CN114395140A - Concentrated aqueous dispersion of environment-friendly fluorine-containing polymer and preparation method and application thereof - Google Patents

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

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CN114395140A
CN114395140A CN202210114172.6A CN202210114172A CN114395140A CN 114395140 A CN114395140 A CN 114395140A CN 202210114172 A CN202210114172 A CN 202210114172A CN 114395140 A CN114395140 A CN 114395140A
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fluoropolymer
aqueous dispersion
optionally
concentrated aqueous
particles
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CN114395140B (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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Guangzhou Shine Polymer Technology Co ltd
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Priority to PCT/CN2023/070710 priority patent/WO2023142949A1/en
Priority to PCT/CN2023/070700 priority patent/WO2023142947A2/en
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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
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2439/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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

Abstract

The invention discloses an environment-friendly fluorine-containing polymer concentrated aqueous dispersion and application of a preparation method thereof, belonging to the technical field of coatings. The concentrated aqueous dispersion of the fluoropolymer disclosed by the invention comprises fluoropolymer particles dispersed in an aqueous solvent and a polyvinylpyrrolidone-based polymer represented by the formula (I), wherein the polyvinylpyrrolidone-based polymer represented by the formula (I) is present, so that the concentrated aqueous dispersion of the fluoropolymer provided by the invention has the advantages of low viscosity and good stability, and the polyvinylpyrrolidone-based polymer represented by the formula (I) has good biodegradability and water solubility and is environmentally friendly. The concentrated aqueous fluoropolymer dispersion provided by the invention can be used for producing fluoropolymer anti-dripping agents, impregnating porous glass, porous metal or serving as dielectric coatings, and has the characteristics of good appearance, low conductivity and the like.

Description

Concentrated aqueous dispersion of environment-friendly fluorine-containing polymer and preparation method and application thereof
Technical Field
The invention relates to the technical field of coatings, in particular to an environment-friendly fluorine-containing polymer concentrated aqueous dispersion and 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 the industries of chemical engineering, aerospace, military and the like, and the fluorine-containing polymer aqueous dispersion is widely applied to corrosion prevention of oil platforms, reactors, aircrafts and oil conveying pipelines and is widely applied to production of non-stick materials in daily life.
The initial aqueous dispersion of fluoropolymer particles obtained from the fluoropolymer units generally has a solids content of less than 30%, contains a large amount of water, is not suitable for direct preparation of coatings and use, and needs to be concentrated to a higher concentration before use, usually the initial aqueous dispersion of fluoropolymer particles having a solids content of generally less than 30% is concentrated to a solids content of about 60% by chemical concentration, electrical concentration or vacuum concentration to obtain a concentrated aqueous dispersion of fluoropolymer.
It is often necessary to add a surfactant to the dispersion during the preparation of concentrated aqueous dispersions of fluoropolymers to help stabilize the fluoropolymer particles in the aqueous phase at a concentration, typically 40-70% solids. However, such surfactants used at present are mainly polyoxyethylene ether surfactants such as nonionic surfactants like trimethylnonyl polyoxyethylene ether (TMN series), fatty alcohol polyoxyethylene ether (APEO series), alkylphenol polyoxyethylene ether (NPEO, opoo) and others such as patent documents CN109517096A, CN1551909A and US2011144255a 1. However, such polyoxyethylene ether surfactants have poor biodegradability and are not environmentally friendly, limiting the wide use of such concentrated aqueous dispersions of fluoropolymers.
Disclosure of Invention
In view of one or more problems of the prior art, a first aspect of the present invention provides a concentrated aqueous dispersion of a fluoropolymer comprising fluoropolymer particles dispersed in an aqueous solvent, a polyvinylpyrrolidone-based polymer represented by the following formula (I) and optionally a non-fluorinated anionic surfactant:
(C6H9NO)n (I)
n in formula (I) can be 9-450;
wherein the total content of polyvinylpyrrolidone-based polymer and optional non-fluorinated anionic surfactant may be 2-16 wt% based on the weight of the fluoropolymer particles.
In some embodiments, the polyvinylpyrrolidone-based polymer may have a molecular weight of 1000-.
In some embodiments, the polyvinylpyrrolidone-based polymer may be selected from one or more of the following: k12, K15, K17, K25 and K30, wherein the K values all represent viscosity grades of aqueous solutions of polyvinylpyrrolidone (PVP).
In some embodiments, the polyvinylpyrrolidone-based polymer may be present in an amount of 2 to 12 wt%, optionally 4 to 10 wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the non-fluorinated anionic surfactant is 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, alkylbenzene sulfonates, α -olefin sulfonates, α -sulfo monocarboxylates, fatty acid ester sulfonates, succinate sulfonates, alkylnaphthalene sulfonates, alkylglycerol ether sulfonates, petroleum sulfonates, lignin sulfonates, alkyl carboxylates; further optionally, the non-fluorinated anionic surfactant is selected from one or more of the following: sodium Dodecyl Sulfate (SDS), ammonium dodecyl sulfate (AESA-70), Sodium Dodecylbenzenesulfonate (SDBS), sodium dodecyl diphenyloxide disulfonate (SLDED), disodium lauryl polyoxyethylene ether sulfosuccinate (MES), sodium dihexylsulfosuccinate, sodium dioctyl sulfosuccinate (OT-75), potassium stearate, sodium dodecyl carboxylate, and sodium dodecyl alcohol polyoxyethylene ether carboxylate.
