CN114381013B - Concentrated aqueous dispersion of fluorine-containing polymer, preparation method and application thereof - Google Patents

Concentrated aqueous dispersion of fluorine-containing polymer, preparation method and application thereof Download PDF

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CN114381013B
CN114381013B CN202210114168.XA CN202210114168A CN114381013B CN 114381013 B CN114381013 B CN 114381013B CN 202210114168 A CN202210114168 A CN 202210114168A CN 114381013 B CN114381013 B CN 114381013B
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aqueous dispersion
fluoropolymer
concentrated aqueous
anionic surfactant
particles
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CN114381013A (en
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潘杰辉
王静会
魏国强
冯璋霓
石建伟
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Entropy Energy Innovative Materials Zhuhai Co ltd
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Entropy Energy Innovative Materials Zhuhai Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/262—Sulfated compounds thiosulfates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance

Abstract

The application discloses a concentrated aqueous dispersion of a fluorine-containing polymer, a preparation method and application thereof, and belongs to the technical field of coatings. The concentrated aqueous dispersion of a fluoropolymer disclosed in the present application comprises fluoropolymer particles dispersed in an aqueous solvent, an anionic surfactant, and optionally a nonionic surfactant selected from polyvinylpyrrolidone-based polymers represented by formula (I), and does not contain polyoxyethylene ether-based surfactants; the total content of anionic surfactant and optional nonionic surfactant is from 2 to 16wt%, based on the weight of the fluoropolymer particles. The concentrated aqueous dispersion of the fluorine-containing polymer disclosed by the application has the characteristics of low viscosity and good stability, is environment-friendly, can be used for producing fluorine-containing polymer anti-dripping agents, impregnating porous glass and porous metal or used as a coating, and has the characteristics of good appearance, wear resistance and the like.

Description

Concentrated aqueous dispersion of fluorine-containing polymer, preparation method and application thereof
Technical Field
The application relates to the technical field of coatings, in particular to a concentrated aqueous dispersion of a fluorine-containing polymer, a preparation method and application thereof.
Background
The fluorine-containing polymer (such as polytetrafluoroethylene and the like) has excellent chemical stability, good electrical property and low surface energy, is widely applied to industries such as chemical industry, aerospace, military and the like, is widely applied to corrosion prevention of petroleum platforms, reactors, aircrafts and petroleum conveying pipelines, and is widely applied to production of materials which are not sticky in daily life.
The initial aqueous dispersion of fluoropolymer particles obtained from the fluoropolymer unit generally has a solids content of less than 30%, contains a significant amount of moisture, is not suitable for direct coating formulation and use, and requires concentration to a relatively high concentration for use, and the initial aqueous dispersion of fluoropolymer particles having a solids content of generally less than 30% can be concentrated to a solids content of about 60% typically by chemical, electro-or vacuum concentration to provide a concentrated aqueous dispersion of fluoropolymer.
In the preparation of concentrated aqueous dispersions of fluoropolymers, it is often necessary to add a surfactant to the dispersion to help stabilize the fluoropolymer particles in the aqueous phase at a certain concentration (typically 40-70% solids). However, such surfactants currently used are mainly polyoxyethylene ether type surfactants such as nonionic surfactants such as trimethylnonylphenol polyoxyethylene ether (TMN series), fatty alcohol polyoxyethylene ether (APEO series), alkylphenol polyoxyethylene ether (NPEO, opoo) and the like, and other anionic surfactants are used in combination, for example, in patent documents CN109517096A, CN1551909a and US2011144255A1. However, such polyoxyethylene ether surfactants are poorly biodegradable and environmentally unfriendly, thereby limiting the wide use of concentrated aqueous dispersions of such fluoropolymers.
Disclosure of Invention
In view of one or more of the problems of the prior art, a first aspect of the present application provides a concentrated aqueous dispersion of a fluoropolymer comprising fluoropolymer particles dispersed in an aqueous solvent, an anionic surfactant and optionally a nonionic surfactant selected from polyvinylpyrrolidone-based polymers represented by the following formula (I):
(C 6 H 9 NO) n (I)
in the formula (I), n is 9-450;
and the concentrated aqueous dispersion of the fluoropolymer does not contain polyoxyethylene ether surfactant;
wherein the total content of the anionic surfactant and optional nonionic surfactant may be from 2 to 16wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the anionic surfactant may comprise a non-fluorinated anionic surfactant, optionally further comprising a fluorinated anionic surfactant; alternatively, the non-fluorinated anionic surfactant may be present in an amount of 2 to 12wt%, alternatively 4 to 10wt%, and the fluorinated anionic surfactant may be present in an amount of 0 to 0.5wt%, alternatively 0 to 0.3wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the non-fluorinated anionic surfactant may be selected from one or more of the following: alkyl sulfates, polyoxyethylene fatty alcohol ether sulfates, fatty acid salts, alcohol ether carboxylates, alkylphenol ether carboxylates, stearates, alkylbenzenesulfonates, alpha-olefin sulfonates, alpha-sulfomonocarboxylates, fatty acid ester sulfonates, succinate sulfonates, alkyl naphthalene sulfonates, alkyl glyceryl ether sulfonates, petroleum sulfonates, lignin sulfonates, alkyl carboxylates; alternatively, the non-fluorinated anionic surfactant may be selected from one or more of the following: sodium Dodecyl Sulfate (SDS), ammonium dodecyl sulfate (AESA-70), sodium Dodecyl Benzene Sulfonate (SDBS), sodium dodecyl diphenyl ether disulfonate (SLDED), disodium dodecyl polyoxyethylene ether sulfosuccinate (MES), sodium dihexyl sulfosuccinate, sodium dioctyl sulfosuccinate (OT-75), potassium stearate, sodium dodecyl carboxylate and sodium dodecyl polyoxyethylene ether carboxylate.
