CN114381013A - 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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CN114381013A
CN114381013A CN202210114168.XA CN202210114168A CN114381013A CN 114381013 A CN114381013 A CN 114381013A CN 202210114168 A CN202210114168 A CN 202210114168A CN 114381013 A CN114381013 A CN 114381013A
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fluoropolymer
optionally
concentrated aqueous
anionic surfactant
weight
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CN114381013B (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
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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
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    • 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
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    • 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
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    • 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
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance

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Abstract

The invention discloses a concentrated aqueous dispersion of a fluorine-containing polymer, a preparation method and application thereof, belonging to the technical field of coatings. Disclosed is 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 polymers represented by formula (I), and not comprising a polyoxyethylene ether-based surfactant; the total content of anionic surfactant and optional nonionic surfactant is from 2 to 16 wt% based on the weight of the fluoropolymer particles. The concentrated aqueous fluoropolymer dispersion disclosed by the invention has the characteristics of low viscosity and good stability, is environment-friendly, can be used for producing a fluoropolymer anti-dripping agent, impregnating porous glass and porous metal or serving 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 invention relates to the technical field of coatings, in particular to a fluoropolymer 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-based surfactants are poor in biodegradability and are not environmentally friendly, thereby limiting the wide use of such concentrated aqueous dispersions of fluoropolymers.
Disclosure of Invention
In view of one or more problems in 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, an anionic surfactant and optionally a nonionic surfactant selected from polyvinylpyrrolidone-based polymers represented by the following formula (I):
(C6H9NO)n (I)
in the formula (I), n is 9-450;
and said concentrated aqueous dispersion of fluoropolymer does not contain polyoxyethylene ether surfactant;
wherein the total content of anionic surfactant and optional nonionic surfactant may be from 2 to 16 wt% 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 from 2 to 12 wt%, optionally from 4 to 10 wt%, and the fluorinated anionic surfactant may be present in an amount of from 0 to 0.5 wt%, optionally from 0 to 0.3 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; 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 fluorinated anionic surfactant may be selected from one or more of the following: perfluoro-2-methyl-3-oxahexanoic acid ammonium, perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid sodium, perfluoro-hexylsodium acetate, and omega-hydrogen perfluoro-potassium heptanate.
In some embodiments, the polyvinylpyrrolidone-based polymer may have a molecular weight of 1000-.
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 6 wt%, and optionally 0 to 3 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.
The second aspect of the present invention provides a process for producing a concentrated aqueous dispersion of a fluoropolymer, which comprises adding an anionic surfactant in a total amount of 2 to 16% by weight 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;
(C6H9NO)n (I)
in the formula (I), n is 9-450; wherein:
said wt% being based on the weight of fluoropolymer particles in the starting aqueous dispersion of fluoropolymer particles;
the concentrated aqueous fluoropolymer dispersion is free of polyoxyethylene ether surfactants.
In some embodiments, the anionic surfactant can be a non-fluorinated anionic surfactant; preferably, the non-fluorinated anionic surfactant may be added in an amount of from 2 to 12 wt%, optionally from 4 to 10 wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the initial aqueous dispersion of fluoropolymer particles contains fluorinated anionic surfactant, which may be present in an amount of 0 to 0.5 wt%, optionally 0 to 0.3 wt%, based on the weight of fluoropolymer particles in the initial aqueous dispersion of fluoropolymer particles.
In some embodiments, the nonionic surfactant can be added in an amount of 0 to 6 wt%, and optionally 0 to 3 wt%, 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 35 wt%, alternatively 20 to 30 wt%, based on the weight of the starting aqueous dispersion of fluoropolymer particles.
In some embodiments, the 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 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. The emulsifier in the initial aqueous dispersion of fluoropolymer particles may be removed by ultrafiltration or by 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 free or substantially free of fluorinated anionic surfactant.
In a third aspect, the present invention also provides the use of the concentrated aqueous fluoropolymer dispersion provided in the first aspect for impregnating porous fabrics, porous metals, as dielectric coatings or in the production of fluoropolymer anti-drip agents.
