WO2022107020A1 - Composition de revêtement comprenant un fluoropolymère durcissable et un hydrofluorochloropropène, et fluoroélastomères issus de celle-ci - Google Patents

Composition de revêtement comprenant un fluoropolymère durcissable et un hydrofluorochloropropène, et fluoroélastomères issus de celle-ci Download PDF

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WO2022107020A1
WO2022107020A1 PCT/IB2021/060660 IB2021060660W WO2022107020A1 WO 2022107020 A1 WO2022107020 A1 WO 2022107020A1 IB 2021060660 W IB2021060660 W IB 2021060660W WO 2022107020 A1 WO2022107020 A1 WO 2022107020A1
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composition
coatable
previous
coatable composition
hydrochlorofluoropropene
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PCT/IB2021/060660
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Yuta Suzuki
Tatsuo Fukushi
Takeshi Machida
Hiroshi Nishioka
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3M Innovative Properties Company
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    • 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
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C09D127/20—Homopolymers or copolymers of hexafluoropropene

Definitions

  • the present disclosure relates to a composition
  • a composition comprising a partially fluorinated amorphous polymer in a liquid solvent comprising hydrochlorofluoropropene. Methods of making an article using the composition are disclosed herein.
  • fluoropolymeric elastomers Due to their elasticity and inertness to chemical reactivity, heat, or both, fluoropolymeric elastomers are useful in making articles such as seals, gaskets, o-rings, and hoses. Many of the copolymers used to make fluoropolymeric elastomers have relatively high viscosities in comparison to non-fluorinated materials used to make elastomers (e.g., silicones for silicone elastomers).
  • solvents such as acetone, 2-butanone, 4-methyl-2 -pentanone, cyclohexanone, methyl formate, ethyl formate, methyl acetate, ethyl acetate, n-butyl acetate, tertbutyl acetate, or dimethyl carbonate are used to reduce the viscosity of the fluoropolymeric compositions.
  • solvents are flammable, and therefore explosion-protected measures are needed for manufacturing processes and equipment.
  • Such cost reductions can include using a partially fluorinated polymer, which is typically cheaper than its perfluororinated counterpart; using a non-flammable, more environmentally friendly solvent; and optionally making products in a continuous fashion versus a batch-type process.
  • a curable composition comprising:
  • the curing initiator is a photoinitiator.
  • the curing initiator is a peroxide cure initiator.
  • a method of making a gasket comprising (i) applying a coatable composition comprising a partially fluorinated amorphous polymer comprising at least one of an iodine, a bromine, and a nitrile cure site; a curing initiator; a crosslinking agent; and a liquid solvent comprising a hydrochlorofluoropropene; and (ii) curing the coatable composition.
  • a and/or B includes, (A and B) and (A or B);
  • backbone refers to the main continuous chain of the polymer
  • crosslink refers to connecting two pre-formed polymer chains using chemical bonds or chemical groups
  • cure site refers to functional groups, which may participate in crosslinking
  • interpolymerized refers to monomers that are polymerized together to form a polymer backbone
  • “monomer” is a molecule which can undergo polymerization which then form part of the essential structure of a polymer
  • perfluorinated means a group or a compound derived from a hydrocarbon wherein all hydrogen atoms have been replaced by fluorine atoms.
  • a perfluorinated compound may however still contain atoms other than fluorine and carbon atoms, like oxygen atoms, chlorine atoms, bromine atoms and iodine atoms; and
  • polymer refers to a macrostructure having a number average molecular weight (Mn) of at least 10,000, 30,000, 50,000, 100,000, 200,000, 500,000, or even at least 1,000,000 dalton and not such a high molecular weight as to cause premature gelling of the polymer.
  • Mn number average molecular weight
  • At least one includes all numbers of one and greater (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).
  • curable fluoropolymer composition comprises a partially fluorinated amorphous polymer in a liquid solvent, wherein the liquid solvent comprises hydrochlorofluoropropene.
  • curable fluoropolymer compositions can be cured via peroxide or actinic radiation.
  • the compounds curable fluoropolymer compositions of the present disclosure have good environmental properties as well as having good performance attributes, such as non-flammability, and ability to cure.
  • the fluoropolymers of the present disclosure are amorphous, meaning that there is an absence of long-range order (i.e., in long-range order the arrangement and orientation of the macromolecules beyond their nearest neighbors is understood).
  • the amorphous polymer has no detectable crystalline character by DSC (differential scanning calorimetry).
  • the fluoropolymer would have no melting point or melt transitions with an enthalpy more than 0.002, 0.01, 0.1, or even 1 Joule/g from the second heat of a heat/cool/heat cycle, when tested using a DSC thermogram with a first heat cycle starting at -85°C and ramped at 10 °C/min to 350°C, cooling to -85°C at a rate of 10°C/min and a second heat cycle starting from -85°C and ramped at 10 °C/min to 350°C.
  • the amorphous fluoropolymers of the present disclosure decompose above a temperature of 350, 325, 300, or even 275°C.
