WO2018012577A1 - Composition de polymère à teneur en fluor, matériau de revêtement à base de résine fluorée, et article revêtu - Google Patents

Composition de polymère à teneur en fluor, matériau de revêtement à base de résine fluorée, et article revêtu Download PDF

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Publication number
WO2018012577A1
WO2018012577A1 PCT/JP2017/025504 JP2017025504W WO2018012577A1 WO 2018012577 A1 WO2018012577 A1 WO 2018012577A1 JP 2017025504 W JP2017025504 W JP 2017025504W WO 2018012577 A1 WO2018012577 A1 WO 2018012577A1
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Prior art keywords
fluoropolymer
vinyl ether
solvent
fluorine
unit
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PCT/JP2017/025504
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English (en)
Japanese (ja)
Inventor
祐二 原
鷲見　直子
高生 廣野
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旭硝子株式会社
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Priority to JP2018527656A priority Critical patent/JP6927216B2/ja
Priority to CN201780043675.6A priority patent/CN109476785B/zh
Publication of WO2018012577A1 publication Critical patent/WO2018012577A1/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
    • C08F214/00—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
    • C08F214/18—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
    • C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/10—Homopolymers or copolymers of unsaturated ethers

Definitions

  • the present invention relates to a fluorine-containing polymer composition, a fluororesin coating material, and a coated article.
  • a composition containing a fluoropolymer and a solvent is suitably used as a raw material for a fluororesin coating material.
  • the fluoropolymer contained in the fluoropolymer composition usually contains fluoroolefin units and units based on other monomers.
  • Patent Document 1 discloses a fluorine-containing polymer composition containing a fluorine-containing polymer containing a fluoroolefin unit, a cyclohexyl vinyl ether unit, and a solvent.
  • storage stability means that there is no increase in the mass average molecular weight of the fluoropolymer contained in a fluoropolymer composition in a heating environment.
  • the present inventor refers to the method described in Patent Document 1 to produce a fluoropolymer composition containing a fluoroolefin unit and a cyclohexyl vinyl ether unit and a solvent, and storage stability thereof. As a result of examining the nature, it has been found that there is a case where it does not meet the current requirement level.
  • This invention is made
  • Another object of the present invention is to provide a fluororesin paint containing a fluoropolymer composition and a coated article.
  • the present inventors have found that the storage stability is affected by the presence of a predetermined impurity component in the fluoropolymer composition, and further, The present invention was completed by knowing that the desired effect could be obtained by adjusting the amount to a predetermined range. That is, the present invention is as follows.
  • a composition containing a fluoropolymer containing a fluoroolefin unit and a cyclohexyl vinyl ether unit and a solvent (excluding toluene and acetone), and the area ratio AR determined by the following area ratio calculation method Is a fluorine-containing polymer composition characterized by comprising 0.1 to 3%. Area ratio calculation method: 200 parts by mass of acetone is added to 100 parts by mass of the fluoropolymer composition to prepare a diluted solution in which the fluoropolymer composition is diluted.
  • the content of the fluoroolefin unit is 30 to 70 mol% with respect to the total units contained in the fluoropolymer, and the content of the cyclohexyl vinyl ether unit is that of the fluoropolymer.
  • Manufacturing method is described in this specification.
  • a method for producing a fluoropolymer by polymerizing a monomer mixture containing a fluoroolefin and cyclohexyl vinyl ether in the presence of a radical polymerization initiator, an alkali metal carbonate and a polymerization solvent The solvent is a mixed solvent of an alcohol having 1 to 6 carbon atoms and an organic solvent having a boiling point of 20 ° C. or higher than the alcohol, and the alkali metal carbonate precipitated by depressurizingly distilling the alcohol from the reaction mixture after polymerization. And removing the alcohol under reduced pressure by distillation under a condition that exceeds the temperature and degree of vacuum normally used for distillation of the alcohol under reduced pressure and the organic solvent is not distilled off under reduced pressure.
  • a method for producing a fluoropolymer comprising obtaining a coalescence.
  • the organic solvent having a boiling point of 110 ° C. or higher, the alcohol is ethanol, and ethanol is distilled off under reduced pressure at a temperature of 65 ° C. or higher and a reduced pressure of 45 Torr or lower.
  • a method for producing a fluoropolymer [13] The cyclohexyl vinyl ether according to [11] or [12], wherein the cyclohexyl vinyl ether contains a compound having a lower boiling point than cyclohexanol, and the area ratio of the compound is 0.15% or less.
  • a method for producing a fluoropolymer comprising obtaining a coalescence.
  • Area ratio Peak of a component-derived peak that appears on the shorter side of the retention time of cyclohexanol with respect to the sum of the peak areas of all peaks in the obtained gas chromatogram in the measurement of cyclohexyl vinyl ether by gas chromatography Percentage of total area.
  • a fluororesin paint comprising the fluoropolymer composition according to any one of [1] to [8].
  • a coated article comprising: an article; and a coating film formed on the article from the fluororesin paint according to [14].
  • the fluorine-containing polymer composition excellent in storage stability can be provided.
  • the fluororesin coating material and coating article containing a fluoropolymer composition can also be provided.