In some embodiments, the fluorinated anionic surfactant may be selected from one or more of the following: ammonium perfluoro-2-methyl-3-oxahexanoate, sodium perfluoro-2, 5-dimethyl-3, 6-dioxanonanoate, sodium perfluorohexyl acetate, potassium omega-hydrogen-containing perfluoroheptanoate.
In some embodiments, the polyvinylpyrrolidone-based polymer may have a molecular weight of 1000 to 100000, alternatively 3000 to 60000.
In some embodiments, the nonionic surfactant may be selected from one or more of the following: k12, K15, K17, K25 and K30.
In some embodiments, the nonionic surfactant may be present in an amount of 0 to 6wt%, alternatively 0 to 3wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the fluoropolymer particles may have a solids content of 40 to 75wt%, alternatively 50 to 70wt%, and further alternatively 55 to 65wt%, based on the weight of the concentrated aqueous dispersion of fluoropolymer.
In some embodiments, the fluoropolymer particles may include polytetrafluoroethylene particles, modified polytetrafluoroethylene particles, or a combination thereof.
In some embodiments, the fluoropolymer particles may have a particle size of 0.15 to 0.40 μm, alternatively 0.20 to 0.35 μm.
In a second aspect, the present application provides a process for producing a concentrated aqueous dispersion of a fluoropolymer, which comprises adding 2 to 16% by weight in total of an anionic surfactant and optionally a nonionic surfactant selected from polyvinylpyrrolidone-based polymers represented by the following formula (I) to a starting aqueous dispersion of fluoropolymer particles and concentrating;
(C 6 H 9 NO) n (I)
in the formula (I), n is 9-450; wherein:
the wt% is based on the weight of fluoropolymer particles in the starting aqueous dispersion of fluoropolymer particles;
the concentrated aqueous dispersion of the fluoropolymer is free of polyoxyethylene ether surfactants.
In some embodiments, the anionic surfactant may be a non-fluorinated anionic surfactant; preferably, the non-fluorinated anionic surfactant may be added in an amount of 2 to 12wt%, alternatively 4 to 10wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the starting aqueous dispersion of fluoropolymer particles contains fluorinated anionic surfactant in an amount of 0 to 0.5wt%, alternatively 0 to 0.3wt%, based on the weight of fluoropolymer particles in the starting aqueous dispersion of fluoropolymer particles.
In some embodiments, the nonionic surfactant can be added in an amount of 0 to 6wt%, alternatively 0 to 3wt%, based on the weight of fluoropolymer particles in the starting aqueous dispersion of fluoropolymer particles.
In some embodiments, the fluoropolymer particles may have a solids content of 15 to 35wt%, alternatively 20 to 30wt%, based on the weight of the starting aqueous dispersion of fluoropolymer particles.
In some embodiments, the method of preparing may further comprise the step of adding a polymerization initiator and an emulsifier to the comonomer of the fluoropolymer to prepare a starting aqueous dispersion of the fluoropolymer particles; wherein the polymerization initiator may comprise a persulfate, an organic peroxide, or a combination thereof, optionally may be ammonium persulfate, potassium persulfate, succinic acid peroxide, or a combination thereof; the emulsifier may comprise a fluorocarbon-based emulsifier, a hydrocarbon-based emulsifier, or a combination thereof, and may be selected from ammonium perfluoro 2-methyl-3-oxahexanoate, sodium perfluoro 2, 5-dimethyl-3, 6-dioxanonanoate, sodium perfluorohexyl acetate, potassium omega-hydrogen-containing perfluoroheptanoate, and the like. The emulsifier in the starting aqueous dispersion of fluoropolymer particles may be removed by ultrafiltration or contact with a strongly basic ion exchange resin, or the like, prior to adding the anionic surfactant to the starting aqueous dispersion of fluoropolymer particles, in which case the concentrated aqueous dispersion of fluoropolymer produced is free or substantially free of fluorinated anionic surfactant.
In a third aspect, the present application also provides the use of the concentrated aqueous dispersion of fluoropolymer provided in the first aspect for impregnating porous fabrics, porous metals, as dielectric coating or in the production of fluoropolymer anti-drip agents.
