WO2013175962A1 - Polymère contenant du fluor et son procédé de fabrication - Google Patents

Polymère contenant du fluor et son procédé de fabrication Download PDF

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Publication number
WO2013175962A1
WO2013175962A1 PCT/JP2013/062941 JP2013062941W WO2013175962A1 WO 2013175962 A1 WO2013175962 A1 WO 2013175962A1 JP 2013062941 W JP2013062941 W JP 2013062941W WO 2013175962 A1 WO2013175962 A1 WO 2013175962A1
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Prior art keywords
fluorine
general formula
monomer
group
integer
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PCT/JP2013/062941
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English (en)
Japanese (ja)
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田中　義人
剣吾 伊藤
三木　淳
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ダイキン工業株式会社
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Publication of WO2013175962A1 publication Critical patent/WO2013175962A1/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
    • C08F214/26—Tetrafluoroethene
    • C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
    • 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
    • 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
    • C08F214/26—Tetrafluoroethene
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • 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
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers

Definitions

  • the present invention relates to a fluoropolymer and a method for producing the same.
  • Polyvinyl alcohol and ethylene-vinyl alcohol copolymer are hydrophilic, have a property of being difficult to permeate gases such as oxygen and nitrogen, and excellent in fuel barrier properties.
  • the copolymer film having excellent water resistance is composed of a copolymer of tetrafluoroethylene and vinyl acetate or a copolymer obtained by saponifying at least a part of an acetate group contained in the copolymer.
  • a fluorine-containing copolymer film having a tetrafluoroethylene content of 1 to 70 mol% contained in the copolymer has been proposed.
  • Patent Document 2 it is pointed out that the copolymer proposed in Patent Document 1 is inferior in productivity and heat resistance, and the quality is deteriorated due to coloring.
  • the protecting group is substituted with a hydrogen atom by a deprotection reaction to form a hydroxyl group, thereby producing a fluorine-containing olefin /
  • a method for producing a vinyl alcohol copolymer has been proposed.
  • Patent Document 3 proposes to introduce a hydrolyzable metal alkoxide into a fluorine-containing olefin / vinyl ester copolymer by a transesterification reaction.
  • the fluorine-containing olefin / vinyl alcohol copolymer disclosed in Patent Document 2 does not have a curing site suitable for the curing reaction and cannot be easily cured. Moreover, the copolymer which introduce
  • the present invention provides a novel fluoropolymer which can be easily cured while having solvent resistance, gas barrier properties, transparency and heat resistance.
  • the present invention is also capable of easily producing a polymer that can be easily cured while having solvent resistance, gas barrier properties, transparency and heat resistance.
  • a novel method for producing a fluoropolymer the amount of which can be easily adjusted.
  • the present invention includes a polymer unit based on a fluorine-containing monomer, a polymer unit based on vinyl alcohol as an arbitrary polymer unit, and a general formula (1): —CH 2 —CH (—O— (L) 1 —R b ) — (1) (Wherein R b is an organic group having at least one hydrolyzable metal alkoxide, L is a divalent organic group, l is 0 or 1). This is a fluorine-containing polymer.
  • R b represents the following general formula (2): -R 11 a (R 12 O) b M ⁇ O-MR 11 g (OR 12) h ⁇ f -R 11 d (OR 12) e (2)
  • M is a metal
  • R 11 is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms
  • R 12 is the same or different and is an alkyl group, an alkoxyalkyl group, or an aryl group.
  • A is an integer of 1 to 3
  • b is an integer of 0 to 4
  • a + b 2 to 5
  • d is 0 or 1
  • e is 0 or 1
  • d + e 1
  • f is an integer of 0 to 10
  • g is an integer of 0 to 3
  • h is an integer of 0 to 3
  • g + h 1 to 3
  • at least 1 of b, e, and h Is preferably a group represented by 1).
  • L is preferably a single bond.
  • the molar ratio of the polymer unit based on the fluorine-containing monomer, the polymer unit based on vinyl alcohol and the polymer unit represented by the general formula (1) is (30 to 70) / (0 to 69) / (1 to 70). Preferably there is.
  • the present invention is a production method for producing the above-mentioned fluorine-containing polymer, wherein a fluorine-containing monomer / vinyl ester copolymer is obtained by copolymerizing a fluorine-containing monomer and a vinyl ester monomer.