  • “Unit” is a general term for an atomic group derived directly from polymerization of a monomer and derived from one molecule of the monomer, and an atomic group obtained by chemically converting a part of the atomic group. .
  • the content (mol%) of each unit with respect to all the units contained in the polymer is determined by analyzing the polymer by nuclear magnetic resonance spectroscopy.
  • a unit based on a specific monomer is represented by adding “unit” to the monomer name.
  • “Number average molecular weight” and “mass average molecular weight” are values measured by gel permeation chromatography using polystyrene as a standard substance.
  • Nanometer average molecular weight is also referred to as “Mn”, and “mass average molecular weight” is also referred to as “Mw”.
  • the “intermediate particle size” means a particle size that is 50% by mass when the mass% is integrated from the smaller particle size.
  • the present composition As a characteristic point of the fluoropolymer composition of the present invention (hereinafter also referred to as “the present composition”), the range of the area ratio AR obtained by the area ratio calculation method described in detail later is a predetermined range. A point is mentioned.
  • the present inventors have found that a predetermined component (impurity component) contained in a trace amount in the composition adversely affects the storage stability of the composition. Specifically, first, the present composition unavoidably contains an impurity component derived from a monomer used for producing a fluoropolymer.
  • the impurity component examples include residues of cyclohexanol used when synthesizing cyclohexyl vinyl ether, residue of by-products generated when synthesizing cyclohexyl vinyl ether, and the like.
  • GC measurement gas chromatography measurement
  • components that appear on the shorter side than the retention time of cyclohexanol however, as will be described later, acetone, toluene and the like are included.
  • the present inventors have found that it affects the storage stability of the composition. Therefore, the present inventors have found that the storage stability is improved by controlling the content of the components to a predetermined amount or less.
  • the detailed reason why the component is related to the storage stability is unknown, it is presumed that the storage stability is deteriorated because the component promotes cross-linking of the fluoropolymers in the composition.
  • a method for calculating the area ratio AR (hereinafter, also referred to as “area ratio calculation method”) will be described in detail.
  • the method for preparing the sample solution used for the GC measurement is as follows. First, a fluoropolymer composition is prepared, 200 parts by mass of acetone is added to 100 parts by mass of the fluoropolymer composition, and a diluted solution is prepared by diluting the fluoropolymer composition. Next, 1% by mass of toluene is added to the diluted solution with respect to the total mass of the diluted solution to prepare a sample solution. As will be described later, in GC measurement, toluene is added to serve as a reference for extracting a peak of a trace component contained in the fluoropolymer composition.
  • GC measurement is performed using the obtained sample solution.
  • the GC measurement is performed under the following conditions using a gas chromatograph (detector: FID) manufactured by Agilent Technologies.
  • FID gas chromatograph
  • sample injection amount 1.0 ⁇ L
  • injection mode Split
  • carrier gas carrier gas
  • He inlet temperature
  • a peak having a peak area 0.5 times or less the peak area of the peak derived from toluene is extracted.
  • a peak related to a trace component contained in the composition is extracted with reference to a peak area of a peak derived from toluene added in a predetermined amount to the composition. Since acetone added to the sample solution is larger than toluene, the acetone peak appears as a larger peak than the toluene peak and is excluded during extraction.
  • the solvent in this composition has more content than toluene normally, the peak corresponding to a solvent is excluded in the case of extraction. That is, the peak related to the trace component (mainly impurity component) contained in this composition can be extracted by extraction.
  • the sum of the peak areas of the extracted peaks is defined as area A.
  • the sum of the peak areas of peaks derived from components appearing on the shorter side than the retention time of cyclohexanol is defined as area B.
  • the extracted peak does not include the peak area of the solvent-derived peak, the peak derived from acetone, and the peak derived from toluene. Therefore, when calculating the area B, the peak derived from the solvent, acetone The peak area of the peak derived from the peak and the peak area of the peak derived from toluene are not included.
  • the range of the area ratio AR in the composition is from 0.1 to 3%, preferably from 0.1 to 3.0%, preferably from 0.1 to 1.5%, from the viewpoint of storage stability of the composition. Is more preferable, and 0.1 to 1.0% is particularly preferable.
  • the area ratio AR exceeds 3%, the storage stability of the composition is inferior.
  • This composition contains a fluoropolymer containing a predetermined unit and a solvent.
  • the fluorine-containing polymer contains a fluoroolefin unit and a cyclohexyl vinyl ether unit.
  • cyclohexyl vinyl ether is also referred to as “CHVE”.
  • a fluoroolefin is an olefin in which one or more hydrogen atoms are substituted with fluorine atoms. In the fluoroolefin, one or more hydrogen atoms not substituted with fluorine atoms may be substituted with chlorine atoms.
  • a fluoroolefin may be used individually by 1 type and may use 2 or more types together.
  • the content of fluoroolefin units is preferably from 30 to 70 mol%, more preferably from 40 to 60 mol%, particularly preferably from 45 to 55 mol%, based on all units contained in the fluoropolymer.
  • the content of the fluoroolefin unit is 30 mol% or more, the weather resistance of a coating film (hereinafter, also referred to as “present coating film”) formed from the fluororesin coating material of the present invention is excellent. If content of a fluoro olefin unit is 70 mol% or less, it will be excellent by the solubility to a solvent and dispersibility of a fluoropolymer.