The concentrated aqueous dispersion of the fluoropolymer provided by the technical scheme contains the anionic surfactant (and optionally the nonionic surfactant selected from polyvinylpyrrolidone-based polymers represented by the formula (I)) and does not contain the polyoxyethylene ether-based surfactant, so that the concentrated aqueous dispersion of the fluoropolymer has the characteristics of low viscosity and good stability, and the anionic surfactant has the characteristics of good biodegradability, water solubility and the like, and is more environment-friendly than the polyoxyethylene ether-based surfactant which is widely used in the prior art and has poor biodegradability. The results of the examples show that the viscosity of the concentrated aqueous dispersion of the fluoropolymer provided by the application is not more than 20 mPas, preferably not more than 18 mPas; the composition has good mechanical stability and storage stability, can be stored for up to 2 months at room temperature without color change and sedimentation, and even has better stability effect than the addition of two surfactants (TMN-10+SDS); and the coating prepared by the concentrated aqueous dispersion of the fluorine-containing polymer provided by the application has good glossiness and transparency and excellent heat resistance and wear resistance.
Detailed Description
Hereinafter, the concentrated aqueous dispersion of the fluoropolymer, the preparation method and application thereof provided by the present application will be described by way of specific embodiments. The following description is provided for a thorough understanding of the present application by those skilled in the art and is not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
In the description herein, unless otherwise indicated, "above" and "below" are intended to include the present number, and the meaning of "several" in "one or several" means two or more.
The concentrated aqueous dispersion of the fluoropolymer is widely applied to the industries of chemical industry, aerospace, military and the like due to the excellent chemical stability, good electrical property and low surface energy. Currently, in the preparation of concentrated aqueous dispersions of fluoropolymers, it is common to concentrate the starting aqueous dispersion of fluoropolymer particles (aqueous dispersion of fluoropolymer particles having a solids content of about 15 to 35% formed by polymerization of the comonomer of the fluoropolymer) with the aid of a nonionic surfactant (typically polyoxyethylene ether-based surfactant) and an anionic surfactant or the like. Widely used polyoxyethylene ether surfactants are less biodegradable and environmentally unfriendly, thereby limiting the application of concentrated aqueous dispersions of such fluoropolymers.
The present inventors have made extensive studies to note that when a metered amount of a non-fluorinated anionic surfactant (and optionally a nonionic surfactant selected from the polyvinylpyrrolidone-based polymers represented by the formula (I)) is added to a starting aqueous dispersion of fluoropolymer particles, which may contain a small amount of a fluorinated anionic surfactant or no fluorinated anionic surfactant, without additionally adding a conventionally used polyoxyethylene ether-based surfactant, a concentrated aqueous dispersion of a fluoropolymer having a low viscosity and good stability can also be obtained, and such a non-fluorinated anionic surfactant and optionally a nonionic surfactant of the polyvinylpyrrolidone-based polymers represented by the formula (I) have good biodegradability and water solubility, and are thus more environmentally friendly than the polyoxyethylene ether-based surfactants used in the prior art.
In a first aspect of the present application, there is provided a concentrated aqueous dispersion of a fluoropolymer comprising fluoropolymer particles dispersed in an aqueous solvent, an anionic surfactant and optionally a nonionic surfactant selected from polyvinylpyrrolidone-based polymers represented by the following formula (I), and not comprising a polyoxyethylene ether-based surfactant;
(C 6 H 9 NO) n (I)
in the formula (I), n is 9-450;
wherein the total content of the anionic surfactant and optional nonionic surfactant may be from 2 to 16wt%, based on the weight of the fluoropolymer particles. When the amount of the surfactant is less than 2% by weight, the increase in viscosity of the aqueous dispersion will not be effectively suppressed, and the stability will be poor, and the product will not be used as a coating; when the amount of the surfactant is more than 16wt%, the content of the surfactant in the concentrated aqueous dispersion may be excessively high, and the viscosity characteristics and stability of the product may be deteriorated.
In some embodiments, the anionic surfactant may be selected from non-fluorinated anionic surfactants, or mixtures of non-fluorinated anionic surfactants and fluorinated anionic surfactants; the non-fluorinated anionic surfactant may be present in an amount of 2 to 12wt%, alternatively 4 to 10wt%, and the fluorinated anionic surfactant may be present in an amount of 0 to 0.5wt%, alternatively 0 to 0.3wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the non-fluorinated anionic surfactant may be selected from one or more of the following: alkyl sulfates, polyoxyethylene fatty alcohol ether sulfates, fatty acid salts, alcohol ether carboxylates, alkylphenol ether carboxylates, stearates, alkylbenzenesulfonates, alpha-olefin sulfonates, alpha-sulfomonocarboxylates, fatty acid ester sulfonates, succinate sulfonates, alkyl naphthalene sulfonates, alkyl glyceryl ether sulfonates, petroleum sulfonates, lignin sulfonates, alkyl carboxylates; alternatively, the non-fluorinated anionic surfactant may be selected from one or more of the following: sodium Dodecyl Sulfate (SDS), ammonium dodecyl sulfate (AESA-70), sodium Dodecyl Benzene Sulfonate (SDBS), sodium dodecyl diphenyl ether disulfonate (SLDED), disodium dodecyl polyoxyethylene ether sulfosuccinate (MES), sodium dihexyl sulfosuccinate, sodium dioctyl sulfosuccinate (OT-75), potassium stearate, sodium dodecyl carboxylate and sodium dodecyl polyoxyethylene ether carboxylate.