In some embodiments, the non-fluorinated anionic surfactant is present in an amount of 0 to 12 wt%, optionally 0 to 10 wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the fluoropolymer particles may have a solids content of 40 to 75 wt%, optionally 50 to 70 wt%, and further optionally 55 to 65 wt%, based on the weight of the concentrated aqueous dispersion of fluoropolymer.
In some embodiments, the fluoropolymer particles may comprise 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, optionally 0.20 to 0.35 μm.
A second aspect of the invention provides a process for the preparation of the concentrated aqueous fluoropolymer dispersion provided by the first aspect of the invention, comprising the steps of:
s1: adding a polyvinylpyrrolidone-based polymer represented by the following formula (I) and optionally a non-fluorinated anionic surfactant to a starting aqueous dispersion of fluoropolymer particles, optionally further adding a polyvinylpyrrolidone-based polymer represented by the following formula (I) to polymerization units of the fluoropolymer at the time of preparing the starting aqueous dispersion of fluoropolymer particles, to obtain a concentrated starting aqueous dispersion of fluoropolymer particles;
s2: concentrating the concentrated starting aqueous dispersion of fluoropolymer particles obtained in step S1;
(C6H9NO)n (I)
n in formula (I) can be 9-450;
wherein the total content of polyvinylpyrrolidone-based polymer represented by formula (I) and the optional non-fluorinated anionic surfactant may be 2 to 16 wt%, optionally 2 to 12 wt%, further optionally 4 to 10 wt%, based on the weight of the fluoropolymer particles in the concentrated starting aqueous dispersion of the fluoropolymer.
In some embodiments, the non-fluorinated anionic surfactant may be added in an amount of 0 to 12 wt%, optionally 0 to 10 wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the fluoropolymer particles in the concentrated starting aqueous dispersion of fluoropolymer particles have a solids content of 15 to 35 wt%, optionally 20 to 30 wt%, based on the weight of the concentrated starting aqueous dispersion of fluoropolymer particles.
In some embodiments, the method of making may further comprise the step of adding a polymerization initiator and an emulsifier to the comonomer of the fluoropolymer to make a starting aqueous dispersion of the fluoropolymer; wherein the polymerization initiator can comprise a persulfate, an organic peroxide, or a combination thereof, optionally can be ammonium persulfate, potassium persulfate, succinic peroxide, or a combination thereof; the emulsifier may include 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-hydrogenperfluoroheptanate, and the like. And the emulsifier in the initial aqueous dispersion of fluoropolymer particles may also be removed by ultrafiltration or by contact with a strongly basic ion exchange resin, before adding the polyvinylpyrrolidone polymer of formula (I) to said initial aqueous dispersion of fluoropolymer particles, in which case the concentrated aqueous dispersion of fluoropolymer is prepared free or substantially free of fluorinated anionic surfactant.
In some embodiments, when the polyvinylpyrrolidone-based polymer represented by formula (I) is added to the polymerization unit of the fluoropolymer in the preparation of the starting aqueous dispersion of the fluoropolymer particles, a concentrated aqueous dispersion of fluoropolymer having more excellent stability can be obtained.
The third aspect of the invention also provides the use of the concentrated aqueous fluoropolymer dispersion provided by the first aspect of the invention for impregnating porous fabrics, porous metals, as a dielectric coating or in the production of fluoropolymer anti-drip agents.
The concentrated aqueous dispersion of a fluoropolymer provided based on the above technical solution contains a polyvinylpyrrolidone (PVP) based polymer represented by formula (I) (and optionally a non-fluorinated anionic surfactant having good biodegradability and water solubility) without containing a polyoxyethylene ether based surfactant, so that the provided concentrated aqueous dispersion of a fluoropolymer can have both a lower viscosity and good stability characteristics, and the polyvinylpyrrolidone (PVP) based polymer (and optionally a non-fluorinated anionic surfactant) has good biodegradability and water solubility characteristics, and thus is more environmentally friendly than the polyoxyethylene ether based surfactants generally used in the prior art. The results of the examples demonstrate that the concentrated aqueous dispersions of fluoropolymers provided by the present invention have a viscosity not exceeding 25 mPas, preferably not exceeding 22 mPas; the prepared coating has the advantages of good mechanical stability and storage stability, long storage time of 5 weeks, 8 weeks or even 10 weeks at room temperature without sedimentation, conductivity of the coating in an elution test of less than 1 mu S, and capability of being used for manufacturing circuit board coatings, impregnating porous fabrics and porous metals, and producing fluoropolymer anti-dripping agents and the like.
Detailed Description
Hereinafter, the concentrated aqueous fluoropolymer dispersion provided by the present invention, and the method for producing and using the same will be described by way of specific embodiments. However, the following description is provided for a sufficient understanding of the present application by those skilled in the art, and is not intended to limit the subject matter described in the claims.
The "ranges" disclosed herein are defined in terms of lower limits and upper limits, with a given range being defined by a selection of one lower limit and one upper limit that define the boundaries of the particular range. Ranges defined in this manner may or may not include endpoints and may be arbitrarily combined, i.e., any lower limit may 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 this application, unless otherwise stated, 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, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers. In addition, when a parameter is an integer of 2 or more, it is equivalent to disclose 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 and alternative embodiments of the present application may be combined with each other to form new solutions, if not specifically stated.
