WO2006077737A1 - Procédé pour la préparation d'une dispersion aqueuse d'un polymère fluoré - Google Patents

Procédé pour la préparation d'une dispersion aqueuse d'un polymère fluoré Download PDF

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Publication number
WO2006077737A1
WO2006077737A1 PCT/JP2005/024115 JP2005024115W WO2006077737A1 WO 2006077737 A1 WO2006077737 A1 WO 2006077737A1 JP 2005024115 W JP2005024115 W JP 2005024115W WO 2006077737 A1 WO2006077737 A1 WO 2006077737A1
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Prior art keywords
fluorine
fluoropolymer
aqueous
surfactant
aqueous dispersion
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PCT/JP2005/024115
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English (en)
Japanese (ja)
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Nobuhiko Tsuda
Chie Sawauchi
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Daikin Industries, Ltd.
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Priority to JP2006553850A priority Critical patent/JPWO2006077737A1/ja
Publication of WO2006077737A1 publication Critical patent/WO2006077737A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/16—Purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and 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
    • C08F14/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/20—Concentration

Definitions

  • the present invention relates to a method for producing an aqueous fluoropolymer dispersion.
  • emulsion polymerization of the fluorine-containing polymer is carried out in the absence of the fluorine-containing emulsifier, so that an aqueous dispersion containing no fluorine-containing emulsifier can be obtained, but tetrafluoroethylene [TFE ]
  • TFE tetrafluoroethylene
  • Fluorine-containing polymer aqueous dispersion power A method for reducing the fluorine-containing emulsifier is, for example, adding a certain amount of water and a specific type of nonionic surfactant to polytetrafluoroethylene [PTFE] aqueous dispersion. Concentration operation was carried out, the fluorine-containing emulsifier adsorbed on the surface of PTFE particles was transferred to the aqueous phase, the aqueous phase was removed after concentration, and this concentration operation was repeated to repeat the concentration in the aqueous dispersion.
  • PTFE polytetrafluoroethylene
  • Patent Document 1 US Application Publication No. 2002Z0198334
  • Patent Document 2 International Publication No. 2003Z078479 Pamphlet
  • an object of the present invention is to provide a method for producing a fluorine-containing polymer aqueous dispersion in which the remaining amount of a fluorine-containing emulsifier and the like is reduced.
  • the present invention is a method for producing an aqueous fluoropolymer dispersion comprising producing an aqueous fluoropolymer dispersion through a concentration step, wherein the concentration step comprises a specific nonionic surfactant and Z Or an aqueous fluoropolymer dispersion in the presence of a specific surfactant
  • the specific nonionic surfactant is a nonionic surfactant having a hydrophilic group molecular weight of not more than 00 and a hydrophobic group having 10 to 20 carbon atoms.
  • the specific anion surfactant is a fluorine-free anionic surfactant having a hydrocarbon group as a hydrophobic group and having a total of 10 to 20 carbon atoms in the hydrocarbon group. This is a method for producing an aqueous fluoropolymer dispersion.
  • the fluorine-containing polymer aqueous dispersion production method of the present invention comprises producing a fluorine-containing polymer aqueous dispersion through a concentration step.
  • the concentration step is a step comprising concentrating the fluoropolymer aqueous dispersion A in the presence of a specific non-one surfactant and Z or a specific key-on surfactant.
  • the concentration in the concentration step is an operation of separating into a supernatant phase not containing a fluorine-containing polymer and a concentrated phase containing a fluorine-containing polymer (hereinafter, sometimes referred to as “separation operation”). .).
  • the fluoropolymer aqueous dispersion A is obtained by dispersing fluoropolymer particles in an aqueous medium.
  • fluorinated polymer aqueous dispersion A refers to an aqueous component before separation into a supernatant phase and a concentrated phase in the concentration step in the present invention. Means spray.
  • the “fluorinated polymer aqueous dispersion A” is the subject of the above-mentioned separation.
  • the “fluorinated polymer aqueous dispersion” described later obtained by the method for producing a fluoropolymer aqueous dispersion of the present invention is described below. Is a concept that distinguishes the two in that they have undergone the above separation.
  • the aqueous fluoropolymer dispersion A is a post-polymerization aqueous dispersion (including primary particles made of a fluoropolymer) after post-treatment such as concentration and dilution after polymerization of the fluoropolymer.
  • it may be a fluoropolymer aqueous dispersion obtained by the above-mentioned post-treatment after the polymerization, and after the separation operation described later is performed once, the separation operation described later is performed once. In the case where two or more operation cycles are performed, a separation operation may be performed.