In some embodiments, the fluorinated anionic surfactant may be selected from one or more of the following: ammonium perfluoro-2-methyl-3-oxahexanoate, sodium perfluoro-2, 5-dimethyl-3, 6-dioxanonanoate, sodium perfluorohexyl acetate, potassium omega-hydrogen-containing perfluoroheptanoate.
In some embodiments, the polyvinylpyrrolidone-based polymer may have a molecular weight of 1000 to 100000, alternatively 3000 to 60000.
In some embodiments, the nonionic surfactant may be selected from one or more of the following: k12, K15, K17, K25 and K30.
In some embodiments, the nonionic surfactant can be present in an amount of 0 to 6wt%, alternatively 0 to 3wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the fluoropolymer particles may have a solids content of 40 to 75wt%, alternatively 50 to 70wt%, and further alternatively 55 to 65wt%, based on the weight of the concentrated aqueous dispersion of fluoropolymer.
In some embodiments, the fluoropolymer particles may include Polytetrafluoroethylene (PTFE) particles, modified polytetrafluoroethylene particles, or a combination thereof. The modified PTFE is a PTFE in which a polymer is copolymerized with a small amount of another comonomer, the content of which is limited to the extent that melt flowability does not occur, and examples of the other comonomer include Hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), perfluoroalkyl vinyl ether (PAVE), vinylidene fluoride (VdF), vinylidene fluoride, hexafluoroethylene, vinylidene fluoride, and the like.
In some embodiments, the fluoropolymer particles may have a particle size of 0.15 to 0.40 μm, alternatively 0.20 to 0.35 μm.
In a second aspect of the present application, there is provided a process for producing a concentrated aqueous dispersion of a fluoropolymer, which comprises adding 2 to 16% by weight in total of an anionic surfactant and optionally a nonionic surfactant selected from polyvinylpyrrolidone-based polymers represented by the following formula (I) to a starting aqueous dispersion of fluoropolymer particles and concentrating;
(C 6 H 9 NO) n (I)
in the formula (I), n is 9-450; wherein:
the wt% is based on the weight of fluoropolymer particles in the starting aqueous dispersion of fluoropolymer particles;
the concentrated aqueous dispersion of the fluoropolymer is free of polyoxyethylene ether surfactants.
In some embodiments, the anionic surfactant is a non-fluorinated anionic surfactant, optionally, the non-fluorinated anionic surfactant may be added in an amount of 2 to 12wt%, further optionally 4 to 10wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the starting aqueous dispersion of fluoropolymer particles contains fluorinated anionic surfactant in an amount of 0 to 0.5wt%, alternatively 0 to 0.3wt%, based on the weight of fluoropolymer particles in the starting aqueous dispersion of fluoropolymer particles.
In some embodiments, the nonionic surfactant can be added in an amount of 0 to 6wt%, alternatively 0 to 3wt%, based on the weight of fluoropolymer particles in the starting aqueous dispersion of fluoropolymer particles.
In some embodiments, the fluoropolymer particles may have a solids content of 15 to 35wt%, alternatively 20 to 30wt%, based on the weight of the starting aqueous dispersion of fluoropolymer particles.
In some embodiments, the method of preparing may further comprise the step of adding a polymerization initiator and an emulsifier to the comonomer of the fluoropolymer to prepare a starting aqueous dispersion of the fluoropolymer particles; wherein the polymerization initiator may comprise a persulfate, an organic peroxide, or a combination thereof, optionally may be ammonium persulfate, potassium persulfate, succinic acid peroxide, or a combination thereof; the emulsifier may be present in an amount of 0.1 to 0.5wt% of the fluoropolymer produced by polymerization and may include fluorocarbon based emulsifiers, hydrocarbon based emulsifiers or combinations thereof, optionally ammonium perfluoro 2-methyl-3-oxahexanoate, sodium perfluoro 2, 5-dimethyl-3, 6-dioxanonanoate, sodium perfluorohexyl acetate, potassium omega-hydrogen perfluoroheptanoate and the like. The resulting concentrated aqueous dispersion of fluoropolymer may contain fluorinated anionic surfactant in an amount determined by the amount of fluorinated emulsifier added, typically in an amount of from 0 to 0.5wt%, optionally from 0 to 0.3wt% based on the amount of fluoropolymer particles, and the emulsifier in the initial aqueous dispersion of fluoropolymer particles may be removed by ultrafiltration or contact with a strongly basic ion exchange resin, or the like, prior to adding the anionic surfactant to the initial aqueous dispersion of fluoropolymer particles, in which case the concentrated aqueous dispersion of fluoropolymer is prepared without or substantially without fluorinated anionic surfactant.
In some embodiments, the concentration may be by chemical concentration, electro-concentration, vacuum concentration, or the like, such that the fluoropolymer particles have a solids content of 40-75wt%, alternatively 50-70wt%, and further alternatively 55-65wt% in the concentrated aqueous dispersion.