  • the amorphous fluoropolymers of the present disclosure are partially fluorinated.
  • a partially fluorinated amorphous polymer comprises both C-F and C-H bonds along the carbon backbone of the polymer chain.
  • the amorphous fluoropolymer of the present disclosure comprises at least 30, 50, 60, 66, 68, 70, or even 71% by weight of fluorine, and no more than 72, or even 73% by weight of fluorine (based on the total weight of the amorphous fluoropolymer).
  • the amorphous fluoropolymer is derived from at least one hydrogencontaining monomer and at least one fluorine-containing monomer. In one embodiment, the amorphous fluoropolymer is derived from a monomer comprising both an olefinic hydrogen and an olefinic fluorine, such as vinylidene fluoride. Hydrogen containing monomers include those known in the art. The hydrogen-containing monomers may or may not contain fluorine atoms.
  • Exemplary hydrogen-containing monomers include: vinylidene fluoride, pentafluoropropylene (e.g., 2-hydropentafluoropropylene), vinyl fluoride, trifluoroethylene, propylene, ethylene, isobutylene, and combinations thereof.
  • Fluorine-containing monomers include those known in the art.
  • the amorphous fluoropolymer comprises interpolymerized units derived from vinylidene fluoride (VDF). In one embodiment, the amorphous fluoropolymer is derived from 30-70 wt % VDF, or even 35-65 wt % VDF.
  • the amorphous fluoropolymer comprises interpolymerized units derived from at least 30, 35, 40, 45, 50, 55, or even 60 wt% and at most 65, 70, or even 75 wt% VDF; and at least 25, 30 or even 35 wt% and at most 40, 45, 50, 60, 65, or even 70 wt% HFP.
  • the amorphous fluoropolymer comprises interpolymerized units derived from at least 30, 35, 40, 45, 50, 55, or even 60 wt% and at most 65, 70, or even 75 wt% VDF; at least 10, 15, 20, or even 25 wt% and at most 27, 30, 35, 40, or even 45 wt% HFP; and at least 3, 5, 7, or even 9 wt% and at most 10, 12, 15, 20, 25, or even 15 wt% TFE.
  • the amorphous fluoropolymer comprises interpolymerized units derived from at least 25, 30, or even 35 wt% and at most 40, 45, 50, 55, or even 65 wt% VDF; at least 15, 20, 25, or even 30 wt% and at most 35, 40, or even 45 wt% HFP; and at least 1, 5, 10 15, 20, or even 30 wt% and at most 30, 35, or even 40 wt% TFE.
  • the amorphous fluoropolymer comprises interpolymerized units derived from at least 30, 35, 40, or even 45 wt% and at most 55, 60, or even 65 wt% VDF; at least 25, 30, or even 35 wt% and at most 40, 45, 50, 55, 60, or even 65 wt% PMVE; and at least 3, 5, or even 7 wt% and at most 10, 15, or even 20 wt% TFE.
  • the amorphous fluoropolymer comprises interpolymerized units derived from at least 30, 35, 40, or even 45 wt% and at most 55, 60, or even 65 wt% VDF; at least 10, 15, 20, 25, or even 35 wt% and at most 40, 45, 50, 55, or even 60 wt% PMVE; and at least 10 15, or even 20 wt% and at most 25, 30, or even 35 wt% TFE.
  • the amorphous fluoropolymer comprises interpolymerized units derived from at least 5, 10, or even 15 wt% and at most 20, 25, or even 30 wt% VDF; at least 5, 10, or even 15 wt% and at most 20, 25, or even 30 wt% propylene; and at least 50, 55, 60, or even 65 wt% and at most 70, 75, 80, or even 85 wt% TFE.
  • perfluorinated ether compounds include for example, perfluorinated alkyl vinyl ether such as perfluorinated methyl vinyl ether (PMVE), perfluorinated alkyl allyl ether such as perfluorinated methyl allyl ether, and perfluorinated alkoxy vinyl ether and perfluorinated alkoxy allyl ether.
  • perfluorinated alkyl vinyl ether such as perfluorinated methyl vinyl ether (PMVE)
  • perfluorinated alkyl allyl ether such as perfluorinated methyl allyl ether
  • perfluorinated alkoxy vinyl ether and perfluorinated alkoxy allyl ether perfluorinated alkoxy vinyl ether.
  • the amorphous fluoropolymer of the present disclosure contains cure sites which facilitate cross-linking of the fluoropolymer. These cure sites comprise at least one of I, Br, and CN.
  • the fluoropolymer may be polymerized in the presence of a chain transfer agent and/or cure site monomers to introduce cure sites into the fluoropolymer.
  • a chain transfer agent and/or cure site monomers are known in the art.
  • Exemplary chain transfer agents include: an iodo-chain transfer agent, a bromo-chain transfer agent, or a chloro-chain transfer agent.
  • the iodo-chain transfer agent may be a perfluorinated iodo-compound.