  • the content of the CHVE unit is preferably 10 to 50 mol%, more preferably 10 to 45 mol%, particularly preferably 15 to 40 mol%, based on all units contained in the fluoropolymer.
  • the content of the CHVE unit is 10 mol% or more, the solubility and dispersibility of the fluoropolymer in a solvent are excellent.
  • the content of the CHVE unit is 50 mol% or less, the weather resistance of the present coating film is excellent.
  • the fluoropolymer may contain units other than fluoroolefin units and CHVE units.
  • monomers other than fluoroolefin and CHVE are referred to as “other monomers”, and units based on the other monomers are referred to as “other units”.
  • Two or more kinds of other units may be contained in the fluoropolymer.
  • the other unit may be a unit having a fluorine atom or a unit having no fluorine atom.
  • the other unit may be a unit having a crosslinkable group described later.
  • the unit other than the unit having a crosslinkable group is the fourth unit.
  • the fluorinated polymer preferably contains at least one other unit.
  • the other unit is preferably a unit having no fluorine atom.
  • the unit having no fluorine atom contained in the fluoropolymer includes at least two other units of a unit having a crosslinkable group and a fourth unit (that is, a unit having no crosslinkable group). It is more preferable.
  • Other monomers that do not have a fluorine atom may be any compound that does not have a fluorine atom and that has a polymerizable group. Specific examples include vinyl ethers, allyl ethers, vinyls that do not have a fluorine atom. Examples include esters, allyl esters, ⁇ -olefins, acrylates and methacrylates.
  • the monomer having no fluorine atom is preferably a vinyl monomer having no fluorine atom from the viewpoint of reactivity with fluoroolefin, and more preferably a vinyl ether or vinyl ester having no fluorine atom. preferable.
  • One preferred embodiment of the other monomer having no fluorine atom is a monomer having a crosslinkable group (hereinafter also referred to as “monomer I”).
  • a monomer having a crosslinkable group hereinafter also referred to as “monomer I”.
  • the crosslinkable group a functional group having active hydrogen (hydroxy group, carboxy group, amino group, etc.), hydrolyzable silyl group (alkoxysilyl group, etc.) and the like are preferable, and a hydroxy group is particularly preferable.
  • Monomer I includes hydroxyalkyl vinyl ether, hydroxyalkyl vinyl ester, hydroxyalkyl allyl ether, hydroxyalkyl allyl ester, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, and the like. From the viewpoint of weather resistance, hydroxyalkyl vinyl ether is preferred. Specific examples of the monomer I include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether, 2-hydroxyethyl allyl ether, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate. Monomer I may be used individually by 1 type, and may use 2 or more types together.
  • a preferred embodiment of the monomer I includes a monomer represented by the following formula (2).
  • X 1 is a hydrogen atom or a methyl group.
  • n1 is 0 or 1.
  • Q 1 is an oxygen atom, —C (O) O— or —O (O) C—, preferably an oxygen atom.
  • R 1 is an alkylene group having 2 to 20 carbon atoms which may have a branched structure or a ring structure, and is preferably a cyclohexane-1,4-dimethylene group or an n-nonylene group.
  • Y is a crosslinkable group, preferably a hydroxy group, a carboxy group or an amino group, more preferably a hydroxy group.
  • the content of the units based on the monomer I is preferably 0 to 20 mol%, more preferably 0 to 18 mol%, based on the total units contained in the fluoropolymer, from the viewpoint of storage stability of the composition. Preferably, 0 to 15 mol% is particularly preferable.
  • Preferable embodiments of the monomer serving as the fourth unit include a monomer having no fluorine atom, a cyclic hydrocarbon group, and a crosslinkable group (hereinafter, also referred to as “monomer II”).
  • monomer II examples include vinyl ethers, allyl ethers, vinyl esters, allyl esters, olefins, acrylates, and methacrylates that do not have a fluorine atom, a cyclic hydrocarbon group, and a crosslinkable group.
  • the monomer II examples include nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, ethyl allyl ether, hexyl allyl ether, carboxylic acid (acetic acid, butyric acid, pivalin). Acid, benzoic acid, propionic acid, etc.) vinyl esters, carboxylic acids (acetic acid, butyric acid, pivalic acid, benzoic acid, propionic acid, etc.) allyl esters, ethylene, propylene, and isobutylene. Monomer II may be used individually by 1 type, and may use 2 or more types together.
  • a monomer represented by the following formula (3) is exemplified.
  • X 2 is a hydrogen atom or a methyl group.
  • n2 is 0 or 1.
  • Q 2 is an oxygen atom, —C (O) O— or —O (O) C—.
  • R 2 is an alkyl group having 2 to 20 carbon atoms which may have a branched structure.
  • the content of the unit based on the monomer II is preferably 0 to 50 mol%, more preferably 5 to 45 mol%, based on the total unit contained in the fluoropolymer, from the viewpoint of storage stability of the composition. Preferably, 15 to 40 mol% is particularly preferable.
  • the content of the fluoroolefin unit, the CHVE unit, the unit based on the monomer I, and the unit based on the monomer II is 30 to 70 mol% in this order with respect to all the units contained in the fluoropolymer. -50 mol%, 0-20 mol%, 0-50 mol% are preferred.