All technical and optional features of the present application may be combined with each other to form new solutions, if not otherwise specified.
The terms "comprises" and "comprising" as used herein mean either open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that other components not listed may also be included or included, or that only listed components may be included or included.
In this application, the term "or" is inclusive, if not 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 not present); a is false (or not present) and B is true (or present); or both a and B are true (or present).
In the description herein, it is to be noted that, unless otherwise specified, the meaning of "one or more" means "several" is two or more.
The concentrated aqueous fluoropolymer dispersion is widely used in chemical, aerospace, military and other industries due to its excellent chemical stability, good electrical properties and low surface energy. In the preparation of concentrated aqueous dispersions of fluoropolymers, it is common practice to concentrate a starting aqueous dispersion of fluoropolymer particles (an aqueous dispersion of fluoropolymer particles having a solids content of about 15 to 35% formed by polymerization of a comonomer of the fluoropolymer) under the action of a nonionic surfactant (polyoxyethylene ether-based surfactant) in combination with an anionic surfactant or the like. However, the commonly used polyoxyethylene ether-based surfactants are poor in biodegradability and not environmentally friendly, limiting the application of concentrated aqueous dispersions of such fluoropolymers.
The present inventors have paid attention to extensive studies that, when a polyvinylpyrrolidone (PVP) -based polymer represented by the formula (I) is added as a surfactant (and optionally a non-fluorinated anionic surfactant having good biodegradability and water solubility) to a starting aqueous dispersion of fluoropolymer particles in a metered amount without adding a polyoxyethylene ether-based surfactant which is generally used, a concentrated aqueous dispersion of a fluoropolymer having a low viscosity, good stability, and low conductivity can be obtained, thereby providing an environmentally friendly concentrated aqueous dispersion of a fluoropolymer.
In a first aspect of the present invention, there is provided a concentrated aqueous dispersion of a fluoropolymer comprising fluoropolymer particles dispersed in an aqueous solvent, a polyvinylpyrrolidone-based polymer represented by the following formula (I) and optionally a non-fluorinated anionic surfactant:
(C6H9NO)n (I)
n in formula (I) can be 9-450;
wherein the total content of polyvinylpyrrolidone-based polymer and optional non-fluorinated anionic surfactant may be 2-16 wt% based on the weight of the fluoropolymer particles. When the total content of the polyvinylpyrrolidone-based polymer and the optional non-fluorinated anionic surfactant is less than 2% by weight, the increase in viscosity of the aqueous dispersion cannot be effectively suppressed, and the dispersion has poor stability, and the obtained product cannot be used as a coating material; when the total content of polyvinylpyrrolidone-based polymer and optional non-fluorinated anionic surfactant is higher than 16 wt%, it may result in excessively high surfactant content in the concentrated aqueous dispersion obtained in production and may deteriorate viscosity characteristics and stability of the product.
In some embodiments, the higher the degree of polymerization of the polyvinylpyrrolidone-based polymer, the higher the average molecular weight, the better the mechanical stability, however, if the degree of polymerization is too high, the larger the average molecular weight, the greater the viscosity of the dispersion, which may result in difficulty in handling. Therefore, the polymerization degree of the polyvinylpyrrolidone polymer in the present invention is preferably 9-450, and the molecular weight is preferably 1000-100000, more preferably 3000-60000, such as 3000-5000, 5000-10000, 10000-20000, 20000-30000, 40000-50000, etc. Alternatively, the polyvinylpyrrolidone-based polymer may be selected from one or more of the following: k12, K15, K17, K25, K30, K60, K90 and K120, wherein preferably one or more selected from the group consisting of K12, K15, K17, K25 and K30, are commercially available, and the above K values all represent viscosity grades of aqueous PVP solutions.
In some embodiments, the polyvinylpyrrolidone-based polymer may be present in an amount of 2 to 12 wt%, optionally 4 to 10 wt%, 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, alkylbenzene sulfonates, α -olefin sulfonates, α -sulfo monocarboxylates, fatty acid ester sulfonates, succinate sulfonates, alkylnaphthalene sulfonates, alkylglycerol ether sulfonates, petroleum sulfonates, lignin sulfonates, alkyl carboxylates; further optionally, 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 Dodecylbenzenesulfonate (SDBS), sodium dodecyl diphenyloxide disulfonate (SLDED), disodium lauryl polyoxyethylene ether sulfosuccinate (MES), sodium dihexylsulfosuccinate, sodium dioctyl sulfosuccinate (OT-75), potassium stearate, sodium dodecyl carboxylate, and sodium dodecyl alcohol polyoxyethylene ether carboxylate.
In some embodiments, the non-fluorinated anionic surfactant is present in an amount of 0 to 12 wt%, optionally 0 to 10 wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the fluoropolymer particles may have a solids content of 40 to 75 wt%, optionally 50 to 70 wt%, and further optionally 55 to 65 wt%, 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 modified by copolymerization with a small amount of other comonomer in a polymer, and the content is not 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, and hexafluoroethylene and vinylidene fluoride.
In some embodiments, the particle size of the fluoropolymer may be 0.15 to 0.40 μm, optionally 0.20 to 0.35 μm, such as 0.20 μm, 0.25 μm, 0.30 μm, 0.35 μm, and the like.