  • Exemplary iodo-perfluoro- compounds include 1,3-diiodoperfluoropropane, 1,4-diiodoperfluorobutane, 1, 6- diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,10-diiodoperfluorodecane, 1,12- diiodoperfluorododecane, 2-iodo- 1 ,2-dichloro-l, 1 ,2-trifluoroethane, 4-iodo- 1,2,4- trichloroperfluorobutan, and mixtures thereof.
  • the iodo-chain transfer agent is of the formula I(CF2)n-O-Rf-(CF2) m I, wherein n is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, m is is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 and Rf is a partially fluorinated or perfluorinated alkylene segment, which can be linear or branched and optionally comprises at least one catenated ether linkage.
  • Exemplary compounds include: I-CF2-CF2-O-CF2-CF2-I, I-CF(CF 3 )-CF2-O-CF2-CF 2 -I, I-CF 2 -CF 2 -O-CF(CF 3 )- CF2-O-CF2-CF2-I, I-(CF(CF 3 )-CF 2 -O)2-CF2-CF 2 -I, I-CF 2 -CF2-O-(CF2)2-O-CF2-CF 2 -I, I-CF2-CF2- O-(CF 2 ) 3 -O-CF2-CF 2 -I, and I-CF 2 -CF 2 -O-(CF 2 ) 4 -O-CF 2 -CF 2 -I, I-CF 2 -CF 2 -CF 2 -O-CF 2 -CF 2 -I, and I- CF2-CF2-CF2-O-CF(CF 3 )-CF2-O-CF2-CF2-I,
  • the bromine is derived from a brominated chain transfer agent of the bromine
  • Cure site monomers if used, comprise at least one of a bromine, iodine, and/or nitrile cure moiety.
  • non-fluorinated bromo-or iodo-olefins e.g., vinyl iodide and allyl iodide, can be used.
  • the amorphous fluoropolymer composition of the present disclose comprises iodine, bromine, and/or nitrile cure sites, which are subsequently used to crosslink the amorphous fluoropolymer.
  • the amorphous fluoropolymer composition of the present disclosure comprises at least 0.1, 0.5, 1, 2, or even 2.5 wt% of iodine, bromine, and/or nitrile groups versus the total weight of the amorphous fluoropolymer.
  • the amorphous fluoropolymer of the present disclosure comprises no more than 3, 5, or even 10 wt% of iodine, bromine, and/or nitrile groups versus the total weight of the amorphous fluoropolymer.
  • the amorphous fluoropolymer comprising cure sites is blended with a second amorphous fluoropolymer, which may or may not comprise bromine, iodine, and/or nitrile cure sites.
  • the curable compositions of the present disclosure comprise a cure initiator.
  • the initiator is a photoinitiator, which when exposed to actinic radiation, causes the composition to at least partially cure.
  • partially cured refers to a state that the crosslinking degree in the fluoropolymer is higher than that in an uncrosslinked fluoropolymer, which can be observed by an increase in the viscosity of the fluoropolymer.
  • the photoinitiators of the present disclosure are effective in causing cross-linking of the curable compositions of the present disclosure when exposed to actinic radiation.
  • Such photoinitiators are known in the art and commercially available.
  • the photoinitiators are soluble or dispersible in the present composition (e.g., solvent) to ensure adequate reaction.
  • Two classes of photoinitiator systems are disclosed herein.
  • a first photoinitiator system comprises a single component, which when exposed to actinic radiation, cleaves forming two radicals.
  • photoinitiators are known in the art.
  • Exemplary photoinitiators of this type include: benzoin ethers (e.g., benzoin methyl ether or benzoin isopropyl ether) or substituted benzoin ethers (e.g., anisoin methyl ether).
  • Other exemplary photoinitiators are substituted acetophenones such as 2,2-diethoxyacetophenone or 2,2- dimethoxy-2 -phenylacetophenone (commercially available under the trade designation “IRGACURE 651” from BASF Corp.
  • photoinitiators are substituted alpha-ketols such as 2-methyl-2-hydroxypropiophenone, aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride, and photoactive oximes such as 1 -phenyl- 1,2- propanedione-2-(O-ethoxycarbonyl)oxime.
  • photoinitiators include, for example, 1- hydroxy cyclohexyl phenyl ketone (commercially available under the trade designation “IRGACURE 184” from BASF Corp.), phenyl bis(2,4,6-trimethyl benzoyl) phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (commercially available underthe trade designation “IRGACURE 819” from BASF Corp.), 1 -[4-(2-hydroxyethoxy)phenyl] -2-hydroxy-2-methyl- 1 -propane- 1 -one (commercially available under the trade designation “IRGACURE 2959” from BASF Corp.), 2 -benzyl -2 -dimethylamino- 1- (4-morpholinophenyl)butanone (commercially available under the trade designation “IRGACURE 369” from BASF Corp.), 2-methyl-l-
  • the optimum amounts of the first photoinitiator system depend on the type used. Typical amounts include, but are not limited to, at least 0.01, 0.05, or even 0.1% wt; and at most 1, 3, or even 5 % wt versus the amount of amorphous fluoropolymer.