  • the present invention is a production method for producing the above-mentioned fluorine-containing polymer, wherein a fluorine-containing monomer / vinyl ester copolymer is obtained by copolymerizing a fluorine-containing monomer and a vinyl ester monomer.
  • a step of obtaining a step of obtaining a fluorine-containing monomer / vinyl alcohol copolymer by hydrolyzing the fluorine-containing monomer / vinyl ester copolymer, the fluorine-containing monomer / vinyl alcohol copolymer and the like
  • Formula (6) X b -R c (6) (Wherein, X b is Cl, Br or I, R c is an organic radical.
  • olefin-containing fluoropolymer by reacting a compound represented by step
  • hydrolyzable metal alkoxide was contained by further alkoxylating reaction with aliphatic alcohol. It is also a manufacturing method characterized by including the process of obtaining a fluoropolymer.
  • the present invention is a production method for producing the above-mentioned fluoropolymer, comprising a fluoromonomer and a general formula (8):
  • CH 2 CH-OR (8)
  • R is a protecting group that can be converted to vinyl alcohol by a deprotection reaction
  • olefin-containing fluoropolymer by reacting a compound represented by step
  • hydrolyzable metal alkoxide was contained by further alkoxylating reaction with aliphatic alcohol. It is also a manufacturing method characterized by including the process of obtaining a fluoropolymer.
  • the compound represented by the general formula (4) is represented by the following general formula (5):
  • M is a metal
  • R 11 is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms
  • R 12 is the same or different and is an alkyl group, an alkoxyalkyl group, or an aryl group.
  • A is an integer of 1 to 3
  • b is an integer of 0 to 4
  • a + b 2 to 5
  • d is 0 or 1
  • e is 0 or 1
  • d + e 1
  • f is an integer of 0 to 10
  • g is an integer of 0 to 3
  • h is an integer of 0 to 3
  • g + h 1 to 3
  • at least 1 of b, e, and h Is preferably 1 or more.).
  • the compound represented by the general formula (6) is represented by the following general formula (7): X b —R 13 — (R 14 —CH ⁇ CH 2 ) c (7) (Wherein X b is Cl, Br or I, R 13 is the same or different and is a (c + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and R 14 is the same or different; —O—, —O—C ( ⁇ O) —, a single bond, and c is an integer of 1 to 10) are preferred.
  • This invention is also a curable composition containing the above-mentioned fluoropolymer.
  • the curable composition of the present invention is preferably a coating agent or an antifouling agent.
  • the present invention is also a cured product obtained by curing the above-described curable composition.
  • the fluoropolymer of the present invention can be easily cured.
  • the cured product obtained by curing the fluoropolymer of the present invention has solvent resistance, gas barrier properties, transparency and heat resistance.
  • the production method of the present invention has a solvent resistance, a gas barrier property, transparency and heat resistance, and can easily produce a fluorine-containing polymer that can be easily cured, and the resulting copolymer has It is also easy to adjust the amount of the cured part.
  • the fluorine-containing polymer of the present invention includes a polymer unit based on a fluorine-containing monomer, a polymer unit based on vinyl alcohol as an arbitrary polymer unit, and a polymer unit represented by the general formula (1). To do.
  • the fluorine-containing monomer is a monomer having a fluorine atom.
  • fluorine-containing monomer examples include tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropylene [HFP], hexafluoroisobutene, and CH 2.
  • PAVE perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], perfluoro (butyl vinyl ether), among others, PMVE. PEVE or PPVE is more preferable.
  • alkyl perfluorovinyl ether derivative those in which Rf 2 is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF 2 ⁇ CF—OCH 2 —CF 2 CF 3 is more preferable.
  • the fluorine-containing monomer is preferably at least one selected from the group consisting of TFE, CTFE and HFP, and more preferably TFE.
  • the fluoropolymer of the present invention has the following general formula (1): —CH 2 —CH (—O— (L) 1 —R b ) — (1) (Wherein R b is an organic group having at least one hydrolyzable metal alkoxide, L is a divalent organic group, and l is 0 or 1).
  • the fluoropolymer of the present invention is a polymer having a hydrolyzable metal alkoxide as a curing site, and the number of curing sites can be easily adjusted when producing the fluoropolymer.