  • the Mn of the fluoropolymer is preferably from 3000 to 40000.
  • the Mw of the fluorinated polymer is preferably from 5,000 to 100,000, more preferably from 5,000 to 80,000.
  • the Mw change rate of the fluoropolymer before and after heating ((Mw after warming) / (Mw before warming)) From the viewpoint of the storage stability of the coalescence, 1.50 or less is preferable, 1.40 or less is more preferable, and 1.30 or less is particularly preferable.
  • the lower limit of the Mw change rate is usually 1.0.
  • Mw change rate is 1.50 or less, the viscosity of a fluoropolymer composition and a fluorine-type coating material can be maintained suitably, and it is excellent in the workability
  • This composition contains the said fluoropolymer and a solvent.
  • the solvent contained in this composition is a solvent other than the solvents (toluene and acetone) used for the measurement of the area ratio AR by the area ratio calculation method. At least a part of the solvent contained in the composition is preferably a solvent used for producing the fluoropolymer from a monomer mixture. Examples of the solvent include water and organic solvents.
  • the solvent used in the polymerization of the monomer mixture (hereinafter also referred to as “polymerization solvent”) is usually an organic solvent other than alcohol and alcohol. Is used.
  • the solvent in the present composition is preferably an organic solvent other than the alcohol used as the polymerization solvent.
  • this organic solvent is preferably an organic solvent having a boiling point higher than that of the alcohol used as a polymerization solvent.
  • the organic solvent in the present composition is preferably an organic solvent composed of at least one selected from the group consisting of an aromatic hydrocarbon solvent, a ketone solvent, an ether ester solvent, an ester solvent, and a weak solvent.
  • the organic solvent is preferably an organic solvent capable of dissolving the fluoropolymer, and the composition is preferably a solution containing the fluoropolymer and the organic solvent in which the fluoropolymer is dissolved.
  • the ether ester is a compound having both an ether bond and an ester bond in the molecule.
  • a weak solvent is a solvent classified into the 3rd type organic solvent in the Japanese Industrial Safety and Health Law.
  • the aromatic hydrocarbon solvent is preferably xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, Solvesso # 100 (registered trademark of Exxon Chemical), Solvesso # 150 (registered trademark of Exxon Chemical), xylene, ethylbenzene, etc. Is more preferable.
  • the ketone solvent is preferably acetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, diisobutyl ketone, cyclohexanone, or the like.
  • the ether ester solvent is preferably ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, methoxybutyl acetate or the like.
  • the ester solvent is preferably methyl acetate, ethyl acetate, n-propyl acetate, isobutyl acetate, t-butyl acetate or the like.
  • Weak solvents include gasoline, coal tar naphtha (including solvent naphtha), petroleum ether, petroleum naphtha, petroleum benzine, turpentine, mineral spirit (including mineral thinner, petroleum spirit, white spirit, and mineral turpentine). Mineral spirit is preferable because it is at least one selected from the group consisting of the above and the flash point is room temperature or higher.
  • the solvent may consist of only one type of solvent or a mixed solvent of two or more types.
  • the content of the solvent in the composition is preferably 30 to 70% by mass, more preferably 45 to 70% by mass, based on the total mass of the composition.
  • the present composition may contain monomer residues used for obtaining the fluoropolymer, and raw material components used for the production of the monomers. It may correspond to a trace component (impurity component).
  • the monomer residue used for obtaining the fluoropolymer include the residue of cyclohexyl vinyl ether and the residue of monomer I (4-hydroxyvinyl ether, etc.) described above.
  • the specific example of the raw material used in order to manufacture a monomer includes the cyclohexanol used in order to manufacture a cyclohexyl vinyl ether.
  • the present invention is also two production methods for producing a fluoropolymer having excellent storage stability.
  • the 1st manufacturing method among the manufacturing methods of this invention is a method of refine
  • the second production method is such that after the monomer is polymerized to produce a fluoropolymer, alcohol as a part of the polymerization solvent is distilled off from the reaction mixture. This is a method for producing a fluorine-containing polymer by distilling off under conditions more severe than those normally required for removal and simultaneously removing impurity components.
  • the fluoropolymer obtained by the method has high storage stability due to the low content of impurity components due to monomers and the like. There is little change. Furthermore, by carrying out the two production methods at the same time, the content of the impurity component can be further reduced as compared with the case where the individual production methods are carried out.
  • Any of the production methods of the present invention is a method suitable for the production of the fluoropolymer composition of the present invention.
  • the production method of the present invention is not limited to the production of the present composition, and the fluoropolymer obtained by the production method of the present invention is a fluoropolymer solution or dispersion other than the present composition. It can also be used for the manufacture of Hereinafter, the production method of the present invention will be described by taking the production of the composition as an example.
  • the first production method of the present invention is a method for producing a fluorine-containing polymer by polymerizing a monomer mixture containing a fluoroolefin and CHVE, which is obtained by purifying CHVE from cyclohexanol contained together with CHVE.
  • the area ratio of the low-boiling compound is CHVE of 0.15% or less, and the purified CHVE is used for the polymerization.