The concentrated aqueous dispersion of the fluoropolymer prepared by the application has the characteristics of lower viscosity, shear stability, high storage stability and the like, and has high CCT (critical cracking thickness) when used as a coating, so the application also provides the application of the concentrated aqueous dispersion of the fluoropolymer in the production of fluoropolymer anti-dripping agents, the impregnation of porous metals, the porous fabrics, the application as dielectric coatings and the like, and the concentrated aqueous dispersion of the fluoropolymer can be widely applied to the fields of chemical industry, machinery, petroleum, medicine, electronics, optics and the like, and has the characteristics of extremely strong wear resistance, good surface glossiness, good film forming property, high film cracking thickness at the film forming limit, crack resistance and the like.
In some embodiments, the porous fabric may be a glass cloth, and the glass cloth is classified into two glass cloths including alkali and alkali-free. When the alkali-containing glass cloth is immersed in the concentrated aqueous dispersion of the fluorine-containing polymer, the fluorine-containing polymer varnished cloth (such as polytetrafluoroethylene varnished cloth) with anti-sticking grade is obtained, and the fluorine-containing polymer varnished cloth can be used for anti-sticking and anti-corrosion treatment of rollers in industries such as packaging sealing of foods, fertilizers, soymilk and blood products, textile and printing and dyeing of clean and sanitary conveyor belts, and industries such as chemical industry, tent and roof leakage prevention, and the like. When the alkali-free glass cloth is impregnated with the concentrated aqueous dispersion of the fluorine-containing polymer, the electric insulation fluorine-containing polymer paint cloth can be prepared, can be used as insulation tanks, inter-turn insulation, wrapping insulation and the like in the aspects of aircraft engines, motors and the like, and can also be used as microwave materials in the aspects of vacuum pumps, radars, electronic instruments, televisions, computers, satellite communication and the like through hot pressing of laminated plates and foil plates.
Examples
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Dipping processing of glass cloth
The alkali-free glass cloth was treated with the concentrated aqueous dispersion of the fluoropolymer prepared by the present application in the following order. Plain weave density of glass cloth: longitudinal 60 (line/25 mm), transverse 46 (line/25 mm), 0.05mm thick. The glass cloth is a plain cloth product which has neat warps and wefts and has no defects of breakage, broken ends and the like after being washed by heat.
(1) The glass cloth was impregnated 1 time with the concentrated aqueous dispersion of fluoropolymer, dried at about 100 c and fired at about 380 c for 3 minutes. Cooling at normal temperature.
(2) The above-mentioned impregnate was sprayed in a concentrated aqueous dispersion of the same fluoropolymer to contain the spray solution, and then dried at about 100℃and fired at about 380℃for 3 minutes. Thereafter, bubbling of the concentrated aqueous dispersion of the coated fluoropolymer was observed.
(3) And (3) repeating the spraying, drying and firing procedures of (2) to obtain the coated glass cloth formed by the membranous substance with the solid content of the fluorine-containing polymer of about 60-65%.
Performance testing
Solids content of the concentrated aqueous dispersion: determined by the weight loss of each aqueous dispersion after drying at 150℃for 1 hour.
Viscosity of the concentrated aqueous dispersion: 500ml was taken at 25℃and the viscosity was measured on a model NDJ-1 rotary viscometer.
Mechanical stability of concentrated aqueous dispersions: adopting a high-rotation-speed emulsifying machine, and testing the conditions: high-speed shearing for 5min at 25 ℃ and 10000rpm of the emulsifying machine, observing whether demulsification is performed or not, and if demulsification is not performed, indicating good stability; otherwise, the stability is poor.
Storage stability of concentrated aqueous dispersions: taking a certain amount of concentrated aqueous dispersion of the fluorine-containing polymer, standing at room temperature, and observing the state of the dispersion every other week.
CCT test of coating formed from concentrated aqueous dispersion: the dispersion to be tested is filled into a container and, if there is foam, removed using a pipette. Degreasing aluminium plate (18X 4 mm) 2 ) Immersed in the dispersion, the plates were removed, dried by hanging at 45 ° and allowed to dry for 5min, then heated at 380 ℃ for 10min, the plates cooled and the cracking of the coating was rated using a microscope. The maximum film thickness without cracking was set to a critical film thickness (μm).
Gloss of coated glass cloth: the light reflectance at an incident angle of 60 ° was measured using a gloss meter.
Abrasion resistance test of coated glass cloth: according to GB/T1768-1979, the abrasion resistance of the coating is judged by testing the loss of weight of the coating after 200 circles of grinding wheels are ground under a weight of 250 g.
Example 1
Into a 5L stainless steel autoclave equipped with a jacket and a horizontal stirrer, 3000g of deionized water and 80g of paraffin were added, the contents of the autoclave were heated to 70℃and the autoclave was evacuated, nitrogen-substituted and then purged with Tetrafluoroethylene (TFE). 0.02g of ammonium persulfate as a polymerization initiator and 3g of a fluorine-containing emulsifier (sodium perfluorohexyl acetate) were added thereto, the reaction pressure was controlled to 2.5MPa, and TFE was continuously fed through a compressor. The starting aqueous dispersion of polytetrafluoroethylene particles is prepared by emulsion polymerization. The solids content of this dispersion was about 30% by weight, and the average particle size of the polytetrafluoroethylene particles was 250nm.