The concentrated aqueous dispersion of a fluoropolymer provided based on the above technical solution contains an anionic surfactant (and optionally a nonionic surfactant selected from polyvinylpyrrolidone polymers represented by formula (I)) but does not contain a polyoxyethylene ether surfactant, so that the concentrated aqueous dispersion of a fluoropolymer has both low viscosity and good stability, and the anionic surfactant has good biodegradability and water solubility, and thus is more environmentally friendly than the polyoxyethylene ether surfactants widely used in the prior art, which have poor biodegradability. The results of the examples demonstrate that the concentrated aqueous dispersions of fluoropolymers provided by the present invention do not have a viscosity exceeding 20 mPas, preferably not exceeding 18 mPas; the sodium dodecyl sulfate has good mechanical stability and storage stability, can be stored for 2 months at room temperature without color change or sedimentation, and even shows better stability effect than that of adding two surfactants (TMN-10+ SDS); and the coating prepared by the concentrated aqueous dispersion of the fluorine-containing polymer provided by the invention has good glossiness and transparency and excellent heat resistance and wear resistance.
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, "above" and "below" are inclusive, and "one or more" means "several" are 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) by the action of a nonionic surfactant (usually a polyoxyethylene ether-based surfactant) in combination with an anionic surfactant or the like. The widely used polyoxyethylene ether surfactants have poor biodegradability and are not environment-friendly, and further, the application of the concentrated aqueous dispersion of the fluorine-containing polymer is limited.
The present inventors have noted through extensive studies that when a non-fluorinated anionic surfactant (and optionally a non-ionic surfactant selected from polyvinylpyrrolidone-based polymers represented by formula (I)) is added to a starting aqueous dispersion of fluoropolymer particles, which may contain a small amount of fluorinated anionic surfactant or no such fluorinated anionic surfactant, in a metered amount, can obtain a concentrated aqueous dispersion of a fluoropolymer having a low viscosity and good stability without adding a polyoxyethylene ether surfactant which is conventionally used, and such a non-fluorinated anionic surfactant and optionally a nonionic surfactant of a polyvinylpyrrolidone polymer represented by the formula (I) have good biodegradability and water solubility, therefore, the surfactant is more environment-friendly compared with polyoxyethylene ether surfactants used in the prior art.
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, 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;
(C6H9NO)n (I)
in the formula (I), n is 9-450;
wherein the total content of anionic surfactant and optional nonionic surfactant may be from 2 to 16 wt% 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 cannot be effectively suppressed and the stability is poor, and the product cannot be used as a coating material; when the amount of the surfactant is more than 16 wt%, it may result in an excessively high content of the surfactant in the concentrated aqueous dispersion and may deteriorate viscosity characteristics and stability of the product.
In some embodiments, the anionic surfactant may be selected from non-fluorinated anionic surfactants, or a mixture of non-fluorinated anionic surfactants and fluorinated anionic surfactants; the non-fluorinated anionic surfactant may be present in an amount of 2 to 12 wt%, optionally 4 to 10 wt%, and the fluorinated anionic surfactant may be present in an amount of 0 to 0.5 wt%, optionally 0 to 0.3 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; 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 fluorinated anionic surfactant may be selected from one or more of the following: perfluoro-2-methyl-3-oxahexanoic acid ammonium, perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid sodium, perfluoro-hexylsodium acetate, and omega-hydrogen perfluoro-potassium heptanate.
In some embodiments, the polyvinylpyrrolidone-based polymer may have a molecular weight of 1000-.
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 6 wt%, and optionally 0 to 3 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, hexafluoroethylene, vinylidene fluoride, and the like.
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.
In a second aspect of the present invention, there is provided a process for producing a concentrated aqueous dispersion of a fluoropolymer, which comprises adding an anionic surfactant in a total amount of 2 to 16% by weight and optionally a nonionic surfactant selected from polyvinylpyrrolidone-based polymers represented by the following formula (I) to a starting aqueous dispersion of particles of a fluoropolymer, and concentrating;
(C6H9NO)n (I)
in the formula (I), n is 9-450; wherein:
said wt% being based on the weight of fluoropolymer particles in the starting aqueous dispersion of fluoropolymer particles;
the concentrated aqueous fluoropolymer dispersion is free of polyoxyethylene ether surfactants.
In some embodiments, the anionic surfactant is a non-fluorinated anionic surfactant, optionally added in an amount of 2 to 12 wt%, further optionally 4 to 10 wt%, based on the weight of the fluoropolymer particles.