  • Rb may have one hydrolyzable metal alkoxide, and may have two or more.
  • the polymerization unit represented by the general formula (1) has the general formula: CH 2 ⁇ CH—O— (L) 1 —R b (In the formula, R b is an organic group having at least one hydrolyzable metal alkoxide, L is a divalent organic group, and l is 0 or 1. Is a polymerized unit based on the monomer represented by
  • R b in the general formula (1) is bonded to the main chain of the fluoropolymer via a urethane bond, and s is 1 and p is In the case of 0, R b is bonded to the main chain of the fluoropolymer via an ester bond.
  • L represents a single bond and R b is bonded via an ether bond. Thus, it is bonded to the main chain of the fluoropolymer.
  • R b represents the following general formula (2): -R 11 a (R 12 O) b M ⁇ O-MR 11 g (OR 12) h ⁇ f -R 11 d (OR 12) e (2)
  • M is a metal
  • R 11 is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms
  • R 12 is the same or different and is an alkyl group, an alkoxyalkyl group, or an aryl group.
  • A is an integer of 1 to 3
  • b is an integer of 0 to 4
  • a + b 2 to 5
  • d is 0 or 1
  • e is 0 or 1
  • d + e 1
  • f is an integer of 0 to 10
  • g is an integer of 0 to 3
  • h is an integer of 0 to 3
  • g + h 1 to 3
  • at least 1 of b, e, and h Is preferably a group represented by 1).
  • examples of the metal represented by M include silicon (Si), titanium (Ti), aluminum (Al), zirconium (Zr), tin (Sn), iron (Fe), sodium ( Na), magnesium (Mg), phosphorus (P), sulfur (S), potassium (K), calcium (Ca), scandium (Sc), vanadium (V), chromium (Cr), manganese (Mn), cobalt ( Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), rubidium (Rb), strontium (Sr), yttrium ( Y), niobium (Nb), molybdenum (Mo), cadmium (Cd), indium (In), antimony (Sb), tellurium (Te), cesium (Cs), barium (Ba), lanthanum (La), hafnium (Hf), tantalum (Ta), tungsten
  • M is preferably silicon (Si), titanium (Ti), aluminum (Al), zirconium (Zr), tin (Sn), or iron (Fe).
  • the “hydrocarbon group having 1 to 20 carbon atoms” in R 11 is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms.
  • the alkylene group may be linear or branched.
  • examples of the “alkyl group” for R 12 include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms.
  • examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, and a hexyl group. Cyclohexyl group, octyl group, cyclodecyl group and the like.
  • Examples of the “alkoxyalkyl group” for R 12 include an alkoxyalkyl group having 2 to 12 carbon atoms.
  • Examples of the “aryl group” for R 12 include an aryl group having 6 to 12 carbon atoms.
  • the number of alkoxy groups contained is preferably 1 to 12, and more preferably 1 to 4.
  • f is preferably an integer of 0 to 4.
  • j is preferably 3 or 4, and k is preferably 1.
  • Preferred examples of the “organic group having at least one hydrolyzable metal alkoxide” for R b include, for example, the following general formula (2-2): — (C n H 2n ) —Si— (OR 12 ) 3 (2-2) (Wherein n is an integer of 1 to 10, and R 12 is the same as in general formula (2)).
  • organic group represented by R b include, for example, the following general formula:
  • the fluorine-containing polymer of the present invention is a molar ratio of a polymer unit based on a fluorine-containing monomer, a polymer unit based on vinyl alcohol, and a polymer unit represented by the general formula (1) (based on a fluorine-containing monomer). It is preferable that (polymerized unit) / (polymerized unit based on vinyl alcohol) / (polymerized unit represented by general formula (1)) is (30 to 70) / (0 to 69) / (1 to 70). More preferably, it is (30 to 70) / (1 to 69) / (1 to 69).
  • the fluoropolymer of the present invention may contain a polymer unit based on a vinyl ester monomer or a vinyl ether monomer in addition to the above three polymer units.
  • the fluoropolymer of the present invention includes a polymer unit based on a fluoromonomer, a polymer unit based on vinyl alcohol, a polymer unit represented by the general formula (1), and a vinyl ester monomer or vinyl ether monomer.