2kg of a starting aqueous dispersion of polytetrafluoroethylene particles containing about 0.2% by weight of sodium perfluorohexyl acetate based on the weight of the polytetrafluoroethylene particles was taken, 6% by weight (based on the weight of the polytetrafluoroethylene particles, the same applies hereinafter) of Sodium Dodecyl Sulfate (SDS) anionic surfactant was added, and vacuum concentration was carried out, and the solid content of the resulting concentrated aqueous dispersion was 60.1% by weight. The results of the performance test are shown in table 1 below.
Example 2
The procedure of example 1 was followed except that sodium dodecylbenzenesulfonate anionic surfactant, expressed as SDBS, was used in place of SDS in example 1 in an amount of 6% by weight, and vacuum concentration was conducted to obtain a concentrated aqueous dispersion having a solids content of about 64.8% by weight. The results of the performance test are shown in table 1 below.
Example 3
The procedure of example 1 was followed except that the SDS of example 1 was replaced with an anionic surfactant of sodium dodecyl diphenyloxide disulfonate represented by 45% of an aqueous SLDED solution in an amount of 6% by weight (based on SLDED dry basis), and vacuum concentration was conducted to obtain a concentrated aqueous dispersion having a solids content of about 61.3%. The results of the performance test are shown in table 1 below.
Example 4
The procedure of example 1 was followed except that SDS was used in an amount of 10% by weight, and vacuum concentration was conducted, and the solid content of the resulting concentrated aqueous dispersion was about 62% by weight. The results of the performance test are shown in table 1 below.
Example 5
The procedure of example 1 was followed except that SDS was used in an amount of 1% by weight, and vacuum concentration was conducted, and the resulting concentrated aqueous dispersion had a solids content of about 60.8% by weight. The results of the performance test are shown in table 1 below.
Example 6
The procedure of example 1 was followed except that SDS was used in an amount of 2% by weight, and vacuum concentration was conducted, and the resulting concentrated aqueous dispersion had a solids content of about 59.2% by weight. The results of the performance test are shown in table 1 below.
Example 7
The procedure of example 1 was followed except that SDS was used in an amount of 8% by weight, and vacuum concentration was conducted, and the resulting concentrated aqueous dispersion had a solids content of about 60.9% by weight. The results of the performance test are shown in table 1 below.
Example 8
The procedure of example 1 was followed except that SDS was used in an amount of 12% by weight and vacuum concentration was conducted, and the resulting concentrated aqueous dispersion had a solids content of about 60.7% by weight. The results of the performance test are shown in table 1 below.
Example 9
The procedure of example 1 was followed except that sodium dihexylsulfonyl succinate anionic surfactant was used in place of SDS in example 1 in an amount of 6% by weight, and vacuum concentration was performed, and the solid content of the resulting concentrated aqueous dispersion was about 55.5% by weight. The results of the performance test are shown in table 1 below.
Example 10
The procedure of example 9 was followed except that the amount of added dihexyl sodium sulfosuccinate anionic surfactant was 4% by weight, and vacuum concentration was performed, and the solid content of the resulting concentrated dispersion was 60.9% by weight. The results of the performance test are shown in table 1 below.
Example 11
The procedure was followed in example 1, except that: (1) Adding a strong alkaline ion exchange resin into the initial aqueous dispersion of the polytetrafluoroethylene particles to remove sodium perfluorohexyl acetate; (2) The SDS in example 1 was replaced with a sodium dodecyl alcohol polyoxyethylene ether carboxylate anionic surfactant in an amount of 6wt% and vacuum-concentrated to give a concentrated aqueous dispersion having a solids content of about 61.2wt%. The results of the performance test are shown in table 1 below.
Example 12
The procedure was followed in example 1, except that: (1) Adding a strong alkaline ion exchange resin into the initial aqueous dispersion of the polytetrafluoroethylene particles to remove sodium perfluorohexyl acetate; (2) The SDS of example 1 was replaced with sodium dodecyl carboxylate anionic surfactant in an amount of 6wt% and vacuum-concentrated to give a concentrated aqueous dispersion having a solids content of about 62.3wt%. The results of the performance test are shown in table 1 below.
Comparative example 1
The procedure of example 1 was followed, except that branched secondary alcohol polyoxyethylene ether (TERGITOL) TM TMN-10) represents a nonionic surfactant instead of SDS in example 1. The resulting concentrated aqueous dispersion had a solids content of about 59.8wt%. The results of the performance test are shown in table 1 below.
Comparative example 2
The procedure of example 1 was followed except that the SDS of example 1 was replaced with a nonionic polymer dispersant represented by Polyacrylamide (PAM). The resulting concentrated aqueous dispersion had a solids content of about 60% by weight. The results of the performance test are shown in table 1 below.
Comparative example 3
The procedure of example 1 was followed, except that the SDS of example 1 was replaced with a polyacrylic acid macromolecular polymer represented by PVOH. The resulting concentrated aqueous dispersion had a solids content of about 60% by weight. The results of the performance test are shown in table 1 below.