In some embodiments, the initial aqueous dispersion of fluoropolymer particles contains fluorinated anionic surfactant, which may be present in an amount of 0 to 0.5 wt%, optionally 0 to 0.3 wt%, based on the weight of fluoropolymer particles in the initial aqueous dispersion of fluoropolymer particles.
In some embodiments, the nonionic surfactant can be added in an amount of 0 to 6 wt%, and optionally 0 to 3 wt%, 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 35 wt%, alternatively 20 to 30 wt%, based on the weight of the starting aqueous dispersion of fluoropolymer particles.
In some embodiments, the 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 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 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. 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 0-0.5 wt%, optionally 0-0.3 wt% based on the amount of fluoropolymer particles, and the emulsifier in the starting aqueous dispersion of fluoropolymer particles may be removed by ultrafiltration or by contact with a strongly basic ion exchange resin, etc., prior to adding anionic surfactant to the starting aqueous dispersion of fluoropolymer particles, in which case the concentrated aqueous dispersion of fluoropolymer may be prepared free or substantially free of fluorinated anionic surfactant.
In some embodiments, the concentration may be 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 from 40 to 75 wt%, optionally from 50 to 70 wt%, and further optionally from 55 to 65 wt%.
The third aspect of the invention also provides the application of the fluoropolymer concentrated aqueous dispersion in the production of fluoropolymer anti-dripping agents, impregnation of porous metals, porous fabrics, dielectric coatings and the like, the fluoropolymer concentrated aqueous dispersion 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 ℃ and fired at about 380 ℃ for 3 min. And (5) placing the mixture in a normal temperature for cooling.
② spraying the above impregnation in the same fluoropolymer concentrated aqueous dispersion to contain the spraying liquid, drying at about 100 ℃ and firing at about 380 ℃ for 3 min. Thereafter, bubbling of the coated fluoropolymer concentrated aqueous dispersion was observed.
Thirdly, repeating the spraying, 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.
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: a fixed amount of the concentrated aqueous fluoropolymer dispersion was taken and stored at room temperature, and the state of the dispersion was observed 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).
Glossiness of the coated glass cloth: the reflectance of light at an incident angle of 60 ° was measured using a gloss meter.
And (3) testing the wear resistance of the coated glass cloth: according to GB/T1768-1979, after grinding 200 circles by a grinding wheel under a weight of 250g, the weight loss of the coating is tested, so as to judge the wear resistance of the coating.
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 (0.02 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 30% by weight and the polytetrafluoroethylene particles have an average particle diameter of 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 was taken, 6% by weight (based on the weight of the polytetrafluoroethylene particles, the same applies hereinafter) of an anionic surfactant of Sodium Dodecyl Sulfate (SDS) was added, and vacuum concentration was carried out, whereby the resulting concentrated aqueous dispersion had a solid content of 60.1% by weight. The results of the performance tests are shown in table 1 below.
Example 2
The procedure of example 1 was followed, except that SDS in example 1 was replaced with sodium dodecylbenzenesulfonate anionic surfactant represented by SDBS in an amount of 6% by weight, and vacuum concentration was performed, and the resulting concentrated aqueous dispersion had a solid content of about 64.8% by weight. The results of the performance tests are shown in table 1 below.
Example 3
The procedure of example 1 was followed, except that SDS in example 1 was replaced with sodium dodecyldiphenyloxide disulfonate anionic surfactant as a 45% aqueous SLDED solution in an amount of 6% by weight (based on the dry weight of the SLDED), and vacuum concentration was carried out to obtain a concentrated aqueous dispersion having a solid content of about 61.3%. The results of the performance tests 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 carried out to obtain a concentrated aqueous dispersion having a solid content of about 62% by weight. The results of the performance tests 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 carried out to obtain a concentrated aqueous dispersion having a solid content of about 60.8% by weight. The results of the performance tests 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 carried out to obtain a concentrated aqueous dispersion having a solid content of about 59.2% by weight. The results of the performance tests 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 carried out to obtain a concentrated aqueous dispersion having a solid content of about 60.9% by weight. The results of the performance tests 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 carried out to obtain a concentrated aqueous dispersion having a solid content of about 60.7% by weight. The results of the performance tests are shown in table 1 below.
Example 9
The procedure of example 1 was followed, except that SDS in example 1 was replaced with dihexyl sodium sulfosuccinate anionic surfactant in an amount of 6% by weight, and vacuum concentration was performed to obtain a concentrated aqueous dispersion having a solid content of about 55.5% by weight. The results of the performance tests are shown in table 1 below.
