polyolefins useful in the invention include polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-1-hexene, poly- 1-octene and related polyolefins
  • Preferred homopolymeric polyolefins include polyethylene (e.g., Dow 25455TM, available from Dow Chemical Co., Midland, MI) and polypropylene (e.g., Shell DS5D45TM, available from Shell Chemicals, Houston, TX, or Exxon 3445TM and 3505TM, available from Exxon Chemicals, Houston, TX)
  • Polyolefins useful in the invention can be present in an amount such that the ratio of fluoropolymer to polyolefin is within the range of 1 99 to 99 1, preferably 25:75 to 75 25, and most preferably 50.50
  • the epoxy resin component preferably comprises from about 10 to about 15 % by weight of the total weight of the mixture, for all ratios of polyolefin fluoropolymer
  • polyamides refers to fully pre-polymerized condensation polymers characterized by the presence of the amide group, -CONH- , in the polymer backbone.
  • Polyamides are prepared, e.g., by the condensation polymerization of a polyfunctional carboxyl-containing species such as a dicarboxylic acid or a dicarboxylic acid halide with a polyfunctional amine, or by self-condensation of a bifunctional molecule that has both amine- and carboxyl- functionality
  • the reactive species can be individually aliphatic, aromatic, carbocyclic, polycyclic, saturated, unsaturated, straight chain or branched
  • Polyamides can be the polymerization product of a single polycarboxyl-functional species with a single polyamine species as well as the polymerization product of a mixture of polycarboxyl species and a mixture of polyamine species Industry has developed a number of routes to polyamides, all of which are intended to be included in the present definition While the general class of
  • Polyamides useful in the invention can be present in an amount such that the ratio of fluoropolymer to polyamide is within the range of 1 99 to 99 1, preferably 25 75 to 75 25, and most preferably 50 50.
  • the epoxy resin component preferably comprises from about 10 to about 15 % by weight of the total weight of the mixture, for all ratios of polyamide fluoropolymer
  • the fluoropolymer-epoxy semi-IPNs are useful as protective coatings, adhesives, self-supported films, and in multilayer assemblies More particularly, the semi-IPNs of the invention are useful as structural adhesives for metals, plastics, glass or ceramics, as free-standing hot melt adhesives, or as protective coatings
  • the fluoropolymer-epoxy semi-IPN can be coated on a flexible substrate to produce an adhesive tape
  • the semi- IPN coatings and films can be in multilayer assemblies for electrical and communication cables
  • the fluoropolymer- epoxy semi-IPN can be coated on a polymeric, preferably polyolefin, more preferably polypropylene, tank or vessel used for storage or transporting hydrocarbon fuels such as gasoline, wherein the semi-IPN of the invention can be an intermediate (or "tie") coating that acts as a binding agent between the polyolefin vessel and a subsequent fluoropolymer (e.g , poly(tie)
  • Tensile Modulus Tensile Strength
  • Instron tensile testing machine Instron Corp., Park Ridge, IL
  • model 1122 equipped with a 5KN load cell, model 2511-317.
  • Cross-head speeds and gauge lengths varied for each test, as indicated.
  • Overlap Shear measurements were obtained essentially according to ASTM D1002-94, "Apparent Shear Strength of Single-Lap-Joint Adhesively Bonded Metal Specimens by Tension Loading.”
  • Cold rolled steel coupons measuring 1 1.43 cm x 2.54 cm x 3.2 mm were thoroughly cleaned with methyl ethyl ketone and heated on a hot plate to temperatures of from about 185 to about 250°C. Films having thicknesses of from about 0.25 and 0.75 mm were applied to the hot metal surface using a silicon rubber roller and allowed to melt.
  • Peak loads and strain to break were recorded from an Instron machine with a 44.5 KN load cell.
  • Dielectric Constant Dielectric constant
  • compositions can be prepared in at least two ways
  • method A dried, dehydrofluorinated THV 200TM powder was mixed in a preheated Brabender internal mixer equipped with sigma blades at 185°C with from 2 to 10% by weight of PR500TM based upon the total weight of the thermoplastic polymer component The samples were then melt pressed to the desired thickness
  • method B a twin screw extrusion machine was used to make the films
  • PR500TM (comprising mixture of epoxies plus fluorene amine curative) was added by means of a side port downstream from the fluoropolymer pellet feeding port Samples were extruded at a screw speed of 90 rpm in a Haake counter- rotating conical twin screw extruder (31 8/20 mm (rear/front)) equipped with a static mixer and a 15.2 cm (6") sheet die The temperature profile from feed to die was (°C)
  • Lamination or adhesion on metals was accomplished using UV or thermal cure.
  • adhesion to take place the substrate needed to be heated above the melting point of the thermoplastic and then irradiated
  • the minimum cycle for thermally cured systems was 5 minutes at 225°C Sylvania 350 BL bulbs (Siemens).
  • thermoset phase Fusion lamps could be used also as long as the radiation dosage was between 2-3 J/cm ⁇
  • the sample was then removed from the heat source and cooled to room temperature Overlap shear tests were used to quantify adhesion at room temperature Data of Table 1 show the adhesive properties obtained when the thermoplastic was molten du ⁇ ng cure of the thermoset