Comparative example 4
The procedure of example 1 was followed, except that the SDS of example 1 was replaced with 5% by weight of a nonionic surfactant represented by TMN-10 and 1% by weight of an anionic surfactant represented by SDS, to obtain a concentrated aqueous dispersion having a solids content of about 60.5% by weight. The results of the performance test are shown in table 1 below.
As is clear from Table 1 above, the concentrated dispersions of comparative examples 1-3 with the addition of a nonionic surfactant did not achieve satisfactory mechanical stability and storage stability; whereas examples 1-4 and 6-12, in which a metered amount of a non-fluorinated anionic surfactant was added to the starting aqueous dispersion of the fluoropolymer (with little or no fluorinated anionic surfactant), a concentrated aqueous dispersion of the fluoropolymer having both low viscosity, good mechanical stability and storage stability could be obtained without the addition of a further non-ionic surfactant. In particular, the concentrated aqueous dispersions of polytetrafluoroethylene obtained have a viscosity of not more than 20 mPas, even not more than 18 mPas, and have good mechanical stability and storage stability, and can be stored for up to 2 months at room temperature without discoloration and sedimentation, especially when the amount of non-fluorinated anionic surfactant added is 4-10% by weight of the amount of polytetrafluoroethylene particles, and have a better stability effect, even better than when two surfactants (comparative example 4, TMN-10+SDS) are added. On the other hand, the coatings prepared using the concentrated aqueous dispersions of polytetrafluoroethylene provided in examples 1-4 and 7-12 of the present application have good gloss, transparency, and generally more excellent abrasion resistance and a larger critical cracking thickness than the coatings obtained from the concentrated aqueous dispersions of polytetrafluoroethylene prepared in comparative examples 1-4.
Examples 13 to 17
Examples 13-17 were conducted in accordance with the procedure of example 1 except that the surfactant and the content used were different. The method comprises the following steps:
the surfactant used in example 13 was 1wt% Sodium Dodecyl Benzene Sulfonate (SDBS) +6wt% BASF PVP K17.
The surfactant used in example 14 was 2wt% Sodium Dodecyl Benzene Sulfonate (SDBS) +5wt% basf PVP k17.
The surfactant used in example 15 was 3wt% sodium dodecyl carboxylate +3wt% basf PVP k17.
The surfactant used in example 16 was 5wt% sodium dihexylsulfonate+1 wt% BASF PVP K17.
The surfactant used in example 17 was 1wt% Sodium Dodecyl Sulfate (SDS) +1wt% BASF PVP K17.
The results of the performance test of the concentrated aqueous dispersions of polytetrafluoroethylene prepared in examples 13-17 are shown in Table 2 below.
Table 2: concentrated aqueous dispersions of polytetrafluoroethylene prepared in examples 13-17 and measurement of impregnation processability
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As is clear from the above description of table 2, when the starting aqueous dispersion of polytetrafluoroethylene particles is concentrated, it is also possible to add thereto a metered amount of a non-fluorinated anionic surfactant and a polyvinylpyrrolidone (PVP) based polymer represented by the formula (I), and the resulting concentrated aqueous dispersion of polytetrafluoroethylene also has both the characteristics of low viscosity, good mechanical stability and storage stability, and the like, and the polyvinylpyrrolidone (PVP) based polymer represented by the formula (I) and the non-fluorinated anionic surfactant have the characteristics of good biodegradability and water solubility, and the like, so that it is more environmentally friendly than the use of polyoxyethylene ether based surfactants having poor biodegradability in the prior art. On the other hand, the concentrated aqueous dispersions prepared in examples 13 to 17 also had a large crack-free thickness (CCT), and when the concentrated aqueous dispersions of polytetrafluoroethylene prepared in examples 13 to 17 were used to impregnate glass cloths, the resulting coatings had good gloss, transparency and excellent abrasion resistance.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present application, and is not intended to limit the present application, but although the present application has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or that equivalents may be substituted for part of the technical features thereof. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (26)

1. A concentrated aqueous dispersion of a fluoropolymer comprising fluoropolymer particles dispersed in an aqueous solvent, an anionic surfactant and a nonionic surfactant selected from polyvinylpyrrolidone-based polymers represented by the following formula (I):
(C 6 H 9 NO) n （I）
in the formula (I), n is 9-450;
and the concentrated aqueous dispersion of the fluoropolymer does not contain polyoxyethylene ether surfactant;
wherein the total content of anionic surfactant and nonionic surfactant is from 2 to 16wt% based on the weight of the fluoropolymer particles;
the anionic surfactant comprises a non-fluorinated anionic surfactant and the non-fluorinated anionic surfactant is present in an amount of 2 to 12wt% based on the weight of the fluoropolymer particles.
2. The concentrated aqueous dispersion of a fluoropolymer according to claim 1 wherein the non-fluorinated anionic surfactant is present in an amount of 4-10wt%.
3. The concentrated aqueous dispersion of fluoropolymer according to claim 1 wherein said anionic surfactant further comprises fluorinated anionic surfactant in an amount of 0-0.5wt% based on the weight of said fluoropolymer particles.
4. A concentrated aqueous dispersion of a fluoropolymer according to claim 3 wherein said fluorinated anionic surfactant is present in an amount of 0-0.3wt%.