  • a second photoinitiator system is a multiple component system wherein a radical is generated through electron transfer to or from a second compound.
  • the photoinitiator system comprises a first component (A) which is a photosensitizer and a second component which comprises at least one of an iodonium salt (B) or an electron donor compound (C).
  • the first component (A) in the photoinitiator system is a photosensitizer compound.
  • the photosensitizer is capable of electromagnetic radiation absorption somewhere within the range of the wavelength(s) of interest (for example if the actinic radiation is in the UV range, the photosensitizer should absorb wavelengths within the UV range).
  • Suitable photosensitizers are believed to include compounds in the following categories: ketones, coumarin dyes (e.g., ketocoumarins), xanthene dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrins, aromatic polycyclic hydrocarbons, p-substituted aminostyryl ketone compounds, aminotriaryl methanes, merocyanines, squarylium dyes and pyridinium dyes.
  • ketones coumarin dyes (e.g., ketocoumarins), xanthene dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrins, aromatic polycyclic hydrocarbons, p-substituted aminostyryl
  • Ketones e.g., monoketones or alpha-diketones
  • ketocoumarins aminoarylketones
  • p- substituted aminostyryl ketone compounds are preferred sensitizers.
  • An exemplary photosensitizer includes 2 -isopropylthioxanthone; 2-chlorothioxanthone (ITX); and 9,10-dibutoxyanthracene.
  • Suitable ketones include monoketones such as 2,2-, 4,4- or 2,4-dihydroxybenzophenone, di-2 -pyridyl ketone, di-2-furanyl ketone, di-2-thiophenyl ketone, benzoin, fluorenone, 2- chlorothioxanthone, acetophenone, benzophenone, and the like.
  • Suitable diketones include aralkyldiketones such as anthraquinone, phenanthrenequinone, and the like.
  • Suitable a-diketones include 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, 2,3-heptanedione, 3,4-heptanedione, 2,3-octanedione, 4,5 -octanedione, benzil, 2,2'- 3 3'- and 4,4'-dihydroxylbenzil, furil, di-3,3'-indolylethanedione, 2,3-bomanedione (camphorquinone), biacetyl, 1,2- cyclohexanedione, 1,2-naphthaquinone, acenaphthaquinone, and the like.
  • the second component can be (i) an iodonium salt, (ii) an electron donor compound, or (iii) an iodonium salt and an electron donor compound.
  • iodonium salts are described in U.S. Pat. Nos. 3,729,313, 3,741,769, 3,808,006, 4,250,053 and 4,394,403, the iodonium salt disclosures of which are incorporated herein by reference.
  • the iodonium salt can be a simple salt (e.g., containing an anion such as Cl’, Br’, Tor C4H5SO3 ) or a metal complex salt (e.g., containing SbFsOH or AsFg ). Mixtures of iodonium salts can be used if desired.
  • Exemplary iodonium salts include bis(4-t-butylphenyl)iodonium hexafluoroantimonate (available under the trade designation “FP5034” from Hampford Research Inc., Stratford, CT), bis(4-t-butylphenyl) iodonium hexafluorophosphate (available under the trade designation “FP5035” from Hampford Research Inc.), (4-methoxyphenyl)phenyl iodonium triflate, bis(4-tert- butylphenyl) iodonium camphorsulfonate, bis(4-tert-butylphenyl) iodonium hexafluoroantimonate, bis(4-tert-butylphenyl) iodonium hexafluorophosphate, bis(4-tert-butylphenyl) iodonium tetraphenylborate, bis(4-tert-
  • Preferred iodonium salts include diaryliodonium salts such as (4- isopropylphenyl)(4-methylphenyl)iodonium tetrakis(pentafluorophenyl) borate, bis(4- methylphenyl) iodonium hexafluorophosphate, bis(4-t-butylphenyl)iodonium hexafluoroantimonate, and bis(4-t-butylphenyl) iodonium hexafluorophosphate.
  • Preferred electron donor compounds include amines (including aminoaldehydes and aminosilanes), ascorbic acid and its salts.
  • the donor can be unsubstituted or substituted with one or more non-interfering substituents.
  • Particularly preferred donors contain an electron donor atom such as a nitrogen, oxygen, phosphorus, or sulfur atom, and an abstractable hydrogen atom bonded to a carbon or silicon atom alpha to the electron donor atom.
  • Preferred amine donor compounds include alkyl-, aryl-, alkaryl- and aralkyl-amines such as triethanolamine, N,N'-dimethylethylenediamine, p-N N-dimethyl-aminophenethanol; aminoaldehydes such as p-N,N-dimethylaminobenzaldehyde, p-N,N-diethylaminobenzaldehyde, and 4-morpholinobenzaldehyde.
  • alkyl-, aryl-, alkaryl- and aralkyl-amines such as triethanolamine, N,N'-dimethylethylenediamine, p-N N-dimethyl-aminophenethanol
  • aminoaldehydes such as p-N,N-dimethylaminobenzaldehyde, p-N,N-diethylaminobenzaldehyde, and 4-morpholinobenzaldehyde.