In a second aspect of the invention, there is also provided a process for the preparation of a concentrated aqueous dispersion of a fluoropolymer comprising the steps of:
s1: adding a polyvinylpyrrolidone-based polymer represented by the following formula (I) and optionally a non-fluorinated anionic surfactant to a starting aqueous dispersion of fluoropolymer particles, optionally further adding a polyvinylpyrrolidone-based polymer represented by the following formula (I) to polymerization units of the fluoropolymer at the time of preparing the starting aqueous dispersion of fluoropolymer particles, to obtain a concentrated starting aqueous dispersion of fluoropolymer particles;
s2: concentrating the concentrated starting aqueous dispersion of fluoropolymer particles obtained in step S1;
(C6H9NO)n (I)
n in formula (I) can be 9-450;
wherein the total content of polyvinylpyrrolidone-based polymer represented by formula (I) and the optional non-fluorinated anionic surfactant may be 2 to 16 wt%, optionally 2 to 12 wt%, further optionally 4 to 10 wt%, based on the weight of the fluoropolymer particles in the concentrated starting aqueous dispersion of fluoropolymer particles. Wherein the polyvinylpyrrolidone-based polymer represented by the formula (I) and optionally the non-fluorinated anionic surfactant are added in a total amount of 2 to 16% by weight in the course of concentration (or in both the course of polymerization and concentration) of the starting aqueous dispersion of the fluoropolymer particles, the problem of viscosity increase of the aqueous dispersion during concentration can be effectively avoided, and a product with good stability is obtained; on the other hand, the use of the polyvinylpyrrolidone-based polymer represented by formula (I) and optionally a non-fluorinated anionic surfactant is more environmentally friendly than the polyoxyethylene ether-based surfactant that is generally used.
In some embodiments, the non-fluorinated anionic surfactant is present in an amount of 0 to 12 wt%, optionally 0 to 10 wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the fluoropolymer particles in the concentrated starting aqueous dispersion of fluoropolymer particles have a solids content of 15 to 35 wt%, optionally 20 to 30 wt%, based on the weight of the concentrated starting aqueous dispersion of fluoropolymer particles.
In some embodiments, the above-described method of preparation 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 is free radical initiated, and can be selected from persulfate with longer half-life, such as potassium persulfate or ammonium persulfate; alternatively, potassium permanganate or oxalic acid with a short half-life may be used. In addition to the preferred persulfate initiators of the present invention, small amounts of short chain dicarboxylic acids capable of reducing coagulum, such as succinic acid or succinic acid-generating initiators such as disuccinic acid peroxide (DSP), may also be added. The amount of the emulsifier may be 0.1 to 0.5 wt% of the fluoropolymer produced by polymerization, which may include a fluorocarbon-based emulsifier, a hydrocarbon-based emulsifier, or a combination thereof, optionally ammonium perfluoro 2-methyl-3-oxahexanoate, sodium perfluoro 2, 5-dimethyl-3, 6-dioxanonanoate, sodium perfluorohexyl acetate, potassium omega-hydrogenperfluoroheptanoate, and the like. And the emulsifier in the initial aqueous dispersion of fluoropolymer particles may be removed by ultrafiltration or by contact with an anion exchange resin before the polyvinylpyrrolidone polymer represented by formula (I) is added to the initial aqueous dispersion of fluoropolymer particles. The concentrated aqueous fluoropolymer dispersion ultimately provided by the present invention may or may not contain an emulsifier, i.e., the concentrated aqueous fluoropolymer dispersion ultimately provided by the present invention may or may not contain a fluorinated anionic surfactant.
In some embodiments, when the polyvinylpyrrolidone-based polymer represented by formula (I) is added to the polymerization unit of the fluoropolymer in the preparation of the starting aqueous dispersion of the fluoropolymer particles, a concentrated aqueous dispersion having lower viscosity and more excellent stability can be obtained.
In some embodiments, the concentration in step S2 can be performed by chemical concentration, electrical concentration, vacuum concentration, or the like, such that the fluoropolymer particles have a solids content in the concentrated aqueous dispersion of 40 to 75 wt%, optionally 50 to 70 wt%, and further optionally 55 to 65 wt%.
Proved by verification, the concentrated aqueous dispersion of the fluorine-containing polymer prepared by the invention has the characteristics of lower viscosity, high shear stability, high storage stability and the like, has high CCT (critical cracking thickness) when being used as a coating, and has low elution conductivity, so the third aspect of the invention also provides the application of the concentrated aqueous dispersion of the fluorine-containing polymer in impregnating porous metal, porous fabrics, being used as a dielectric coating or producing a fluorine-containing polymer anti-dripping agent and the like, 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 gloss, good film forming property, high film forming limit film cracking thickness, crack resistance and the like.