  • the fluorine-containing polymer constituting the fluorine-containing polymer particle is a polymer having a fluorine atom bonded to a carbon atom.
  • fluorine-containing polymer examples include an elastomeric fluorine-containing polymer and a fluorine-containing polymer constituting a resin.
  • the elastomeric fluorine-containing polymer is an amorphous fluorine-containing polymer having rubber elasticity, and usually has a monomer unit of 30 to 80 mol% of the first monomer. is there.
  • the “first monomer” means that a monomer unit occupying the most molar ratio among all monomer units in the molecular structure of the elastomeric fluoropolymer. Means a monomer. Examples of the first monomer include vinylidene fluoride [VDF] and tetrafluoroethylene [TFE].
  • the “monomer unit” such as the monomer unit of the first monomer means a part derived from the corresponding monomer, which is a part of the molecular structure of the fluorine-containing polymer.
  • the TFE unit is a part of the molecular structure of the fluorine-containing polymer, is a part derived from TFE, and is represented by one (CF—CF 3) —.
  • TFE-based polymers include TFE Z propylene copolymer, TFEZ perfluorobule ether [PAVE] copolymer, V DF polymers include VDFZHFP copolymer, VDFZ black trifluoroethylene [C
  • TFE copolymer, VDFZTFE copolymer, VDFZPAVE copolymer, VDFZTFEZ HFP copolymer, VDFZTFEZCTFE copolymer, VDFZTFEZPAVE copolymer and the like.
  • Examples of the fluorine-containing polymer constituting the resin include non-melt processable fluorine-containing polymers and melt strength fluorine-containing polymers.
  • non-melting power fluorine-containing polymer examples include polytetrafluoroethylene [PTFE].
  • the PTFE is a concept including not only a TFE homopolymer but also a modified polytetrafluoroethylene [modified PTFE].
  • modified PTFE means a copolymer of TFE and a trace monomer other than TFE, which is non-melt processable.
  • the trace monomer examples include fluoroolefins such as HFP and CTFE, fluoro having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms (alkyl butyl etherol); Rosioxol; perfluoroalkylethylene; ⁇ -hydroperfluoroolefin.
  • fluoroolefins such as HFP and CTFE
  • fluoro having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms alkyl butyl etherol
  • Rosioxol perfluoroalkylethylene
  • ⁇ -hydroperfluoroolefin examples include fluoroolefins such as HFP and CTFE, fluoro having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms (alkyl butyl etherol); Rosioxol; perfluoroalkylethylene; ⁇ -hydroper
  • the content of the trace monomer units derived from the trace monomer in the total monomer units is usually in the range of 0.001 to 2 mol%.
  • the content (mol%) of the trace monomer unit in the total monomer units means the monomer from which the above “all monomer units” is derived, that is, the content. This means the mole fraction (mol%) of the trace monomer derived from the trace monomer unit in the total amount of the monomer that constitutes the fluoropolymer.
  • melt-resistant fluorine-containing polymer examples include, for example, ethylene ZTFE copolymer [ETF E], TFEZHFP copolymer [FEP], TFEZ perfluoro (alkyl butyl ether) copolymer [TFEZPAVE copolymer] ], PVDF, PVD copolymer, polyfluoride bur [p VF ] and the like.
  • TFEZPAVE copolymers include TFEZ perfluoro (methyl vinyl ether) [PMVE] copolymer [MFA], TFEZ perfluoro (ethyl vinyl ether) [PEVE ], TFEZ perfluoro (propyl butyl ether) [PPVE] copolymer, and the like. Among them, MFA and TFEZPPVE copolymer are preferred. TFEZPPVE copolymer is more preferred.
  • the fluoropolymer is more preferably PTFE, which is preferably a perfluoropolymer or a fluoropolymer that is substantially perfluoro.
  • the fluoropolymer particles constituting the fluoropolymer aqueous dispersion A preferably have an average primary particle diameter of 50 to 500 nm from the viewpoint of dispersion stability.
  • the average primary particle size is more preferably lower limit of lOOnm and more preferable upper limit force of 00 nm.
  • the above average primary particle size is measured by measuring the transmittance of 550 nm projection light per unit length of an aqueous dispersion with the fluorine-containing polymer concentration adjusted to 0.22 mass%, and the unidirectional diameter in a transmission electron micrograph.
  • the transmittance force is determined based on a calibration curve with the average particle diameter determined in the above.
  • the fluoropolymer aqueous dispersion A preferably contains 1 to 50% by mass of a fluoropolymer.