  • Suitable ether donor compounds include 4,4'-dimethoxybiphenyl, 1,2,4-trimethoxybenzene and 1,2,4,5-tetramethoxybenzene.
  • the photosensitizer and at least one of the iodonium salt or electron donor are present in "photochemically effective amounts", that is, amounts of each component are sufficient to enable at least partial crosslinking of the fluoropolymer upon exposure to the actinic radiation.
  • the curable composition of the present disclosure contains about 0.005 to about 10 parts (more preferably about 0. 1 to about 4 parts) each of iodonium salt, sensitizer and donor.
  • the amounts of each component are independently variable and thus need not be equal, with larger amounts generally providing faster cure, but shorter shelf life.
  • Sensitizers with high extinction coefficients (e.g., above about 10,000) at the desired wavelength of irradiation for photopolymerization generally are used in reduced amounts.
  • at least 0.01, 0.05, or even 0.1% wt; and at most 1, 3, or even 5 %wt of the photosensitizer is used versus the amount of amorphous fluoropolymer;
  • the iodonium salt is used, at least 0.001, 0.01, 0.05, or even 0.1% wt; and at most 1, 3, or even 5 %wt of the iodonium salt is used versus the amount of the amorphous fluoropolymer;
  • the electron donor is used, at least 0.001, 0.01, 0.05, or even 0.1% wt; and at most 1, 3, or even 5 %wt of the electron donor is used versus the amount of amorphous fluoropolymer.
  • a three component photoinitiator system comprising the photosensitizer, iodonium salt and an electron donor is described in U.S. Pat. No. 5,545,676 (Palazzotto, et al.), herein incorporated by reference with respect to the various components.
  • the photoinitiator/photosensitizer is activated by irradiation with actinic radiation.
  • actinic radiation refers to electromagnetic radiation in the ultraviolet, visible, and infrared wavelengths.
  • the curing initiator is a peroxide.
  • the peroxide is an organic peroxide, preferably, a tertiary butyl peroxide having a tertiary carbon atom attached to peroxy oxygen.
  • Exemplary peroxides include: benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-di-methyl-2,5-di-tert-butylperoxyhexane, 2,4-dichlorobenzoyl peroxide, l,l-bis(tert- butylperoxy)-3,3,5-trimethylchlorohexane, tert-butyl peroxy isopropylcarbonate (TBIC), tert-butyl peroxy 2-ethylhexyl carbonate (TBEC), tert-amyl peroxy 2-ethylhexyl carbonate, tert-hexylperoxy isopropyl carbonate, carbonoperoxoic acid, O,O'-l,3-propanediyl OO, OO'-bis( 1,1 -dimethylethyl) ester, tert-butylperoxy benzo
  • the amount of peroxide used generally will be at least 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, or even 1.5; at most 2, 2.25, 2.5, 2.75, 3, 3.5, 4, 4.5, 5, or even 5.5 parts by weight per 100 parts of the amorphous fluoropolymer.
  • the curable fluoropolymer composition further comprises a crosslinking agent.
  • the crosslinking agent is a multifunctional polyunsaturated compound, which includes allyl-containing cyanurates, isocyanurates, and phthalates, homopolymers of dienes, and co-polymers of dienes and vinyl aromatics.
  • allyl-containing cyanurates include allyl-containing cyanurates, isocyanurates, and phthalates, homopolymers of dienes, and co-polymers of dienes and vinyl aromatics.
  • these crosslinking agents are commercially available including di- and triallyl compounds, divinyl benzene, vinyl toluene, vinyl pyridine, 1,2-cis-poly butadiene and their derivatives.
  • TAIC tri(methyl)ally
  • the amount of crosslinking agent used generally will be at least 0.1, 0.5, or even 1 part by weight per 100 parts of amorphous fluoropolymer; and at most 2, 2.5, 3, or even 5 parts by weight per 100 parts of amorphous fluoropolymer.
  • compositions of the present disclosure comprise additional components, which facilitate the processing or final properties of the resulting article.
  • additional components which facilitate the processing or final properties of the resulting article.
  • conventional adjuvants such as, for example, fillers, acid acceptors, process aids, or colorants may be added to the curable composition.
  • Exemplary fillers include: an organic or inorganic filler such as clay, silica (SiC>2), alumina, iron red, talc, diatomaceous earth, barium sulfate, wollastonite (CaSiCE), calcium carbonate (CaCO,).
  • calcium fluoride, magnesium oxide, titanium oxide, iron oxide and carbon particles (such as graphite or carbon black, carbon fibers, and carbon nanotubes), silicon carbide, boron nitride, molybdenum sulfide, pigment, high temperature plastics, an electrically conductive filler, a heat-dissipating filler, and the like may be added as an optional additive to the composition.
  • Those skilled in the art are capable of selecting specific fillers at required amounts to achieve desired physical characteristics in the vulcanized compound.