In some embodiments, the porous fabric may be a glass cloth, and the glass cloth is classified into both alkali-containing and alkali-free glass cloths. When the alkali-containing glass cloth is impregnated with the concentrated aqueous dispersion of the fluorine-containing polymer, the anti-sticking fluoropolymer varnished cloth (such as polytetrafluoroethylene varnished cloth) is obtained, and can be used for packaging and sealing of foods, chemical fertilizers, soymilk and blood products, anti-sticking and anti-corrosion treatment of rollers in the industries of textile, printing and dyeing of clean and sanitary conveyor belts, chemical industry and the like, leakage prevention of tents and roofs and the like. When the alkali-free glass cloth is impregnated with the concentrated aqueous dispersion of the fluorine-containing polymer, an electrically insulating fluorine-containing polymer varnished cloth can be prepared, and can be used as an insulating groove, inter-turn insulation, wrapping insulation and the like in the aspects of aircraft engines, motors and the like, and can also be used as a microwave material in the aspects of vacuum pumps, radars, electronic instruments, televisions, computers, satellite communication and the like by hot pressing to form a laminated plate and an attached foil plate.
Examples
Hereinafter, examples of the present application will be described. The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the present disclosure. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Impregnation of glass cloth
Alkali-free glass cloth was treated with the concentrated aqueous fluoropolymer dispersion prepared according to the present invention in the following order. Plain weave density of glass cloth: 60 (lines/25 mm) in length and 46 (lines/25 mm) in width, and 0.05mm in thickness. The glass cloth is a product of plain cloth which is neat in longitude and latitude and free of defects such as breakage and broken ends after hot washing.
First, a glass cloth was impregnated with a concentrated aqueous dispersion of a fluoropolymer 1 time, dried at about 100 ℃, baked at about 280 ℃ and 290 ℃ and then sintered for 3 min. And (5) placing the mixture in a normal temperature for cooling.
② immersing the impregnated product in the same concentrated aqueous dispersion of a fluoropolymer to contain the impregnation solution, drying the impregnated product at about 100 ℃ and firing the dried impregnated product at about 380 ℃ for 3 minutes. Thereafter, bubbling of the coated fluoropolymer concentrated aqueous dispersion was observed.
Thirdly, repeating the impregnation, drying and firing procedures to obtain the glass cloth with the coating formed by the film-shaped material with the solid content of the fluorine-containing polymer of 60-65 percent and the film thickness of 80 mu m.
Performance testing
Solid content of concentrated aqueous dispersion: determined by the weight loss of each aqueous dispersion after drying at 150 ℃ for 1 hour.
Viscosity of concentrated aqueous dispersion: 500ml of the suspension was measured for viscosity at 25 ℃ on a rotational viscometer model NDJ-1.
Mechanical stability of concentrated aqueous dispersions: adopting a high-rotation-speed emulsifying machine, and testing conditions: shearing at high speed for 5min at 25 ℃ and at 10000rpm of an emulsifying machine, and observing whether demulsification exists or not, wherein if demulsification does not exist, the stability is good; otherwise, the stability is poor.
Storage stability of concentrated aqueous dispersions: taking a certain amount of the concentrated aqueous dispersion of the fluorine-containing polymer, standing the concentrated aqueous dispersion at room temperature, and observing the state of the dispersion once every other week;
CCT test of coatings formed from concentrated aqueous dispersions: the dispersion to be tested is filled into a container and, if foamed, removed using a pipette. Degreasing aluminum plate (18X 4 mm)2) Immersed in the dispersion, the panels were taken out and hung at an angle of 45 ° to dry, the panels were dried for 5min and then heated at 380 ℃ for 10min, the panels were cooled and the cracks of the coating were rated using a microscope. The maximum film thickness without cracking was defined as the critical film thickness (. mu.m).
And (3) testing the chromaticity of the coated glass cloth: l, a and b of the coated glass cloth were tested using a Konika Mentenda CM-5 colorimeter, and changes in the chromaticity values Δ L, Δ a and Δ b were calculated by subtracting the chromaticities L0, a0 and b0 of the glass cloth before coating. When the yellowing index Δ b is less than 1, the dispersion is considered to be good, and when the value is equal to or greater than 1, the dispersion is considered to be poor. When cracks in the coating were observed, the dispersion was considered poor.
Elution conductivity of coated glass cloth: the coated glass cloth was immersed in distilled water 10 times the mass for 1 week, and the conductivity of the eluate was measured with a conductivity meter manufactured by Lacom. The conductivity was less than 1. mu.S, indicating that the ionic component was hardly dissolved, and was considered to be good; on the other hand, the conductivity exceeding 1. mu.S was considered to be poor.
Example 1
3000g of deionized water and 80g of paraffin were placed in a 5L stainless steel autoclave equipped with a jacket and a horizontal stirrer, the contents of the autoclave were heated to 70 ℃ and the autoclave was evacuated, purged with Tetrafluoroethylene (TFE) after nitrogen substitution. Polymerization initiator ammonium persulfate 0.02g, fluorine-containing emulsifier (sodium perfluorohexyl acetate) 3g, BASF PVP K12 (based on the weight of polytetrafluoroethylene particles, the same applies hereinafter) 1 wt% were added, the reaction pressure was controlled to 2.5MPa, and TFE was continuously fed through the compressor. An initial aqueous dispersion of polytetrafluoroethylene particles is prepared by an emulsion polymerization process. The solids content of this dispersion was about 20% by weight and the mean particle diameter of the polytetrafluoroethylene particles was about 250 nm.
2kg of a starting aqueous dispersion of polytetrafluoroethylene particles containing about 0.2% by weight of sodium perfluorohexylacetate based on the weight of the polytetrafluoroethylene particles were taken, 5% by weight of BASF PVP K12 was added, and vacuum concentration was carried out to give a concentrated aqueous dispersion having a solid content of 60.9% by weight. Has good storage stability, and no precipitation appears after being placed for 10 weeks. The results of the performance tests are shown in table 1 below.