  • Area ratio Sum of the peak areas of peaks derived from components appearing on the shorter side of the retention time of cyclohexanol with respect to the sum of the peak areas of all peaks in the obtained gas chromatogram in CHVE measurement by gas chromatography Percentage.
  • the present inventors have found that in GC measurement, most of the components that appear on the shorter side than the retention time of cyclohexanol are low boiling point compounds contained in CHVE used as a raw material. In addition, it is considered that this low boiling point compound is at least a part of the impurity component that lowers the storage stability of the fluoropolymer solution. Therefore, if the amount of the low boiling point compound contained together with CHVE is reduced by distillation of CHVE, a fluoropolymer having excellent storage stability can be produced. Moreover, the area ratio AR in the fluorine-containing polymer composition of the present invention can be reduced. That is, the fluoropolymer composition of the present invention can be produced by this first production method.
  • the area ratio is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less.
  • the lower limit is not particularly limited and is 0%.
  • a method for producing a fluoropolymer by polymerizing a monomer mixture containing a fluoroolefin and CHVE known methods can be used except that purified CHVE is used.
  • the polymerization medium a solvent or a dispersion medium can be used, and it is preferable to use an organic solvent capable of dissolving the produced fluoropolymer.
  • the production method is the same as the second production method described below except for the conditions for distilling off the alcohol under reduced pressure, and the use of the second production method described later is more preferred including the conditions for destilling off the alcohol under reduced pressure.
  • the second production method of the present invention is a method for producing a fluoropolymer by polymerizing a monomer mixture containing a fluoroolefin and CHVE in the presence of a radical polymerization initiator, an alkali metal carbonate and a polymerization solvent.
  • the polymerization solvent is a mixed solvent of an alcohol having 1 to 6 carbon atoms and an organic solvent having a boiling point higher than that of the alcohol by 20 ° C. or higher (hereinafter also referred to as “high boiling organic solvent”).
  • the alcohol is distilled off under reduced pressure to remove the precipitated alkali metal carbonate, the vacuum distillation of the alcohol exceeds the temperature and degree of pressure normally used for vacuum distillation of the alcohol, and the organic solvent
  • This is a production method characterized in that the fluoropolymer dissolved in the organic solvent is obtained under the condition that the solvent is not distilled off under reduced pressure.
  • stricter removal conditions than normal alcohol removal conditions are set so that when the alcohol having 1 to 6 carbon atoms is removed, the low-boiling compounds are also removed. For example, when the alcohol is distilled off under reduced pressure, the low-boiling compounds are removed together by distilling off under reduced pressure or higher temperature.
  • the difference between the boiling point of the alcohol used and the high boiling point organic solvent is larger so that even the high boiling point organic solvent is not removed during the alcohol removal, and the boiling point of the high boiling point organic solvent is that of the alcohol used together. It is preferably 30 ° C. or higher than the boiling point, more preferably 50 ° C. or higher.
  • the alcohol having 1 to 6 carbon atoms is preferably ethanol, and more specifically, when ethanol is used, the temperature is 65 ° C. or higher (the upper limit is preferably 85 ° C.) and 45 Torr or lower (preferably 30 Torr or lower). The lower limit is preferably 5 Torr), and it is preferable to perform distillation under reduced pressure.
  • the area ratio AR in the polymer composition of the present invention can be reduced by the second production method. That is, the fluoropolymer composition of the present invention can be produced by this second production method.
  • the second production method of the present invention preferably includes the following steps 1 to 3 from the viewpoint of productivity.
  • Step 1 polymerization step: polymerization of a monomer mixture containing a fluoroolefin and CHVE, which is a mixed solvent of a radical polymerization initiator, an alkali metal carbonate, and an alcohol having 1 to 6 carbon atoms and a high boiling organic solvent.
  • Step 2 preparation step: a step of removing the alcohol from the fluoropolymer solution to reduce the content of the alcohol and precipitating the alkali metal carbonate.
  • Step 3 removable step: A step of filtering the fluoropolymer solution obtained in the above step 2 to remove the precipitated alkali metal carbonate and obtaining a fluoropolymer dissolved in a high-boiling organic solvent.
  • the monomer mixture in Step 1 may contain other monomers (monomer I, monomer II, etc.) as necessary in addition to fluoroolefin and CHVE.
  • a specific example of the alkali metal carbonate used in Step 1 is potassium carbonate.
  • the mass ratio of the alkali metal carbonate to the total monomer in the monomer mixture is 0.005 / 1 to 0.00. 013/1 is preferable, and 0.008 / 1 to 0.012 / 1 is more preferable.
  • the polymerization solvent in Step 1 only needs to contain an alcohol having 1 to 6 carbon atoms and a high-boiling organic solvent. Besides these solvents, conventionally known solvents for polymerization can be used.
  • the solvent contained in the present composition is the same as the high-boiling organic solvent in the polymerization solvent, and is obtained in Step 3. It is preferable to use the fluoropolymer solution as it is as the present composition.
  • the alcohol having 1 to 6 carbon atoms include methanol, ethanol, n-propanol, i-propanol, tert-butanol, pentanol, and hexanol. Ethanol is preferable from the viewpoint of solubility of potassium carbonate.