  • the fluoropolymer aqueous dispersion A contains 10 to 30% by mass of the fluoropolymer.
  • the content of the fluoropolymer may be within the above range at the start of the separation operation in the concentration step.
  • the aqueous medium constituting the fluoropolymer aqueous dispersion A is not particularly limited as long as it is a liquid containing water, and can be stored in water, for example, non-fluorine such as alcohol, ether, ketone, and paraffin wax. It also contains the organic solvent containing Z and fluorine-containing organic solvent.
  • the fluoropolymer aqueous dispersion A includes the fluoropolymer particles and the aqueous medium described above.
  • a surfactant may also be included.
  • the surfactant contained in the fluoropolymer aqueous dispersion A is not particularly limited, and for example, a fluorine-containing emulsifier, a fluorine-free emulsifier, and the like can be used.
  • the aqueous fluoropolymer dispersion A may contain one or more of the surfactants.
  • the fluorinated emulsifier is not particularly limited as long as it has an emulsifying effect due to the strength of the fluorinated compound, but those having an average molecular weight of 1000 or less are preferably easy to remove and have an average molecular weight. More preferred are those that are 500 or less.
  • fluorine-containing emulsifier those having a fluorine-containing compound having 5 to 12 carbon atoms are also preferable. When the number of carbon atoms is less than 5, generally, an emulsifying action cannot be exhibited.
  • fluorine-containing emulsifier examples include fluorine-containing carboxylic acid compounds such as fluorine-containing carboxylic acid compounds and fluorine-containing sulfonic acid compounds.
  • a compound made of a compound is more preferred, and a compound having a compound strength of a fluorine-containing carboxylic acid having 5 to 12 carbon atoms is more preferred.
  • perfluorooctanoic acid or a salt thereof is preferable.
  • perfluorooctanoic acid or a salt thereof may be abbreviated as “PFOA” hereinafter.
  • examples of the counter ion forming the salt include an alkali metal ion or NH +.
  • examples of the alkali metal ion include Na +, Ka +.
  • the concentration of the fluoroemulsifier is preferably 5 parts by mass or less with respect to 100 parts by mass of the aqueous medium. More preferably, the amount is 0.3 parts by mass or less. If it is in the said range, it may be 0.005 mass part or more with respect to 100 mass parts of aqueous media, and may be 0.01 mass part or more.
  • the concentration of the fluorinated emulsifier is determined by HPLC measurement after Soxhlet extraction is performed by adding an equal amount of methanol to the fluoropolymer aqueous dispersion to be measured. Is obtained under certain conditions.
  • non-fluorine-containing emulsifier examples include “non-ionic surfactants having HLB of 10 to 15” described later.
  • non-ionic surfactant having HLB of 10 to 15 The content of the “non-ionic surfactant having HLB of 10 to 15” will be described later.
  • the fluoropolymer aqueous dispersion A may contain an emulsifier used in the polymerization of the fluoropolymer (hereinafter, also referred to as "polymerization emulsifier" in the present specification).
  • polymerization emulsifier used in the polymerization of the fluoropolymer
  • concentration step in the present invention when the fluoropolymer aqueous dispersion A contains the above-described polymerization emulsifier, not only the specific surfactant but also the polymerization emulsifier is used as the surfactant. It may be.
  • polymerization emulsifier examples include the above-described fluorine-containing emulsifiers such as PFOA.
  • the fluoropolymer aqueous dispersion A can be prepared by polymerizing the fluoropolymer by a known method such as suspension polymerization or emulsion polymerization.
  • fluorine-containing monomer non-fluorine-containing monomer, and additive such as a polymerization initiator and a chain transfer agent in each of the above polymerizations
  • additive such as a polymerization initiator and a chain transfer agent in each of the above polymerizations
  • known ones can be used as appropriate.
  • the above-described polymerization emulsifier can be used.
  • Each of the above polymerizations is preferably carried out in the presence of a fluorine-containing emulsifier in an amount of 0.0001 to 10% by mass of the aqueous medium from the viewpoint of polymerization efficiency.
  • the amount of the fluorinated emulsifier is preferably 0.001% by mass or more of the aqueous medium, more preferably 1% by mass or more.
  • the polymerization is preferably carried out at a temperature of 10 to 120 ° C, for example, when preparing a fluorine-containing polymer having an average particle diameter in the above-mentioned range.
  • ⁇ LOMPa, preferably 1. OMPa or higher, more preferably 6.2 MPa or lower.