Example 2
3000g of deionized water and 80g of paraffin were placed in a 5L stainless steel autoclave equipped with a jacket and a horizontal stirrer, the contents of the autoclave were heated to 70 ℃ and the autoclave was evacuated, purged with Tetrafluoroethylene (TFE) after nitrogen substitution. Polymerization initiator ammonium persulfate 0.02g, fluorine-containing emulsifier (sodium perfluorohexyl acetate) 3g, BASF PVP K17 1 wt% were added, reaction pressure was controlled to 2.5MPa, and TFE was continuously fed through the compressor. An initial aqueous dispersion of polytetrafluoroethylene particles is prepared by an emulsion polymerization process. The dispersion has a solids content of about 25% by weight and the polytetrafluoroethylene particles have an average particle diameter of about 250 nm.
2kg of an initial aqueous dispersion of polytetrafluoroethylene particles were taken, and concentrated in vacuo by adding 5% by weight of BASF PVP K17 to give a concentrated aqueous dispersion having a solids content of 61.8% by weight. Has good storage stability, and no precipitation appears after being placed for 10 weeks. The results of the performance tests are shown in table 1 below.
Example 3
According to example 2, except that 2kg of the starting aqueous dispersion of polytetrafluoroethylene particles was taken and concentrated under vacuum by adding 4% by weight of BASF PVP K17, the resulting concentrated aqueous dispersion had a solids content of about 62.4% by weight and was stable on storage and did not precipitate after standing for 10 weeks. The results of the performance tests are shown in table 1 below.
Example 4
According to example 2, except that 2kg of the starting aqueous dispersion of polytetrafluoroethylene particles was taken, 9 wt% of BASF PVP K17 was added thereto and the concentrate was concentrated under vacuum, the resulting concentrated aqueous dispersion had a solids content of about 61.7 wt%, good storage stability and no precipitation occurred after 10 weeks of storage. The results of the performance tests are shown in table 1 below.
Example 5
3000g of deionized water and 80g of paraffin were placed in a 5L stainless steel autoclave equipped with a jacket and a horizontal stirrer, the contents of the autoclave were heated to 70 ℃ and the autoclave was evacuated, purged with Tetrafluoroethylene (TFE) after nitrogen substitution. Polymerization initiator ammonium persulfate 0.02g, fluorine-containing emulsifier (sodium perfluorohexyl acetate) 3g, BASF PVP K30 1 wt% were added, reaction pressure was controlled to 2.5MPa, and TFE was continuously fed through the compressor. An initial aqueous dispersion of polytetrafluoroethylene particles is prepared by an emulsion polymerization process. The dispersion had a solids content of about 30% by weight and the polytetrafluoroethylene particles had an average particle diameter of 250 nm.
2kg of an initial aqueous dispersion of polytetrafluoroethylene particles were taken, and concentrated in vacuo by adding 5% by weight of BASF PVP K30 to give a concentrated aqueous dispersion having a solids content of 61.6% by weight. Has good storage stability, and no precipitation appears after being placed for 10 weeks. The results of the performance tests are shown in table 1 below.
Example 6
According to example 5, except that 2kg of the starting aqueous dispersion of polytetrafluoroethylene particles was taken, 3% by weight of BASF PVP K30 was added thereto and the concentration in vacuo was carried out, the resulting concentrated aqueous dispersion had a solids content of about 61.4% by weight. A small amount of precipitate appeared upon standing for 8 weeks. The results of the performance tests are shown in table 1 below.
Example 7
According to example 5, except that 2kg of the starting aqueous dispersion of polytetrafluoroethylene particles was taken, 7 wt% of BASF PVP K30 was added thereto and vacuum concentrated, the resulting concentrated aqueous dispersion had a solids content of about 62.2 wt% and a small amount of precipitation occurred after 5 weeks of standing. The results of the performance tests are shown in table 1 below.
Example 8
3000g of deionized water and 80g of paraffin were placed in a 5L stainless steel autoclave equipped with a jacket and a horizontal stirrer, the contents of the autoclave were heated to 70 ℃ and the autoclave was evacuated, purged with Tetrafluoroethylene (TFE) after nitrogen substitution. Polymerization initiator ammonium persulfate (0.02 g) and fluorine-containing emulsifier (perfluorohexylsodium acetate) (3 g) were added thereto, and TFE was continuously fed through a compressor while controlling the reaction pressure at 2.5 MPa. An initial aqueous dispersion of polytetrafluoroethylene particles is prepared by an emulsion polymerization process. The dispersion has a solids content of about 20% by weight and the polytetrafluoroethylene particles have an average particle diameter of 250 nm.
2kg of an initial aqueous dispersion of polytetrafluoroethylene particles was taken, 6% by weight of BASF PVP K17 was added, and vacuum concentration was carried out, and the resulting concentrated aqueous dispersion had a solid content of 61.6% by weight and a small amount of precipitation appeared after standing for 8 weeks. The results of the performance tests are shown in table 1 below.
Example 9
According to example 8, except that 2kg of the starting aqueous dispersion of polytetrafluoroethylene particles was taken, 2 wt% of BASF PVP K17 was added thereto and vacuum concentrated, the resulting concentrated aqueous dispersion had a solids content of about 55.2 wt%, and a small amount of precipitation appeared after 5 weeks of standing. The results of the performance tests are shown in table 1 below.