5. The concentrated aqueous dispersion of a fluoropolymer according to claim 1 wherein said non-fluorinated anionic surfactant is selected from one or more of the following: alkyl sulfates, fatty acid salts, alcohol ether carboxylates, alkylphenol ether carboxylates, alkylbenzene sulfonates, alpha-olefin sulfonates, alpha-sulfomonocarboxylic acid salts, fatty acid ester sulfonates, alkyl naphthalene sulfonates, alkyl glyceryl ether sulfonates, petroleum sulfonates, lignin sulfonates.
6. The concentrated aqueous dispersion of a fluoropolymer according to claim 5 wherein said fatty acid salt is selected from stearates.
7. The concentrated aqueous dispersion of a fluoropolymer according to claim 5 wherein said fatty acid salt is selected from alkyl carboxylates.
8. The concentrated aqueous dispersion of a fluoropolymer according to claim 5 wherein said fatty acid ester sulfonate is selected from succinate sulfonate.
9. The concentrated aqueous dispersion of a fluoropolymer according to claim 5 wherein said non-fluorinated anionic surfactant is selected from one or more of the following: sodium dodecyl sulfate, ammonium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl diphenyl ether disulfonate, sodium dihexyl sulfosuccinate, sodium dioctyl sulfosuccinate, potassium stearate, sodium dodecyl carboxylate.
10. A concentrated aqueous dispersion of a fluoropolymer according to claim 3 wherein said fluorinated anionic surfactant is selected from one or more of the following: ammonium perfluoro-2-methyl-3-oxahexanoate, sodium perfluoro-2, 5-dimethyl-3, 6-dioxanonanoate, sodium perfluorohexyl acetate, potassium omega-hydrogen-containing perfluoroheptanoate.
11. The concentrated aqueous dispersion of a fluoropolymer according to claim 1, wherein said polyvinylpyrrolidone-based polymer has a molecular weight of 1000-100000.
12. The concentrated aqueous dispersion of a fluoropolymer according to claim 10 wherein said polyvinylpyrrolidone-based polymer has a molecular weight of 3000-60000.
13. The concentrated aqueous dispersion of a fluoropolymer according to claim 1 wherein said nonionic surfactant is selected from one or more of the following: k12, K15, K17, K25 and K30.
14. The concentrated aqueous dispersion of fluoropolymer according to any one of claims 1-13, wherein the fluoropolymer particles have a solids content of 40-75wt% based on the weight of the concentrated aqueous dispersion of fluoropolymer.
15. The concentrated aqueous dispersion of fluoropolymer according to claim 14 wherein the fluoropolymer particles have a solids content of 50-70 wt%.
16. The concentrated aqueous dispersion of fluoropolymer according to claim 15 wherein the fluoropolymer particles have a solids content of 55-65wt%.
17. The concentrated aqueous dispersion of fluoropolymer of any one of claims 1-13, wherein the fluoropolymer particles comprise polytetrafluoroethylene particles, modified polytetrafluoroethylene particles, or a combination thereof.
18. The concentrated aqueous dispersion of a fluoropolymer according to any one of claims 1-13 wherein the particle size of the fluoropolymer particles is 0.15-0.40 μm.
19. The concentrated aqueous dispersion of fluoropolymer according to claim 18 wherein said fluoropolymer particles have a particle size of 0.20-0.35 μm.
20. A process for producing a concentrated aqueous dispersion of a fluoropolymer according to any one of claims 1 to 19, which comprises adding 2 to 16wt% in total of an anionic surfactant and a nonionic surfactant selected from polyvinylpyrrolidone-based polymers represented by the following formula (I) to a starting aqueous dispersion of fluoropolymer particles and concentrating;
(C 6 H 9 NO) n （I）
in the formula (I), n is 9-450; wherein:
the wt% is based on the weight of fluoropolymer particles in the starting aqueous dispersion of fluoropolymer particles;
the concentrated aqueous dispersion of the fluoropolymer does not contain polyoxyethylene ether surfactant;
the anionic surfactant comprises non-fluorinated anionic surfactant, and the addition amount of the non-fluorinated anionic surfactant is 2-12 wt%.
21. The method of claim 20, wherein the non-fluorinated anionic surfactant is added in an amount of 4-10wt%.
22. The production method according to claim 20, wherein the starting aqueous dispersion of the fluoropolymer particles contains a fluorinated anionic surfactant in an amount of 0 to 0.5. 0.5wt% based on the weight of the fluoropolymer particles in the starting aqueous dispersion of the fluoropolymer particles.
23. The method of claim 22, wherein the fluorinated anionic surfactant is present in an amount of 0-0.3wt%.
24. The method of any of claims 20-23, wherein the fluoropolymer particles have a solids content of 15-35wt% based on the weight of the starting aqueous dispersion of fluoropolymer particles.
25. The production process according to claim 24, wherein the fluoropolymer particles have a solids content of 20-30wt%.
26. Use of a concentrated aqueous dispersion of a fluoropolymer according to any one of claims 1 to 19 for impregnating porous fabrics, porous metals, as a coating or in the production of fluoropolymer anti-drip agents.
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