Example 10
The procedure of example 9 was followed except that the amount of dihexyl sodium sulfosuccinate anionic surfactant added was 4% by weight, and vacuum concentration was performed to obtain a concentrated dispersion having a solid content of 60.9% by weight. The results of the performance tests are shown in table 1 below.
Example 11
The procedure was followed as in example 1, except that: (1) adding a strongly basic ion exchange resin to the obtained starting aqueous dispersion of polytetrafluoroethylene particles to remove sodium perfluorohexyl acetate therein; (2) the SDS of example 1 was replaced with sodium lauryl alcohol polyoxyethylene ether carboxylate anionic surfactant in an amount of 6% by weight, and vacuum concentration was carried out to obtain a concentrated aqueous dispersion having a solid content of about 61.2% by weight. The results of the performance tests are shown in table 1 below.
Example 12
The procedure was followed as in example 1, except that: (1) adding a strongly basic ion exchange resin to the obtained starting aqueous dispersion of polytetrafluoroethylene particles to remove sodium perfluorohexyl acetate therein; (2) the SDS of example 1 was replaced with sodium dodecylcarboxylate anionic surfactant in an amount of 6% by weight, and concentrated in vacuo to give a concentrated aqueous dispersion having a solid content of about 62.3% by weight. The results of the performance tests are shown in table 1 below.
Comparative example 1
The procedure is as in example 1, except that a branched secondary alcohol polyoxyethylene ether (TERGITOL) is usedTMTMN-10) was used instead of SDS in example 1. The resulting concentrated aqueous dispersion had a solids content of about 59.8 wt%. The results of the performance tests are shown in table 1 below.
Comparative example 2
The procedure of example 1 was followed except that a nonionic polymeric substance dispersant represented by Polyacrylamide (PAM) was used in place of SDS in example 1. The resulting concentrated aqueous dispersion had a solids content of about 60% by weight. 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 SDS in example 1 was replaced with 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 tests are shown in table 1 below.
Comparative example 4
The procedure of example 1 was followed except that the SDS in example 1 was replaced with a nonionic surfactant represented by 5% by weight of TMN-10 and an anionic surfactant represented by 1% by weight of SDS, and the resulting concentrated aqueous dispersion had a solid content of about 60.5% by weight. The results of the performance tests are shown in table 1 below.
Figure BDA0003495716290000111
As is apparent from Table 1 above, the concentrated dispersions of comparative examples 1 to 3, in which a nonionic surfactant was added, failed to achieve satisfactory mechanical stability and storage stability; whereas the addition of a metered amount of non-fluorinated anionic surfactant to the starting aqueous fluoropolymer dispersion (containing little or no fluorinated anionic surfactant) in examples 1-4 and 6-12, without the additional addition of a non-ionic surfactant, enables concentrated aqueous fluoropolymer dispersions to be obtained which combine low viscosity, good mechanical stability and storage stability. Specifically, the concentrated aqueous dispersions of polytetrafluoroethylene obtained do not exceed 20 mPas or even 18 mPas in viscosity, have good mechanical stability and storage stability, can be stored at room temperature for up to 2 months without discoloration or sedimentation, and have a better stability effect especially when the amount of non-fluorinated anionic surfactant added is 4 to 10% by weight based on the amount of polytetrafluoroethylene particles, and even show a better stability effect than when two surfactants are added (comparative example 4, TMN-10+ SDS). On the other hand, the coatings prepared using the concentrated aqueous dispersions of polytetrafluoroethylene provided in inventive examples 1-4 and 7-12 had good gloss, transparency, and generally more excellent wear resistance and greater critical crack 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 carried out following the procedure of example 1, except that the surfactant was used and in varying amounts. The method specifically comprises the following steps:
the surfactant used in example 13 was 1 wt% Sodium Dodecylbenzenesulfonate (SDBS) +6 wt% BASF PVP K17.
The surfactant used in example 14 was 2 wt% Sodium Dodecylbenzenesulfonate (SDBS) +5 wt% BASF PVP K17.
The surfactant used in example 15 was 3 wt% sodium dodecyl carboxylate +3 wt% BASF PVP K17.
The surfactant used in example 16 was 5 wt% sodium dihexyl sulfosuccinate +1 wt% BASF PVP K17.