Example 10
According to example 8, except that 2kg of the starting aqueous dispersion of polytetrafluoroethylene particles was taken, 12% by weight of BASF PVP K17 was added thereto and vacuum concentration was carried out, the resulting concentrated aqueous dispersion had a solid content of about 64.2% by weight, and a small amount of precipitation appeared after leaving for 5 weeks. The results of the performance tests are shown in table 1 below.
Comparative examples 1 to 4
Comparative example 1 the procedure of example 1 was followed except that the surfactant used was polyvinyl alcohol (PVOH, BASF, molecular weight 20000). The resulting concentrated aqueous dispersion had a solids content of about 60% by weight. A small amount of precipitate appeared after 4 weeks of standing. The results of the performance tests are shown in table 1 below.
Comparative example 2 the procedure of example 1 was followed except that the surfactant used was polyacrylamide (PAM, BASF, molecular weight 1000). The resulting concentrated aqueous dispersion had a solids content of about 60% by weight. After standing for 1 week, a partial precipitate appeared and the storage stability was poor. The results of the performance tests are shown in table 1 below.
Comparative example 3 the procedure of example 1 was followed except that the surfactant used was a branched secondary alcohol polyoxyethylene ether (TERGITOL)TMTMN-10, molecular weight 500-. The resulting concentrated aqueous dispersion had a solids content of about 59.8 wt%. A small amount of precipitate appeared after 4 weeks of standing. The results of the performance tests are shown in table 1 below.
Comparative example 4 the procedure of example 8 was followed except that 5 wt% BASF PVP K30 and 1 wt% TMN-10 were used as the surfactants. The resulting concentrated aqueous dispersion had a solids content of about 60% by weight. A small amount of precipitate appeared after 4 weeks of standing. The results of the performance tests are shown in table 1 below.
Figure BDA0003495715980000121
As can be seen from Table 1 above, the concentrated aqueous dispersions obtained in comparative examples 1 to 3 using one of the other nonionic surfactants failed to achieve satisfactory mechanical stability and storage stability; while examples 1 to 7 in which a polyvinyl pyrrolidone (PVP) based polymer represented by the formula (I) was metered stepwise during the preparation of the starting aqueous dispersion of polytetrafluoroethylene particles and during the subsequent concentration, and examples 8 to 10 in which a polyvinyl pyrrolidone (PVP) based polymer represented by the formula (I) was metered directly into the starting aqueous dispersion of polytetrafluoroethylene particles as a surfactant, concentrated aqueous dispersions of fluoropolymers having both low viscosity, good mechanical stability and storage stability could be obtained. Specifically, the obtained concentrated aqueous dispersions of polytetrafluoroethylene each have a viscosity of not more than 25 mPas, preferably not more than 22 mPas, and each have good mechanical stability and storage stability, can be stored at room temperature for a long period of 5 weeks, 8 weeks, or even 10 weeks without sedimentation, and even exhibit a better stability effect than when two surfactants are added (comparative example 4, TMN-10+ K30). Especially when the total amount of the polyvinylpyrrolidone (PVP) -based polymer represented by formula (I) added is 4 to 10 wt%, there is a better stabilization effect, and since the polyvinylpyrrolidone (PVP) -based polymer represented by formula (I) has good biodegradability, a concentrated aqueous dispersion of polytetrafluoroethylene prepared using the same is environmentally friendly.
On the other hand, the concentrated aqueous dispersions prepared in examples 1 to 10 had larger crack-free thicknesses (CCT) than those of comparative examples 1 to 4, and when the glass cloth was impregnated with the concentrated aqueous dispersions of polytetrafluoroethylene prepared in examples 1 to 10, the whiteness of the glass cloth (yellowness index Δ b was less than 1) was good, and the conductivity of the elution test was low (<1 μ S).
Examples 11 to 15
Examples 11-15 were carried out following the procedure of example 8, except that the surfactant was used and in varying amounts. The method specifically comprises the following steps:
the surfactant used in example 11 was 10 wt% BASF PVP K17+1 wt% Sodium Dodecylbenzenesulfonate (SDBS).
The surfactant used in example 12 was 5 wt% BASF PVP K17+2 wt% Sodium Dodecylbenzenesulfonate (SDBS).
The surfactant used in example 13 was 5 wt% BASF PVP K17+5 wt% sodium dodecyl carboxylate.
The surfactant used in example 14 was 1 wt% BASF PVP K17+10 wt% sodium dihexyl sulfosuccinate.
The surfactant used in example 15 was 1 wt% BASF PVP K17+1 wt% Sodium Dodecyl Sulfate (SDS).
The results of the performance testing of the concentrated aqueous dispersions of polytetrafluoroethylene prepared in examples 11-15 are shown in Table 2 below.