  • the polymerized aqueous dispersion obtained after polymerization preferably has a fluorine-containing polymer concentration of 5 to 40% by mass, more preferably 15 to 35% by mass.
  • the concentration step in the present invention is performed in the presence of a specific non-one surfactant and Z or a specific key-on surfactant.
  • the specific nonionic surfactant has a molecular weight of a hydrophilic group of 00 or less and a nonionic compound having a hydrophobic group having 10 to 20 carbon atoms.
  • the hydrophilic group preferably has a molecular weight of 150 to 350.
  • the number of carbon atoms in the hydrophobic group is within the above range, it is preferably 16 or less.
  • the hydrophilic group is a repeating unit to which alkylene oxide is added (one O—R—, where R represents an alkylene group having 2 to 4 carbon atoms). Powerful groups are preferred.
  • the repeating unit of alkylene oxide may be an oxypropylene group! /, But an oxyethylene group is preferred.
  • the hydrophilic group is preferably one having an alkylene oxide repeating unit of 7 or less, and preferably having an oxyethylene group strength of 5 or less. More preferred.
  • the hydrophilic group may be one in which a hydrocarbon group (including a polyoxyalkylene group) has a hydroxyalkyl group as a side chain! /.
  • non-ionic surfactant those having HLB of 5 or more and less than 10 are particularly preferable.
  • cloud point concentration sometimes referred to as phase separation method or heat concentration method
  • a non-ionic surfactant having an HLB power of less than 10 was not used for concentration because of its low cloud point.
  • the present invention can include concentration using a nonionic surfactant having an HLB of 5 or more and less than 10.
  • TDS-50 (Daiichi Kogyo Seiyaku Co., Ltd.) is preferably used.
  • the specific anion surfactant is a fluorine-free anionic surfactant having a hydrocarbon group as a hydrophobic group and a total carbon number of 10 to 20 carbon atoms.
  • the total number of carbon atoms of the hydrocarbon group means that when the fluorine-free ionic surfactant has only one hydrocarbon group as a hydrophobic group in one molecule, Means the number of carbon atoms of the hydrocarbon group, and when the fluorine-free cation surfactant has two or more hydrocarbon groups as hydrophobic groups in one molecule, It means the total number of carbon atoms obtained by summing up the carbon number of each hydrogen group.
  • the hydrocarbon group that the non-fluorine-containing surfactant, which is the specific surfactant, has as a hydrophobic group is preferably an alkyl group.
  • R 1 represents an alkyl group having 8 to 20 carbon atoms, preferably 10 to 20 carbon atoms, and M 1 represents H, NH, Na or K), or a salt thereof,
  • R 1 represents an alkyl group having 8 to 20 carbon atoms, preferably 10 to 20 carbon atoms, and M 1 represents H, NH, Na or K
  • M 1 represents H, NH, Na or K
  • R 2 and R 4 are the same or different and each represents an alkyl group having 4 to 12 carbon atoms
  • R 3 represents an alkylene group having 1 to 3 carbon atoms
  • M 2 represents H
  • NH Represents Na or K, provided above
  • the carbon number of each alkyl group represented by R 2 and R 4 is 10 to 20 in total.
  • the sulfodicarboxylic acid ester or its salt represented by) is preferred! /.
  • the preferred lower limit of the carbon number of the alkyl group represented by R 1 is 10
  • the preferred upper limit is 16
  • the more preferred upper limit is 14. It is.
  • Na is preferred.
  • alkyl sulfuric acid represented by the general formula (I) or the general formula (II) or a salt thereof examples include sodium dodecyl sulfate [SDS].
  • the alkyl group represented by R 2 and R 4 each has a preferred lower limit of 5 carbon atoms, a more preferred lower limit of 6, and a preferred upper limit of 10, A more preferred upper limit is 8.
  • the alkyl groups represented by R 2 and R 4 may be the same or different from each other. Yes.
  • the number of carbon atoms of the alkylene group represented by R 3 is not particularly limited as long as it is within the above range, but the preferable upper limit is 2, more preferably 1.
  • Na is preferred.
  • Examples of the sulfodicarboxylic acid ester represented by the general formula ( ⁇ ) or a salt thereof include sodium dioctylsulfosuccinate.
  • the specific non-ionic surfactant and Z or the specific cationic surfactant are present in a total of 1 to 50 parts by mass with respect to 100 parts by mass of the fluoropolymer. .
  • the preferred upper limit of the amount of the specific surfactant present relative to 100 parts by mass of the fluoropolymer is the sum of suppressing the increase in viscosity and suppressing the increase in the amount of specific surfactant transferred into the supernatant phase. It is 20 parts by mass.