The surfactant used in example 17 was 1 wt% Sodium Dodecyl Sulfate (SDS) +1 wt% BASF PVP K17.
The results of the performance testing 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 Dip processability measurements
Figure BDA0003495716290000121
Figure BDA0003495716290000131
As is apparent from the above description 2, when the starting aqueous dispersion of polytetrafluoroethylene particles is concentrated, a non-fluorinated anionic surfactant and a polyvinylpyrrolidone (PVP) based polymer represented by formula (I) may be added thereto at the same time in a metered amount, and the concentrated aqueous dispersion of polytetrafluoroethylene prepared also has 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 have both good biodegradability and water solubility, and thus is 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 13 to 17 also have a large crack-free thickness (CCT), and when the glass cloth is impregnated with the concentrated aqueous dispersion of polytetrafluoroethylene prepared in examples 13 to 17, the resulting coating has good gloss, transparency and excellent abrasion resistance.
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 (12)

1. 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):
(C6H9NO)n (I)
in the formula (I), n is 9-450;
and said concentrated aqueous dispersion of fluoropolymer does not contain polyoxyethylene ether surfactant;
wherein the total content of anionic surfactant and optional nonionic surfactant is from 2 to 16 wt% based on the weight of the fluoropolymer particles.
2. A concentrated aqueous fluoropolymer dispersion according to claim 1, wherein said anionic surfactant comprises a non-fluorinated anionic surfactant; optionally, the non-fluorinated anionic surfactant is present in an amount of from 2 to 12 wt%, optionally from 4 to 10 wt%, based on the weight of the fluoropolymer particles;
further optionally, the anionic surfactant further comprises fluorinated anionic surfactant, optionally in an amount of 0-0.5 wt%, optionally 0-0.3 wt%, based on the weight of the fluoropolymer particles.
3. Concentrated aqueous fluoropolymer dispersion according to claim 2, 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;
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 fluorinated anionic surfactant is selected from one or more of the following: perfluoro-2-methyl-3-oxahexanoic acid ammonium, perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid sodium, perfluoro-hexylsodium acetate, and omega-hydrogen perfluoro-potassium heptanate.
4. A concentrated aqueous fluoropolymer dispersion according to claim 1, wherein the polyvinylpyrrolidone polymer has a molecular weight of 1000-;
optionally, the nonionic surfactant is selected from one or more of the following: k12, K15, K17, K25 and K30;
further optionally, the nonionic surfactant is present in an amount of 0 to 6 wt%, optionally 0 to 3 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. A process for producing a concentrated aqueous dispersion of a fluoropolymer according to any of claims 1 to 7 which comprises adding to a starting aqueous dispersion of particles of fluoropolymer an anionic surfactant and optionally a nonionic surfactant selected from polyvinylpyrrolidone-based polymers represented by the following formula (I) in a total amount of 2 to 16% by weight and concentrating;
(C6H9NO)n (I)
in the formula (I), n is 9-450; wherein:
said wt% being based on the weight of fluoropolymer particles in the starting aqueous dispersion of fluoropolymer particles;
the concentrated aqueous fluoropolymer dispersion is free of polyoxyethylene ether surfactants.
9. The method of claim 8, wherein the anionic surfactant comprises a non-fluorinated anionic surfactant, optionally added in an amount of 2-12 wt%, further optionally 4-10 wt%;
optionally, the initial aqueous dispersion of fluoropolymer particles contains fluorinated anionic surfactant in an amount of 0 to 0.5 wt%, optionally 0 to 0.3 wt%, based on the weight of fluoropolymer particles in the initial aqueous dispersion of fluoropolymer particles.
10. The process according to claim 8, wherein the nonionic surfactant is added in an amount of 0 to 6 wt%, optionally 0 to 3 wt%, based on the weight of the fluoropolymer particles in the starting aqueous dispersion of fluoropolymer particles.
11. The process of any one of claims 8 to 10, wherein the fluoropolymer particles have a solids content of 15 to 35 wt%, optionally 20 to 30 wt%, based on the weight of the starting aqueous dispersion of fluoropolymer particles.
12. Use of a concentrated aqueous fluoropolymer dispersion according to any one of claims 1 to 7 for impregnating porous fabrics, porous metals, as a coating or in the production of fluoropolymer anti-drip agents.
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