Table 2: concentrated aqueous dispersions of polytetrafluoroethylene prepared in examples 11-15 and Dip processability measurements
Figure BDA0003495715980000131
Figure BDA0003495715980000141
As is clear from the results shown in table 2, when the starting aqueous dispersion of polytetrafluoroethylene particles was concentrated, the polyvinylpyrrolidone (PVP) based polymer represented by formula (I) and the non-fluorinated anionic surfactant were added thereto in a metered amount at the same time, and the concentrated aqueous dispersion of polytetrafluoroethylene prepared also had both low viscosity and good mechanical stability and storage stability, and the polyvinylpyrrolidone (PVP) based polymer represented by formula (I) and the non-fluorinated anionic surfactant had both good biodegradability and water solubility, so that the concentrated aqueous dispersion was more environmentally friendly than the conventional use of a polyoxyethylene ether based surfactant having poor biodegradability. On the other hand, the concentrated aqueous dispersions prepared in examples 11 to 15 also had large crack-free thicknesses (CCT), and when the glass cloth was impregnated with the concentrated aqueous dispersions of polytetrafluoroethylene prepared in examples 11 to 15, the whiteness (yellowness index Δ b was less than 1 in each) of the glass cloth was good, and the conductivity of the elution test was low (<1 μ S).
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the invention as defined by the appended claims. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (11)

1. A concentrated aqueous dispersion of a fluoropolymer comprising fluoropolymer particles dispersed in an aqueous solvent, a polyvinylpyrrolidone-based polymer represented by the following formula (I) and optionally a non-fluorinated anionic surfactant:
(C6H9NO)n (I)
in the formula (I), n is 9-450;
wherein the total content of polyvinylpyrrolidone-based polymer and optional non-fluorinated anionic surfactant is 2-16 wt% based on the weight of the fluoropolymer particles.
2. A concentrated aqueous fluoropolymer dispersion according to claim 1, wherein the polyvinylpyrrolidone polymer has a molecular weight of 1000-;
further optionally, the polyvinylpyrrolidone polymer is selected from one or more of the following: k12, K15, K17, K25 and K30.
3. Concentrated aqueous fluoropolymer dispersion according to claim 1, wherein the polyvinylpyrrolidone polymer is present in an amount of 2-12 wt%, optionally 4-10 wt%, based on the weight of the fluoropolymer particles.
4. Concentrated aqueous fluoropolymer dispersion according to claim 1, wherein the non-fluorinated anionic surfactant is 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, alkylbenzene sulfonates, α -olefin sulfonates, α -sulfo monocarboxylates, fatty acid ester sulfonates, succinate sulfonates, alkylnaphthalene sulfonates, alkylglycerol ether sulfonates, petroleum sulfonates, lignin sulfonates, alkyl carboxylates;
further optionally, the 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, disodium lauryl polyoxyethylene ether sulfosuccinate, sodium dihexyl sulfosuccinate, sodium dioctyl sulfosuccinate, potassium stearate, sodium dodecyl carboxylate and sodium dodecyl alcohol polyoxyethylene ether carboxylate;
further optionally, the non-fluorinated anionic surfactant is present in an amount of 0 to 12 wt%, optionally 0 to 10 wt%, based on the weight of the fluoropolymer particles.
5. Concentrated aqueous fluoropolymer dispersion according to any of claims 1 to 4 wherein the fluoropolymer particles have a solids content of 40 to 75 wt%, optionally 50 to 70 wt%, further optionally 55 to 65 wt%, based on the weight of the concentrated aqueous fluoropolymer dispersion.
6. The concentrated aqueous fluoropolymer dispersion according to any of claims 1-4, wherein the fluoropolymer particles comprise polytetrafluoroethylene particles, modified polytetrafluoroethylene particles, or a combination thereof.
7. Concentrated aqueous fluoropolymer dispersion according to any of claims 1 to 4 wherein the fluoropolymer particles have a particle size of 0.15 to 0.40 μm, optionally 0.20 to 0.35 μm.
8. Process for the preparation of a concentrated aqueous dispersion of a fluoropolymer according to any of claims 1 to 7 comprising the steps of:
s1: adding a polyvinylpyrrolidone-based polymer represented by the following formula (I) and optionally a non-fluorinated anionic surfactant to a starting aqueous dispersion of fluoropolymer particles, optionally further adding a polyvinylpyrrolidone-based polymer represented by the following formula (I) to polymerization units of the fluoropolymer at the time of preparing the starting aqueous dispersion of fluoropolymer particles, to obtain a concentrated starting aqueous dispersion of fluoropolymer particles;
s2: concentrating the concentrated starting aqueous dispersion of fluoropolymer particles obtained in step S1;
(C6H9NO)n (I)
in the formula (I), n is 9-450;
wherein the total content of polyvinylpyrrolidone-based polymer represented by formula (I) and optionally non-fluorinated anionic surfactant is 2 to 16 wt%, optionally 2 to 12 wt%, further optionally 4 to 10 wt%, based on the weight of the fluoropolymer particles in the concentrated starting aqueous dispersion of fluoropolymer particles.
9. Process for the preparation according to claim 8, wherein the fluoropolymer particles in the concentrated starting aqueous dispersion of fluoropolymer particles have a solids content of 15-35 wt%, optionally 20-30 wt%, based on the weight of the concentrated starting aqueous dispersion of fluoropolymer particles.
10. The method of claim 8 or 9, wherein the non-fluorinated anionic surfactant is added in an amount of 0-12 wt%, optionally 0-10 wt%, based on the weight of the fluoropolymer particles.
11. Use of a concentrated aqueous fluoropolymer dispersion according to any one of claims 1 to 7 for impregnating porous fabrics, porous metals, as dielectric coatings or in the production of fluoropolymer anti-drip agents.
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