  • the specific non-one surfactant and the Z or specific key-on surfactant are added after the above-mentioned fluoropolymer polymerization.
  • “added after polymerization of the fluorine-containing polymer” means adding after the completion of the polymerization reaction rather than being added as an emulsifier in the polymerization reaction for obtaining the fluorine-containing polymer.
  • the timing of “adding after the fluoropolymer polymerization” may be added at any time as long as it is after the completion of the fluoropolymer polymerization reaction and before the separation operation described later. For example, adding after performing a post-treatment such as dilution after completion of the fluoropolymer reaction can be said to be “added after polymerization of fluoropolymer”.
  • the separation operation is not particularly limited.
  • known separation methods such as cloud point concentration, phase separation concentration using centrifugation, electric concentration, ultrafiltration concentration, ion exchange concentration, etc.
  • the operation by a method is mentioned.
  • the separation operation is carried out in the presence of a specific non-ionic surfactant.
  • a specific anionic surfactant phase separation concentration using cloud point concentration, centrifugation, etc. is preferred.
  • phase separation and concentration using centrifugation is preferable, but other separation operations may be possible by using other surfactants in combination.
  • a non-surfactant having an HLB of 10 to 15 is used in combination.
  • the fluorine-containing polymer is precipitated with a nonionic surfactant having an HLB of 10 to 15, and the above-mentioned specific surfactant is a fluorine-containing polymer aqueous dispersion A containing a fluorine-containing emulsifier.
  • a fluorine-containing polymer aqueous dispersion A containing a fluorine-containing emulsifier.
  • the non-ionic surfactant that can be used for the cloud point concentration generally has an HLB of 10 to 15.
  • nonionic surfactant having an HLB of 10 to 15 examples include, for example, the following general formula (IV):
  • R 5 is a linear or branched alkyl group having 8 to 19, and preferably 10 to 16 carbon atoms;
  • a 1 is a polyoxyalkylene chain having 8 to 58 carbon atoms
  • a polyoxyalkylene alkyl ether represented by the following general formula (V): R 6 — CHO— A 2 — H (V)
  • R 6 is a linear or branched alkyl group having 4 to 12 carbon atoms, and A 2 is a polyoxyalkylene chain having 8 to 58 carbon atoms.
  • Examples thereof include those composed of oxyethylene alkyl kiln ether.
  • the nonionic surfactant having an HLB of 10 to 15 is preferably added in an amount of 3 to 50% by mass of the fluoropolymer.
  • the separation operation comprises an operation of separating the fluoropolymer aqueous dispersion A into a supernatant phase and a concentrated phase under the condition that the field coefficient exceeds 1. It may be.
  • the above “field coefficient” is the ratio [GZG] of the gravitational acceleration [G] under a certain gravitational acceleration condition to the standard heavy acceleration [G] on the ground.
  • the product of the field factor and the processing time T is 1 X 10 5 to 1 X 10 in that separation of the supernatant phase and the concentrated phase can be performed quickly and efficiently.
  • the condition that is 7 in this specification In some cases, it is called “specific gravity acceleration conditions”. ) Is preferred.
  • the separation operation When the separation operation is performed under the specific gravity acceleration condition, aggregation of the fluorine-containing polymer transferred to the concentrated phase can be suppressed, and the fluorine-containing polymer that is not substantially aggregated in the concentrated phase. Can be dispersed again in a dispersion medium such as an aqueous medium.
  • An example of the separation operation performed under the specific gravity acceleration condition includes centrifugation.
  • the concentration step includes increasing the amount of water in the fluoropolymer aqueous dispersion A by dilution or the like, if necessary, in order to improve selectivity in two-phase separation. It may be preferable to adjust the fluoropolymer concentration within the above-mentioned range.
  • the amount of water in the fluoropolymer aqueous dispersion A is relatively large, for example, even if the fluoropolymer aqueous dispersion A contains a fluorinated emulsifier, the fluorinated polymer aqueous dispersion A will contain a fluorinated polymer throughout the separation operation. Basic polymer strength Easily to separate the fluorine-containing emulsifier.
  • the fluoropolymer aqueous dispersion production method of the present invention may further include a fractionation step comprising removing the supernatant phase in addition to the concentration step.
  • the fractionation step is not particularly limited as long as the supernatant phase can be removed.
  • the fractionation step can be performed by a known fractionation operation such as filtration or decantation.
  • the fluorinated emulsifier contained in the supernatant phase can be discharged out of the system as the supernatant phase obtained by the separation operation is removed.