  • EponTM 828 aromatic epoxy (Shell Chemicals, Houston, TX) (photo cu ⁇ ng system)
  • PR500TM mixture of epoxies + fluorene diamine curative (3M Co , St Paul, MN) (thermal cunng system)
  • G3003 Maleated polypropylene wa ⁇ (Eastman Chemical Co Kingsport
  • DS7C50TM nonfunctionalized fully saturated stereoregular polyolefin (Shell Chemicals,
  • Table 1 Data in Table 1 show the increase in modulus realized with different compositions.
  • the tensile properties listed are those obtained by curing with fusion lamps at room temperature, that is, curing when the thermoplastic was in the solid state. Low adhesion developed if the thermoplastic was not molten during cure of the thermoset. Increases in tensile modulus were observed when cure took place after the thermoplastic crystallized.
  • THV/polyolefin/epoxy extrudates had a very good appearance and were easy to extrude.
  • DS7C50 was a polypropylene with a rubbery phase content of 20%. The rubbery phase was a fully saturated ethylenc(55%)/propylene copolymer(45%) The molecular weight ratio of rubber to polypropylene homopolymer was 1.5. This rubber content in polypropylene provided optimum adhesive properties in THV/polyolefin/epoxy semi-IPNs
  • THV semi-IPN coatings and films can be in multilayer assemblies for electrical and communication cables
  • Epoxy- fluoropolymer semi-IPNs of the invention were prepared by extrusion. Fluoropolymer, epoxy resin, and catalyst were mixed in a Haake conical twin screw extruder (rear diameter: 31.8 mm; front diameter: 20 mm) equipped with Zenith HPB gear pumps having a capacity of 0.16 mL/turn for pumping monomer into the extruder. Temperature setpoints in the extruder typically were all set at 271° C, and actual zone temperatures typically were 234 - 273 - 271 - 271 °C. Six samples were prepared:
  • FEP-100 was poly(tetrafluoroethylene-co- hexafluoropropylene), available from Dupont Chemical Co., Wilmington, DE; EP- 610 was poly(ethylene-co-tetrafluoroethylene), available from Daikin, Japan; Kynar 740 was poly(vinylidene fluoride), available from Elf Atochem, Philadelphia, PA, and MP was N-methyl-4-picolinium hexafluorophosphate (prepared as in Example 6).
  • Samples of approximately 380 micrometers thickness were tested qualitatively for adhesion to steel, polyimide film, and TeflonTM film substrates by placing the extrudate (10.16 cm x 2.54 cm) on the substrate and heating the construction to 271° for 5 minutes.
  • Samples 3D and 3F showed limited adhesion to steel, but none to polyimide or Teflon.
  • Samples 3A, 3B, 3C, and 3E showed no adhesion to any substrates under these conditions.
  • Samples 3D and 3F showed adhesion to steel.
  • Sample 3B showed slightly greater adhesion to Teflon than to steel, but all other samples showed no adhesion to Teflon.
  • Samples 3D and 3F showed some adhesion to polyimide film.
  • Adhesion of Sample 3D to steel was further shown as follows Five strips of Sample 3D, measuring 15 x 2.54 x 0.03 cm, were placed on steel bars measuring 11.4 x 2.54 x 0.03 cm and heated to 299° C for 15 minutes. On cooling, peel values were obtained by placing the steel bar in one clamp of an Instron instrument and excess sample film in the other clamp to measure the 180° peel test. A gauge length of 7.62 cm was used, and crosshead speed was 5.08 cm/ min. Data are shown in Table 3b below.
  • a semi-IPN construction comprising THV 200 and an 3.4% by weight ERL-4221 epoxy resin (Shell Chemical Co., Houston, TX) was prepared in an extruder with a temperature profile of 192 - 222 - 221 - 219° C and a pellet feed rate of 14.2 g/min.
  • the cast wheel was kept at 20° C, line speed setting was 25 Triarylsulfonium hexafluorophosphate (FX-512 Activated Epoxy Curative, 3M Company, St. Paul, MN) catalyst concentration was 1% by weight
  • PET poly(ethylene terephthalate) release liner
  • ScotchparTM polyester film 3M St. Paul, MN
  • the two samples were placed on a hot plate at 190° C and irradiated with a Sylvania 350 Blacklight UV generating bulb (Siemens Corp./Osram Sylvania Inc. Danvers, MA) at a distance of 1 cm for 5 minutes.
  • Semi-IPNS of the invention comprising blends of THV 500 fluoropolymer and compatible polymers were prepared in a twin-screw extruder as described above. Composition of the blends is shown in Table 5.
  • Catalyst S triarylsulfonium hexafluorophosphate (FX-512 Activated Epoxy Curative, 3M Company, St. Paul, MN)
  • Examples 5A - 5E were heated at 185° C on a Teflon-covered hot plate under UV irradiation (Sylvania Blacklight bulbs) at a distance of 1cm for 5 minutes while in contact with the following polymer films:
  • PET release liner (ScotchparTM polyester film)
  • Polyolefin 1150-1TM Eastman Chemicals, Kingsport, TN
  • Examples 5A - 5E showed adhesion to PET (Film 1) and Nylon (Film 3)
  • Example 5B also showed adhesion to wax-filled polyethylene (TeniteTM 1550P) (Film 4) and metallocene polyolefin (Film 5);
  • Example 5C also showed adhesion to polyolefin 1150-1 (Film 2), metallocene polyolefin (Film 5) and polypropylene-epoxy (Film 6)
  • Example 5 Data of Example 5 show that cured blends of nylon or functionalized polyolefins with THV-Epoxy semi-IPNS of the invention exhibited good adhesion to a number of polymeric substrates.
  • the blends can be useful as tie layers in multilayer polymeric constructions to help adhere a protective coating to a polymeric substrate such as polyethylene
  • N-Methyl-4-picolinium hexafluorophosphate catalyst (Catalyst MP) was prepared as follows:

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Abstract

Composition durcissable comprenant une résine époxy durcissable, une quantité efficace d'un agent durcissant pour la résine époxy, un fluoropolymère non réticulé totalement prépolymérisé et éventuellement une polyoléfine ou un polyamide. Il est possible de déshydrofluorer jusqu'à 20 % en poids du fluoropolymère afin d'obtenir un réseau polymère à semi-interpénétration qui adhère mieux aux substrats. Les réseaux polymères à semi-interpénétration comprenant un fluoropolymère et une résine époxy sont utiles comme revêtements de protection, comme adhésifs tels que des bandes adhésives, et dans des ensembles multicouches.
PCT/US1997/013561 1996-08-26 1997-08-01 Composition de reseaux polymeres a semi-interpenetration comprenant un fluoropolymere et une resine epoxy WO1998008906A1 (fr)

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EP97936354A EP0920482A1 (fr) 1996-08-26 1997-08-01 Composition de reseaux polymeres a semi-interpenetration comprenant un fluoropolymere et une resine epoxy
AU39043/97A AU3904397A (en) 1996-08-26 1997-08-01 Fluoropolymer-epoxy resin semi-interpenetrating network composition
JP10511654A JP2000516983A (ja) 1996-08-26 1997-08-01 フルオロポリマー―エポキシ樹脂半相互貫入網目構造組成物

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MASCIA L ET AL: "MECHANICAL PROPERTIES AND THERMAL AGEING OF A PERFLUOROETHER- MODIFIED EPOXY RESIN IN CASTINGS AND GLASS FIBRE COMPOSITES", COMPOSITES, vol. 26, no. 5, 1 May 1995 (1995-05-01), pages 379 - 385, XP000508199 *

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AU3904397A (en) 1998-03-19

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