  • the filler components may result in a compound that is capable of retaining a preferred elasticity and physical tensile, as indicated by an elongation and tensile strength value, while retaining desired properties such as retraction at lower temperature (TR-10).
  • the filler content is between 0.01 to 10 % or up to 30 % or even up to 50 % by weight based on the total weight of the composition.
  • Conventional adjuvants may also be incorporated into the composition of the present disclosure to enhance the properties of the resulting composition.
  • acid acceptors may be employed to facilitate the cure and thermal stability of the compound. Suitable acid acceptors may include magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic lead phosphite, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, hydrotalcite, alkali stearates, magnesium oxalate, or combinations thereof.
  • the acid acceptors are preferably used in amounts ranging from about 1 to about 20 parts per 100 parts by weight of the polymer.
  • the partially fluorinated amorphous polymers disclosed herein are dissolved and/or dispersed in a liquid solvent comprising a hydrochlorofluoropropene to form the curable compositions.
  • the hydrochlorofluoropropene is an isomer, which may be cis or trans in configuration.
  • hydrochlorofluoropropene compounds include: cis-l-Chloro-3,3,3- trifluoropropene, 2-chloro-3,3,3-trifluoropropene; I,2-dichloro-3,3,3-trifluoropropene; 1,1- dichloro-3,3-difluoro-l-propene; and 3 -chloro-3, 3 -difluoro- 1 -propene.
  • These hydrochlorofluoropropene compounds may be cis or trans or a blend thereof.
  • the hydrochlorofluoropropene has a boiling point above room temperature at ambient pressures. In one embodiment, the hydrochlorofluoropropene has a boiling point greater than 23, 25, 30, or even 35 °C.
  • the coatable composition comprises at least 10, 20, 30 or even 40 wt % of the liquid solvent. In one embodiment, the coatable composition comprises at most 50, 60, 70, 80, 90, or even 99 wt % of the liquid solvent.
  • the amorphous fluoropolymer content of the curable compositions is preferably as high as possible, for example, at concentrations from at least 50, 75, 80, 85, or even 90 % by weight; and at most 95, 98, 99, or even 99.5 % by weight based on the total weight of the curable composition.
  • the hydrochlorofluoropropene substantially solubilizes the partially fluorinated amorphous polymer.
  • 80, 100, 150, or even 200 grams of the partially fluorinated amorphous polymer dissolves in 100 mL of the hydrochlorofluoropropene.
  • the partially fluorinated amorphous polymers dissolved and/or dispersed in the liquid solvent are coatable.
  • the compositions have a viscosity at 25°C of at least 50, 100, 500, 1000, 2000, 4000, 6000 or even 10000 cP (centiPoise).
  • the compositions have a viscosity at 25°C of at most 2000, 4000, 6000, 8000, 10000, 15000, 20000, 50000, 100000, 200000, 500000, or even 1000000 cP.
  • the low viscosities can enable the coating compositions to be dispensible.
  • liquid solvents may be present in the curable fluoropolymer composition, typically as a result of carriers or impurities in the components. Ideally, these additional liquid solvents are kept to a minimum.
  • the liquid solvent consists essentially of the hydrochlorofluoropropene, meaning that the inert liquid present in the curable fluoropolymer composition comprises at least 90, 95, 98, 99, or even 99.9 wt % of the hydrochlorofluoropropene. In some embodiments, no additional liquid is present other than the hydrochlorofluoropropene.
  • the hydrochlorofluoropropene is used as a liquid solvent to at least partially dissolve the partially fluoropolymer.
  • Hydrochlorofluoropropene is unique because it is able to at least partially solubilize the partially fluorinated amorphous polymer and has a good environmental profile and is non-flammable making it especially useful.
  • the hydrochlorofluoropropene and/or the curable fluoropolymer composition of the present disclosure has a low environmental impact.
  • the hydrochlorofluoropropene and/or the curable fluoropolymer composition of the present disclosure may have a global warming potential (GWP) of less than 10, 5, 2, or 1.
  • GWP is a relative measure of the global warming potential of a compound based on the structure of the compound. See paragraphs [0020]-[0022] of U.S. Publ. No. 2015/0083979 (Costello et al.) for discussion on how to determine the GWP.
  • the hydrochlorofluoropropene and/or the curable fluoropolymer composition of the present disclosure have an atmospheric lifetime of less than 10 years, or even less than 5 years when tested as disclosed in paragraph [0060] of U.S. Publ. No. 2020/0002589 (Uamanna).
  • Non-flammability can be assessed by using standard methods such as ASTM D-3278-96 e-l“Standard Test Method for Flash Point of Uiquids by Small Scale Closed-Cup Apparatus”.
  • the hydrochlorofluoropropene and/or the curable fluoropolymer composition of the present disclosure is non-flammable based on closed-cup flashpoint testing following ASTM D-3278-96 e-1.
  • the curable composition comprising the partially fluorinated amorphous polymer, the cure initiator, crosslinking agent, liquid solvent, and optional additives can be combined together, using techniques known in the art, and cured.