  • the method for producing an aqueous fluoropolymer dispersion of the present invention may comprise a concentration step performed in the presence of the above-mentioned specific surfactant and another concentration step other than the concentration step.
  • the “other concentration step” is a step different from the above-described concentration step in that the cloud point concentration method, the electric concentration method, and the like are performed in the absence of the above-mentioned specific surfactant.
  • the separation operation is performed once and then the fractionation operation is performed once. Even if the operation cycle is performed more than once.
  • the removal rate of the fluorine-containing emulsifier and the like can usually be increased by performing the operation cycle twice or more. Choose the number of operation cycles from the balance with ease of operation.
  • the method for producing an aqueous fluoropolymer dispersion of the present invention comprises the above-described concentration step and fractionation step, and further, with respect to the concentrated phase obtained by the fractionation step, the target fluoropolymer aqueous dispersion It may include a post-process for performing fine adjustment for imparting characteristics.
  • the fine adjustment is not particularly limited.
  • a stirring operation in which the concentrated phase obtained by the fractionation step is appropriately stirred to obtain a uniform aqueous dispersion, (2) the concentrated phase is a desired fluorine-containing polymer concentration (3)
  • additive agents such as surfactants and film-forming aids. It can be carried out by blending operation, etc.
  • the present invention performs the cloud point concentration in the presence of the above-mentioned specific surfactant, not only the concentration of the fluorine-containing polymer but also the removal of the fluorine-containing emulsifier can be performed efficiently. It is.
  • Conventional cloud point concentration is a force capable of precipitating a fluorine-containing polymer using a nonionic surfactant having an HLB of 10 to 15 and having a HLB of 10 to 15.
  • ON Surfactant cannot transfer fluorinated emulsifier to the supernatant phase during cloud point concentration when the substitution efficiency of the fluorinated emulsifier is extremely poor, and therefore the fluorinated emulsifier cannot be removed. It was.
  • the aqueous fluoropolymer dispersion obtained by the method of the present invention is the above-mentioned fluoropolymer monoaqueous dispersion A force, and is obtained by dispersing fluoropolymer particles in an aqueous medium. It is.
  • the fluoropolymer aqueous dispersion is added to the surfactant (preferably a surfactant other than the fluoroemulsifier) and the fluoropolymer aqueous dispersion A in addition to the fluoropolymer particles and the aqueous medium. It may contain various additives.
  • the aqueous fluoropolymer dispersion obtained by the method of the present invention preferably has a fluoropolymer concentration of S30 to 80% by mass.
  • the fluorine-containing polymer concentration has a more preferable lower limit of 50% by mass, and a more preferable lower limit of 5%. 5% by mass, a particularly preferred lower limit is 60% by mass, a more preferred upper limit is 75% by mass, and a further preferred upper limit is 70% by mass.
  • the specific surfactant is preferably 15 parts by mass or less with respect to 100 parts by mass of the fluoropolymer. If the amount exceeds 15 parts by mass with respect to 100 parts by mass of the fluoropolymer, a dispersion effect commensurate with the abundance may not be obtained, and if it is necessary to reduce the concentration to the desired specific surfactant, it is removed. Processing becomes complicated.
  • the above-mentioned specific surfactant concentration has a more preferable upper limit of 10 parts by mass with respect to 100 parts by mass of the fluorine-containing polymer, and a more preferable upper limit of 5 parts by mass, in that the effect of allowing the specific surfactant to exist is obtained. It is preferably 5 parts by mass or more.
  • the aqueous fluoropolymer dispersion obtained by the method of the present invention is preferably such that the concentration of the fluoroemulsifier is not more than lOOOppm of the fluoropolymer in terms of maintaining the properties of the fluoropolymer. 10 ppm or less is more preferred 10 ppm or less is more preferred 1 ppm or less is particularly preferred.
  • the fluoropolymer aqueous dispersion has a high fluoropolymer concentration as described above, it is excellent in handleability and can be easily processed into a fluoropolymer powder, a fluoropolymer molded body, and the like.
  • the aqueous fluoropolymer dispersion is a high-purity fluoropolymer with a low concentration of various surfactants, so that the heat-resistant properties of the fluoropolymer are not deteriorated due to the fluoroemulsion. It is possible to cover a fluoropolymer molded article having excellent physical properties such as property, chemical resistance, durability, weather resistance, surface characteristics, and mechanical characteristics.