  • the high boiling point organic solvent in the polymerization solvent include aromatic hydrocarbon solvents, alcohol solvents other than alcohols having 1 to 6 carbon atoms, ketone solvents, ether ester solvents, ester solvents, weak solvents, and the like. An organic solvent having a boiling point of 20 ° C. or more higher than that of alcohol is used.
  • the aromatic hydrocarbon solvent, the ketone solvent, the ether ester solvent, the ester solvent, and the weak solvent are organic solvents that satisfy the high boiling point condition among the solvents preferably contained in the present composition.
  • the alcohol solvent other than the alcohol having 1 to 6 carbon atoms include octyl alcohol and dodecyl alcohol.
  • the high-boiling organic solvent is more preferably an aromatic hydrocarbon solvent, an ether ester solvent, or an alcohol solvent other than an alcohol having 1 to 6 carbon atoms, particularly preferably an aromatic hydrocarbon solvent.
  • the high boiling point organic solvent is preferably an organic solvent having a boiling point of 110 ° C. or higher.
  • toluene (bp: 110 ° C.), ethylbenzene
  • aromatic hydrocarbon solvents such as (bp: 136 ° C.) and xylene (bp: 138 to 144 ° C.).
  • the content of the alcohol having 1 to 6 carbon atoms is preferably 10 to 95% by mass and more preferably 20 to 90% by mass with respect to the total mass of the polymerization solvent.
  • the monomer mixture is preferably copolymerized by solution polymerization in the presence of at least part of potassium carbonate in the presence of a radical polymerization initiator, an alkali metal carbonate, and the polymerization solvent.
  • a radical polymerization initiator an alkali metal carbonate
  • the “state in which at least a part of the alkali metal carbonate is dissolved” means that a part of the alkali metal carbonate is dissolved in the solvent, but at least a part of the alkali metal carbonate is not dissolved but dispersed (floating or precipitated). It is a state that may be included.
  • radical polymerization initiator examples include azo initiators (2,2′-azobisisobutyronitrile, 2,2′-azobiscyclohexane carbonate nitrile, 2,2′-azobis (2,4-dimethyl). Valeronitrile), 2,2′-azobis (2-methylbutyronitrile), etc., ketone peroxide (cyclohexanone peroxide, etc.), hydroperoxide (tert-butyl hydroperoxide, etc.), diacyl peroxide (benzoyl peroxide) Oxide), dialkyl peroxide (di-tert-butyl peroxide, etc.), peroxyketal (2,2-di- (tert-butylperoxy) butane, etc.), alkyl perester (tert-butyl peroxypivalate) (PBPV) and the like) Oxide initiator (diisopropyl peroxydicarbonate, etc.).
  • azo initiators 2,2′-azobisis
  • a conventionally known chain transfer agent may be added as necessary.
  • the polymerization reaction is preferably carried out under conditions of a polymerization temperature of 65 ° C. ⁇ 10 ° C. and a polymerization time of 6 hours to 36 hours.
  • the polymerization temperature may be appropriately set according to the decomposition start temperature and half-life of the initiator used.
  • the polymerization reaction may be stopped by a polymerization inhibitor such as hydroquinone monomethyl ether after cooling.
  • step 2 the alcohol solvent having 1 to 6 carbon atoms is removed from the solution of the fluoropolymer obtained in step 1, and is preferably reduced to 0 to 0.03% by mass with respect to the polymerization solvent.
  • carbonate is precipitated in the solution.
  • the method for removing the alcohol having 1 to 6 carbon atoms include a method of concentrating under reduced pressure heating with a reduced pressure distillation apparatus.
  • preliminary filtration before removing the alcohol having 1 to 6 carbon atoms.
  • the preliminary filtration is performed for the purpose of roughly separating the alkali metal carbonate or the modified product thereof dispersed as a solid (including suspended or precipitated) in the fluoropolymer solution.
  • these should just be removed in the following removal process.
  • step 3 the fluoropolymer solution obtained by removing the alcohol solvent having 1 to 6 carbon atoms obtained in the precipitation step was filtered to remove the precipitated alkali metal carbonate and dissolved in an organic solvent. This is a step of obtaining a fluoropolymer.
  • Examples of the filtration method include filtration using diatomaceous earth.
  • Diatomaceous earth includes diatomaceous earth having an intermediate particle size of 25 to 40 ⁇ m, and the amount used is preferably 0.05 to 0.10 g / cm 2 with respect to the filtration area.
  • the filtration is performed using filter paper No. It is preferable to transfer the solution to a pressure filter equipped with 63, filter under a pressure of 0.01 to 0.5 MPa, and perform circulation filtration until the appearance of the filtrate is visually free of haze.
  • the composition can be suitably used for a fluororesin paint (clear paint or the like).
  • the fluororesin paint of the present invention can be prepared by further adding a paint compounding component such as a resin other than a curing agent and a fluoropolymer to the present composition.
  • the fluororesin paint may be a one-pack type paint or a two-pack type paint. In the case of the two-component type, the curing agent is preferably mixed immediately before use.
  • the curing agent is preferably a curing agent capable of crosslinking with the crosslinkable group of the monomer I.
  • the curing agent is preferably a curing agent for coatings such as a normal temperature curing isocyanate curing agent, a thermosetting block isocyanate curing agent, or a melamine curing agent.