  • the cure initiator is a peroxide initiator, allowing the coatable composition to be thermally cured.
  • the cure initiator is a photoinitiator, allowing the coatable composition to be photochemically cured.
  • the curable composition is at least partially cured using thermal radiation, whereby the curable composition is exposed to temperatures greater than 120, 140, 160, 180, 200, 220, or even 250°C; and less than the decomposition temperature of the fluoropolymer or its components (e.g., less than 300, or even 275°C), causing the peroxide cure initiator to activate, resulting in the crosslinking (or curing) of the composition.
  • curing is performed in an oven.
  • the curable composition is at least partially cured using actinic radiation.
  • the curable composition is exposed to wavelengths from at least 180, 200, 210, 220, 240, 260, or even 280 nm; and at most 700, 800, 1000, 1200, or even 1500 nm.
  • the curable composition is exposed to wavelengths from at least 180, 210, or even 220 nm; and at most 340, 360, 380, 400, 410, 450, or even 500 nm.
  • the curable composition is exposed to wavelengths from at least 400, 420, or even 450 nm; and at most 700, 750, or even 800 nm.
  • the curable composition is exposed to wavelengths from at least 800, 850, or even 900 nm; and at most 1000, 1200, or even 1500 nm.
  • Any light source as long as part of the emitted light can be absorbed by the photo-initiator or photo-initiator system, may be employed as a radiation source, such as, a high or low pressure mercury lamp, a cold cathode tube, a black light, a light emitting diode, a laser, and a flash light.
  • a radiation source such as, a high or low pressure mercury lamp, a cold cathode tube, a black light, a light emitting diode, a laser, and a flash light.
  • the preferred source is one exhibiting a relatively long wavelength UV-contribution having a dominant wavelength of 300-400 nm.
  • UV radiation is generally classed as UV-A, UV-B, and UV-C as follows: UV-A: 400 nm to 320 nm; UV-B: 320 nm to 290 nm; and UV-C: 290 nm to 100 nm.
  • the dosage of the actinic radiation is 10-1000 watts.
  • the curable composition is coated onto a substrate and then exposed to either thermal radiation or actinic radiation.
  • the curable composition is coated onto a substrate using techniques known in the art including, for example, dip coating, spray coating, spin coating, blade or knife coating, bar coating, roll coating, and pour coating (i.e., pouring a liquid onto a surface and allowing the liquid to flow over the surface)).
  • Substrates may include, metals (such as carbon steel, stainless steel, and aluminum), plastics (such as polyethylene, or polyethylene teraphthalate), or release liners, which are a temporary support comprising a backing layer coated with a release agent (such as a silicone, fluoropolymer, or polyutherane).
  • a thin coating of the curable composition is disposed on a substrate, for example a coating thickness of at least 10 nm or even 100 nm to at most 1 pm, 10 pm, or even 100 pm.
  • the thin coating is substantially crosslinked, meaning that when tested following the Gel Content Measurement described below, there is at least 65, 70, 80, or even 90% gelling.
  • the coating compositions can be processed in a continuous fashion.
  • the coating composition is coated onto a web, and then transported to a curing station containing the radiation (thermal or electromagnetic) source.
  • the cured fluoroelastomer composition can then be transported to a cutting station, whereby articles of desired shapes are cut from the web of fluoroelastomer.
  • Such a process can enable faster processing of articles, due to the continuous nature of the processing.
  • the low flammability and/or good environmental profde of the hydrofluoropropene enables the coating compositions to be continuously processed without the necessity of making equipment explosion proof.
  • the coating composition is coated directly onto the article and cured in place.
  • a gasket for a part e.g., a head
  • the coating composition could be coated directly onto the part and then cured. Such a process would enable made-to-order parts and eliminates cutting and/or the need for a mold.
  • the articles of the present disclosure are shaped and can include gaskets, ring lip seals, washer seals, O-rings, grooved seals, etc.
  • Viscosities reported in Tables 3 and 4 were determined using a B type viscometer, available under the trade designation “Model BM” from TOKYO KEIKI INC., Tokyo, Japan, using either 30 or 60 rpm and a No. 4 rotor, at 23 °C.
  • Example 1 (EX-1) and Comparative Example 1 (CE-1) Fluoropolymer, Coagent, UV Initiator, and Solvent as indicated in Table 3 were weighed into glass jars. Jars were rotated until Fluoropolymer, Coagent and UV Initiator were dissolved into the solvent completely. Viscosity of the solutions was measured and is recorded in Table 3.
  • the solutions were dispensed from a dispenser available under the trade designation “MODEL SHOT MINI 200SX” from Musashi Engineering, Inc., Tokyo, Japan using a 20 gauge (0.61 mm inner diameter) nozzle at room temperature onto substrates. Dispensed solutions were pre-dried according to conditions indicated in Table 3 and then cured by exposure to UV light from a H type bulb in a system available under the trade designation “MODEL DRS” from Heraeus Nobelight Americal LLC, Buford, GA. The UV energy output of the UV source is provided in Table 2, below. The samples were cured by 10 passes through the UV source at a line speed of 13.4 m/min. Samples were tested for gel content before and after UV curing. The results are presented in Table 3.