  • the fluorine-containing polymer aqueous dispersion production method of the present invention has the above-mentioned configuration, the fluorine-containing polymer mono-aqueous dispersion containing very little contaminants such as a fluorine-containing emulsifier easily and efficiently. Can be prepared.
  • Average particle size determined by measuring the transmittance of 55 Onm projection light with respect to the unit length of the aqueous dispersion with the fluorine-containing polymer concentration adjusted to 0.22% by mass and the directional direction diameter in the transmission electron micrograph. Based on the calibration curve with the diameter, it was determined from the transmittance.
  • HPLC measurement was performed under the following conditions.
  • PFOA perfluorooctanoic acid ammonium
  • the efficiency of transferring PFOA to the aqueous phase (efficiency of removing PFOA from the fluoropolymer aqueous dispersion A) can be compared.
  • PFOA perfluorooctanoic acid ammonium
  • the PFOA concentration was 994 ppm of the fluorine-containing polymer (resin solid content). In other words, 67% of PFOA has been transferred to the water phase.
  • TFE homopolymer concentration 34% by weight, average particle size 280 ⁇ m, pH3, PFOA concentration 22.8ppm of rosin solids
  • sodium dodecyl sulfonate average molecular weight 272, reagent
  • 50 ml of the obtained TFE homopolymer aqueous dispersion A-2 The mixture was placed in a centrifuge tube having a capacity and centrifuged in the same manner as in Example 1 to separate into a supernatant phase (aqueous phase) and a concentrated phase.
  • the PFOA concentration was 550 ppm of the fluorine-containing polymer (resin solid content). In other words, 37% of PFOA has shifted to the water phase.
  • TFE homopolymer aqueous dispersion (TFE homopolymer concentration 34% by mass, average particle size 280 ⁇ m, pH 3, PFOA concentration 2900ppm with respect to the solid content of rosin), sodium dioctylsulfosuccinate (average molecular weight 443) 056mmol ZgTFE homopolymer was added and mixed, and dispersed uniformly.
  • the obtained aqueous TFE homopolymer dispersion A-3 was placed in a 50 ml centrifuge tube and centrifuged in the same manner as in Example 1 to separate the supernatant phase (aqueous phase) and the concentrated phase.
  • the PFOA concentration was 690 ppm of the fluorine-containing polymer (solid resin). In other words, 46% of PFOA has shifted to the water phase.
  • TFE homopolymer concentration 34% by weight, average particle size 280 ⁇ m, pH 3, PFOA concentration 2900ppm with respect to the solid content of resin), polyoxyethylene octylphenol ether TritonX-100 (EO number 9) 5 and an average molecular weight of 624) were added so as to be a 0.056 mmol molZgTFE homopolymer, mixed and dispersed uniformly.
  • the obtained TFE homopolymer aqueous dispersion was placed in a 50 ml centrifuge tube and subjected to centrifugal separation in the same manner as in Example 1 to separate into a supernatant phase (aqueous phase) and a concentrated phase.
  • the PFOA concentration was 355 ppm of the fluorine-containing polymer (solid resin). In other words, 24% of PFOA has shifted to the water phase.
  • TFE homopolymer aqueous dispersion TFE homopolymer concentration 34% by weight, average particle size 280 ⁇ m, pH3, PFOA concentration 2900ppm with respect to solids of resin
  • Tilphenol ether TritonX-100 EO number 9.5, average molecular weight 624 was added to be a 0.16 mm olZgTFE homopolymer, mixed and dispersed uniformly.
  • the obtained TFE homopolymer aqueous dispersion was placed in a 50 ml centrifuge tube and centrifuged in the same manner as in Example 1 to separate the supernatant phase (aqueous phase) and the concentrated phase.
  • the PFOA concentration was 680 ppm of the fluorine-containing polymer (solid resin). In other words, 46% of PFOA has shifted to the water phase.
  • TFE homopolymer concentration 34% by mass, average particle size 280 ⁇ m, pH 3, PFOA concentration 2900ppm with respect to the solid content of rosin), sodium octyl sulfonate (average molecular weight 216), 0.056mmolZgTFE The mixture was added to form a homopolymer, mixed and dispersed uniformly.
  • the obtained TFE homopolymer aqueous dispersion was placed in a 50 ml centrifuge tube, centrifuged as in Example 1, and separated into a supernatant phase (aqueous phase) and a concentrated phase.
  • the PFOA concentration was 26 ppm of the fluorine-containing polymer (solid resin). In other words, 1.7% of PFOA has shifted to the water phase.