  • the content of the curing agent in the fluororesin coating is preferably 1 to 100 parts by mass and more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the fluoropolymer.
  • a known resin blended in the fluororesin coating can be used as appropriate.
  • CAB cellulose acetate butyrate
  • NC nitrocellulose
  • a coating resin such as a polymer made of acrylic acid or an ester thereof, or polyester may be blended.
  • silane coupling agents such as silane coupling agents, ultraviolet absorbers, curing accelerators, light stabilizers, colorants, matting agents, and the like can be added as necessary.
  • the coated article of the present invention has a coating film formed on the surface of the article by the fluororesin paint of the present invention.
  • articles to be painted include transportation equipment (automobiles, trains, aircraft, etc.), civil engineering members (bridge members, steel towers, etc.), industrial equipment (waterproof material sheets, tanks, pipes, etc.), building materials (building exteriors) , Doors, window gate members, monuments, poles, etc.), road members (road median strips, guardrails, sound barriers, etc.), communication equipment, electrical and electronic parts, and surface sheets and back sheets for solar cell modules.
  • the thickness of the coating film is preferably 10 to 200 ⁇ m, and more preferably 10 to 100 ⁇ m.
  • the fluororesin paint may be applied directly to the surface of the article, or may be applied after performing a known surface treatment (such as a base treatment) on the surface of the article.
  • a known surface treatment such as a base treatment
  • Specific examples of the fluororesin coating application method include spray coating, air spray coating, brush coating, dipping method, roll coater, and flow coater.
  • the drying temperature after coating is preferably about 15 ° C to 300 ° C.
  • GC measurement was performed under the above-described conditions using 6850 Series II (detector: FID) manufactured by Agilent Technologies. From the obtained chromatogram, the area ratio AR was determined by the method described above. In addition, the retention time of cyclohexanol was confirmed by measuring cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade).
  • CHVE 1 to 3 described in Table 1 below were used.
  • area ratio (%) of compounds having a lower boiling point than cyclohexanol” column in Table 1 is the peak of all peaks in the gas chromatogram obtained by performing the above-described GC measurement using each CHVE. It represents the ratio (area ratio) of the sum of the peak areas of the peaks derived from the components appearing on the shorter time side than the retention time of cyclohexanol with respect to the sum of the areas. The lower the area ratio, the smaller the proportion of components having a lower boiling point than cyclohexanol.
  • CHVE3 is a commercial product
  • CHVE1 is CHVE obtained by distillation of CHVE3 (distillation yield 70%)
  • CHVE2 is CHVE obtained by distillation of CHVE3 (distillation yield 90%).
  • Example 1 A stainless steel pressure-resistant reactor with an agitator (internal volume 2500 mL) was charged with xylene (587 g), ethanol (168 g), ethyl vinyl ether (EVE) (206 g), 4-hydroxyvinyl ether (HBVE) (129 g), cyclohexyl vinyl ether 1 (CHVE1). ) (208 g), potassium carbonate (11 g), and tert-butyl peroxypivalate (PBPV) (3.5 g) were charged, and dissolved oxygen in the liquid was removed by pressurizing and purging with nitrogen and degassing.
  • xylene 587 g
  • ethanol 168 g
  • EVE ethyl vinyl ether
  • HBVE 4-hydroxyvinyl ether
  • CHVE1 cyclohexyl vinyl ether 1
  • PBPV tert-butyl peroxypivalate
  • chlorotrifluoroethylene (CTFE) (660 g) was introduced, the temperature was gradually raised, and the reaction was continued while maintaining the temperature at 65 ° C. After 12 hours, the reactor was cooled with water to stop the reaction. After cooling the reaction solution to room temperature, the unreacted monomer was purged and the reactor was opened. The obtained reaction solution was added to filter paper No. 1 for viscosity adjustment. The solution was transferred to a pressure filter equipped with 63, and potassium carbonate was filtered off at a pressure of 0.05 MPa, and then 0.1 g of hydroquinone monomethyl ether (HQMME) was added. Subsequently, ethanol in the reaction solution was distilled off under reduced pressure heating at 65 ° C.
  • CFE chlorotrifluoroethylene
  • Example 2 A fluoropolymer composition 2 was obtained according to the same procedure as in Example 1 except that CHVE2 was used instead of CHVE1. Subsequently, as a result of analyzing the fluoropolymer composition 2 by GC measurement mentioned above, it was confirmed that the area ratio AR was 3.0%.
  • Example 3 Into a stainless steel pressure resistant reactor (internal volume 2500 mL) with a stirrer, xylene (587 g), ethanol (168 g), EVE (206 g), HBVE (129 g), CHVE2 (208 g), potassium carbonate (11 g) and PBPV (3. 5 g) was charged, and dissolved oxygen in the liquid was removed by pressurization / purging with nitrogen and deaeration. Next, CTFE (660 g) was introduced, the temperature was gradually raised, and the reaction was continued while maintaining the temperature at 65 ° C. After 12 hours, the reactor was cooled with water to stop the reaction. After cooling the reaction solution to room temperature, the unreacted monomer was purged and the reactor was opened.