  • Example 2 EX-2
  • Comparative Example 2 CE-2
  • Fluoropolymer, Coagent, Peroxide, and Solvent as indicated in Table 4 were weighed into glass jars. Jars were rotated until Fluoropolymer, Coagent and Peroxide were dissolved into the solvent completely. The viscosity of the solutions was measured. Viscosity results are presented in Table 4.
  • the solutions were dispensed from a dispenser available under the trade designation “MODEL SHOT MINI 200SX” from Musashi Engineering, Inc. using a 20 gauge (0.61 mm inner diameter) nozzle at room temperature onto substrates. Dispensed solutions were pre-dried and heat cured according to conditions listed in Table 4. Samples were tested for gel content before and after UV curing. The results are presented in Table 4.

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Abstract

L'invention concerne une composition durcissable comprenant un polymère amorphe partiellement fluoré ayant un site de durcissement d'iode, de brome et/ou de nitrile ; un initiateur de durcissement ; un agent de réticulation ; et un solvant liquide comprenant un hydrochlorofluoropropène. L'invention concerne également des procédés de durcissement de la composition durcissable et des articles obtenus à partir de celle-ci.
PCT/IB2021/060660 2020-11-23 2021-11-17 Composition de revêtement comprenant un fluoropolymère durcissable et un hydrofluorochloropropène, et fluoroélastomères issus de celle-ci WO2022107020A1 (fr)

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Citations (11)

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Publication number Priority date Publication date Assignee Title
US3729313A (en) 1971-12-06 1973-04-24 Minnesota Mining & Mfg Novel photosensitive systems comprising diaryliodonium compounds and their use
US3741769A (en) 1972-10-24 1973-06-26 Minnesota Mining & Mfg Novel photosensitive polymerizable systems and their use
US3808006A (en) 1971-12-06 1974-04-30 Minnesota Mining & Mfg Photosensitive material containing a diaryliodium compound, a sensitizer and a color former
US4250053A (en) 1979-05-21 1981-02-10 Minnesota Mining And Manufacturing Company Sensitized aromatic iodonium or aromatic sulfonium salt photoinitiator systems
US4394403A (en) 1974-05-08 1983-07-19 Minnesota Mining And Manufacturing Company Photopolymerizable compositions
US5225504A (en) 1992-02-14 1993-07-06 Nok Corporation Process for producing peroxide-vulcanizable, fluorine-containing elastomer
US5545676A (en) 1987-04-02 1996-08-13 Minnesota Mining And Manufacturing Company Ternary photoinitiator system for addition polymerization
US20150083979A1 (en) 2012-04-04 2015-03-26 3M Innovative Properties Company Fluorinated Nitriles as Dielectric Gases
WO2019230456A1 (fr) * 2018-05-28 2019-12-05 Ａｇｃ株式会社 Procédé de production d'un propène contenant du fluor
WO2019239288A1 (fr) * 2018-06-12 2019-12-19 3M Innovative Properties Company Compositions de revêtement contenant un polymère fluoré et articles obtenus à partir de celles-ci
US20200002589A1 (en) 2017-03-21 2020-01-02 3M Innovative Properties Company Heat transfer fluids and methods of using same

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3729313A (en) 1971-12-06 1973-04-24 Minnesota Mining & Mfg Novel photosensitive systems comprising diaryliodonium compounds and their use
US3808006A (en) 1971-12-06 1974-04-30 Minnesota Mining & Mfg Photosensitive material containing a diaryliodium compound, a sensitizer and a color former
US3741769A (en) 1972-10-24 1973-06-26 Minnesota Mining & Mfg Novel photosensitive polymerizable systems and their use
US4394403A (en) 1974-05-08 1983-07-19 Minnesota Mining And Manufacturing Company Photopolymerizable compositions
US4250053A (en) 1979-05-21 1981-02-10 Minnesota Mining And Manufacturing Company Sensitized aromatic iodonium or aromatic sulfonium salt photoinitiator systems
US5545676A (en) 1987-04-02 1996-08-13 Minnesota Mining And Manufacturing Company Ternary photoinitiator system for addition polymerization
US5225504A (en) 1992-02-14 1993-07-06 Nok Corporation Process for producing peroxide-vulcanizable, fluorine-containing elastomer
US20150083979A1 (en) 2012-04-04 2015-03-26 3M Innovative Properties Company Fluorinated Nitriles as Dielectric Gases
US20200002589A1 (en) 2017-03-21 2020-01-02 3M Innovative Properties Company Heat transfer fluids and methods of using same
WO2019230456A1 (fr) * 2018-05-28 2019-12-05 Ａｇｃ株式会社 Procédé de production d'un propène contenant du fluor
WO2019239288A1 (fr) * 2018-06-12 2019-12-19 3M Innovative Properties Company Compositions de revêtement contenant un polymère fluoré et articles obtenus à partir de celles-ci

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