  • the method for producing an aqueous fluoropolymer dispersion of the present invention makes it possible to prepare an aqueous fluoropolymer dispersion with very few contaminants such as a fluorine-containing emulsifier easily and efficiently.
  • the aqueous fluoropolymer dispersion is excellent as a material for a fluoropolymer molded article having excellent physical properties such as heat resistance, chemical resistance, durability, weather resistance, surface characteristics, and mechanical properties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Il est exposé un procédé pour la préparation d'une dispersion aqueuse d'un polymère fluoré ayant une quantité réduite d'un émulsifiant fluoré ou similaire restant dans la dispersion. Le procédé comprend de préparer une dispersion aqueuse d'un polymère fluoré via une étape de concentration, ladite étape de concentration comprenant de concentrer une dispersion aqueuse d'un polymère fluoré A en présence d'un tensioactif non ionique spécifique et/ou d'un tensioactif anionique spécifique. Le tensioactif non ionique spécifique a un groupe hydrophile ayant un poids moléculaire inférieur ou égal à 400 et un groupe hydrophobe ayant 10 à 20 atomes de carbone. Le tensioactif anionique spécifique est un tensioactif anionique non fluoré lequel a un groupe hydrocarboné en tant que groupe hydrophobe et a un total de 10 à 20 atomes de carbone dans le groupe hydrocarboné.
PCT/JP2005/024115 2004-12-28 2005-12-28 Procédé pour la préparation d'une dispersion aqueuse d'un polymère fluoré WO2006077737A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111413432A (zh) * 2020-04-20 2020-07-14 山东东岳高分子材料有限公司 含氟聚合物乳液产品中痕量pfoa的检测方法
WO2022191286A1 (fr) * 2021-03-10 2022-09-15 ダイキン工業株式会社 Procédé de production de dispersion aqueuse de fluoropolymère
CN115466343A (zh) * 2021-06-11 2022-12-13 中昊晨光化工研究院有限公司 一种聚醚二酸或其盐类表面活性剂及其应用

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US3037953A (en) * 1961-04-26 1962-06-05 Du Pont Concentration of aqueous colloidal dispersions of polytetrafluoroethylene
WO2003078479A1 (fr) * 2002-03-20 2003-09-25 Asahi Glass Company, Limited Composition de dispersion aqueuse de polytetrafluoroethylene et procede de production de cette derniere
WO2004050719A1 (fr) * 2002-11-29 2004-06-17 Daikin Industries, Ltd. Procede de purification d'emulsions aqueuses de fluoropolymere, emulsions purifiees et produits finis fluores
JP2005008775A (ja) * 2003-06-19 2005-01-13 Asahi Glass Co Ltd ポリテトラフルオロエチレン水性分散液組成物およびその製造方法
JP2005126715A (ja) * 2003-10-21 2005-05-19 Solvay Solexis Spa フルオロポリマー分散液の製造方法

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EP1364972B1 (fr) * 2002-05-22 2006-08-30 3M Innovative Properties Company Procédé de réduction de la teneur en surfactant fluoré dans des dispersions aqueuses de fluoropolymére
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US3037953A (en) * 1961-04-26 1962-06-05 Du Pont Concentration of aqueous colloidal dispersions of polytetrafluoroethylene
WO2003078479A1 (fr) * 2002-03-20 2003-09-25 Asahi Glass Company, Limited Composition de dispersion aqueuse de polytetrafluoroethylene et procede de production de cette derniere
WO2004050719A1 (fr) * 2002-11-29 2004-06-17 Daikin Industries, Ltd. Procede de purification d'emulsions aqueuses de fluoropolymere, emulsions purifiees et produits finis fluores
JP2005008775A (ja) * 2003-06-19 2005-01-13 Asahi Glass Co Ltd ポリテトラフルオロエチレン水性分散液組成物およびその製造方法
JP2005126715A (ja) * 2003-10-21 2005-05-19 Solvay Solexis Spa フルオロポリマー分散液の製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111413432A (zh) * 2020-04-20 2020-07-14 山东东岳高分子材料有限公司 含氟聚合物乳液产品中痕量pfoa的检测方法
WO2022191286A1 (fr) * 2021-03-10 2022-09-15 ダイキン工業株式会社 Procédé de production de dispersion aqueuse de fluoropolymère
CN115466343A (zh) * 2021-06-11 2022-12-13 中昊晨光化工研究院有限公司 一种聚醚二酸或其盐类表面活性剂及其应用
CN115466343B (zh) * 2021-06-11 2023-10-27 中昊晨光化工研究院有限公司 一种聚醚二酸或其盐类表面活性剂及其应用

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