  • reaction solution was added to filter paper No. After transferring to a pressure filter equipped with 63, potassium carbonate was filtered off at a pressure of 0.05 MPa, and 0.1 g of HQMME was added. Subsequently, ethanol in the reaction solution was distilled off under reduced pressure heating at 65 ° C. and 15 Torr using a vacuum distillation apparatus. Next, 0.06 g / cm 2 of diatomaceous earth (intermediate particle size: 30.1 ⁇ m) with respect to the filtration area was added to the reaction solution and mixed and stirred. The solution was transferred to a pressure filter equipped with 63, filtered twice at a pressure of 0.02 MPa, and diatomaceous earth was separated by filtration to obtain a fluoropolymer composition P3.
  • the concentration was adjusted so that the mass concentration of the fluoropolymer in the fluoropolymer composition P3 was 60% by mass to obtain the fluoropolymer composition 3.
  • the area ratio AR was 1.3%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention fournit une composition de polymère à teneur en fluor qui se révèle excellente en termes de stabilité au stockage. Cette composition de polymère à teneur en fluor contient un polymère à teneur en fluor qui contient à son tour une unité de fluorooléfine et une unité d'éther vinylique de cyclohexyle, et un solvant, et présente une proportion de surface (AR) obtenue par un procédé de calcul de proportion de surface qui est comprise entre 0,1 et 3%.
PCT/JP2017/025504 2016-07-14 2017-07-13 Composition de polymère à teneur en fluor, matériau de revêtement à base de résine fluorée, et article revêtu WO2018012577A1 (fr)

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CN201780043675.6A CN109476785B (zh) 2016-07-14 2017-07-13 含氟聚合物组合物、氟树脂涂料、涂装物品

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JPH10109952A (ja) * 1996-10-02 1998-04-28 Maruzen Petrochem Co Ltd シクロヘキシルビニルエーテルの分離方法
JPH10158208A (ja) * 1996-11-25 1998-06-16 Maruzen Petrochem Co Ltd シクロヘキシルビニルエーテルの分離回収方法
WO2010095722A1 (fr) * 2009-02-23 2010-08-26 旭硝子株式会社 Procédé de production de solution de copolymère de fluorooléfine et procédé de production de composition de peinture
JP2010229049A (ja) * 2009-03-26 2010-10-14 Maruzen Petrochem Co Ltd 高純度ビニルエーテルの製造法
WO2012165443A1 (fr) * 2011-05-30 2012-12-06 旭硝子株式会社 Composition de copolymère à teneur en fluor et son procédé de fabrication
WO2014054545A1 (fr) * 2012-10-03 2014-04-10 旭硝子株式会社 Procédé de fabrication d'une solution de copolymère contenant du fluor et composition de revêtement
WO2015056751A1 (fr) * 2013-10-17 2015-04-23 旭硝子株式会社 Composition de type solution contenant un copolymère d'oléfine fluorée, son procédé de production, et composition de matériau de revêtement
WO2017122701A1 (fr) * 2016-01-14 2017-07-20 旭硝子株式会社 Solution contenant une résine fluorée, procédé de production d'une solution contenant une résine fluorée, composition de revêtement et objet revêtu

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JPS6021686B2 (ja) * 1980-08-08 1985-05-29 旭硝子株式会社 常温硬化可能な含フツ素共重合体
DE60235213D1 (de) * 2001-09-27 2010-03-11 Asahi Glass Co Ltd Zusammensetzung für Fluorharz-Pulverlack
CN1294217C (zh) * 2003-12-15 2007-01-10 上海三爱富新材料股份有限公司 可溶型含氟涂料树脂及其制备方法
TW201527386A (zh) * 2013-11-13 2015-07-16 Asahi Glass Co Ltd 含有氟烯烴共聚物之溶液組成物、其製造方法及塗料組成物

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JPS61174210A (ja) * 1985-01-29 1986-08-05 Asahi Glass Co Ltd 含フツ素共重合体の製造方法
JPH10109952A (ja) * 1996-10-02 1998-04-28 Maruzen Petrochem Co Ltd シクロヘキシルビニルエーテルの分離方法
JPH10158208A (ja) * 1996-11-25 1998-06-16 Maruzen Petrochem Co Ltd シクロヘキシルビニルエーテルの分離回収方法
WO2010095722A1 (fr) * 2009-02-23 2010-08-26 旭硝子株式会社 Procédé de production de solution de copolymère de fluorooléfine et procédé de production de composition de peinture
JP2010229049A (ja) * 2009-03-26 2010-10-14 Maruzen Petrochem Co Ltd 高純度ビニルエーテルの製造法
WO2012165443A1 (fr) * 2011-05-30 2012-12-06 旭硝子株式会社 Composition de copolymère à teneur en fluor et son procédé de fabrication
WO2014054545A1 (fr) * 2012-10-03 2014-04-10 旭硝子株式会社 Procédé de fabrication d'une solution de copolymère contenant du fluor et composition de revêtement
WO2015056751A1 (fr) * 2013-10-17 2015-04-23 旭硝子株式会社 Composition de type solution contenant un copolymère d'oléfine fluorée, son procédé de production, et composition de matériau de revêtement
WO2017122701A1 (fr) * 2016-01-14 2017-07-20 旭硝子株式会社 Solution contenant une résine fluorée, procédé de production d'une solution contenant une résine fluorée, composition de revêtement et objet revêtu

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