  • the polymerization units based on vinyl ether monomers) are preferably (30 to 70) / (0 to 69) / (1 to 70) / (0 to 69), (30 to 70) / (0 to 65).
  • / (5-70) / (0-65) is more preferable. More preferably, it is (30 to 70) / (1 to 65) / (5 to 69) / (0 to 65). Particularly preferred is (30 to 70) / (1 to 65) / (5 to 68) / (1 to 65).
  • vinyl ester monomer examples include vinyl acetate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and the like.
  • vinyl ester monomer vinyl acetate and vinyl stearate are preferable. More preferred is vinyl acetate.
  • vinyl ether monomer examples include t-butyl vinyl ether, 1,1-dimethylpropyl vinyl ether, methoxymethyl vinyl ether, tetrahydrofuryl vinyl ether, tetrahydropyranyl vinyl ether, vinyloxytrimethylsilane, or vinyloxydimethylphenylsilane.
  • vinyl ether monomer t-butyl vinyl ether is preferable.
  • These vinyl ether monomers may be used individually by 1 type, and may use 2 or more types together.
  • the fluorine-containing polymer of the present invention may contain a polymer unit based on another monomer copolymerizable with the fluorine-containing monomer.
  • Polymeric units based on the above other monomers are polymerized units based on monomers not containing fluorine atoms (however, polymerized units based on vinyl alcohol, polymerized units represented by general formula (1) and vinyl ester monomer) (Excluding polymer-based polymerized units).
  • Examples of the other monomer include at least selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, vinyl chloride, vinylidene chloride, a hydroxyl group-containing vinyl ether monomer, and an unsaturated carboxylic acid.
  • One fluorine-free ethylenic monomer is preferred.
  • Examples of the hydroxyl group-containing vinyl ether monomer include 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether.
  • the fluoropolymer of the present invention preferably has a weight average molecular weight of 1,000 to 3,000,000, more preferably 5,000 to 1,000,000, and still more preferably 10,000 to 600,000.
  • the fluorine-containing polymer of the present invention is a step of copolymerizing a fluorine-containing monomer and a vinyl ester monomer to obtain a fluorine-containing monomer / vinyl ester copolymer.
  • This manufacturing method may be referred to as the first manufacturing method of the present invention.
  • a method for copolymerizing a fluorinated monomer and a vinyl ester monomer and a method for hydrolyzing a fluorinated monomer / vinyl ester copolymer have been well known in the art. Can also be performed in the present invention. By hydrolyzing the fluorinated monomer / vinyl ester copolymer, the acetate group is converted to a hydroxyl group, and a fluorinated monomer / vinyl alcohol copolymer is obtained.
  • the fluorine-containing monomer / vinyl ester copolymer obtained by copolymerizing a fluorine-containing monomer and a vinyl ester monomer has a molar ratio of the fluorine-containing monomer to the vinyl ester monomer
  • the (fluorinated monomer) / (vinyl ester monomer) is preferably (30 to 70) / (70 to 30), more preferably (40 to 60) / (60 to 40).
  • Hydrolysis of the fluorinated monomer / vinyl ester copolymer is preferably carried out so that the degree of saponification is 1 to 100%, more preferably 30 to 100%.
  • the degree of saponification is determined by the integral value of protons derived from acetyl groups (C H 3 C ( ⁇ O) —) near 2.1 ppm before and after saponification, and 2.2 to 2.7 ppm by 1 H-NMR. It can be measured by quantifying the integral value of protons derived from the main chain methylene group (—C H 2 —CH—).
  • 1 H-NMR GEMINI-300 manufactured by VARIAN
  • Vinyl ester monomers do not contain fluorine atoms.
  • Examples of the vinyl ester monomer include vinyl acetate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and the like.
  • vinyl ester monomer vinyl acetate and vinyl stearate are preferable. More preferred is vinyl acetate.
  • the compound represented by the general formula (4) used in the step of obtaining the fluoropolymer includes the following general formula (5):
  • M is a metal
  • R 11 is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms
  • R 12 is the same or different and is an alkyl group, an alkoxyalkyl group, or an aryl group.
  • A is an integer of 1 to 3
  • b is an integer of 0 to 4
  • a + b 2 to 5
  • d is 0 or 1
  • e is 0 or 1
  • d + e 1
  • f is an integer of 0 to 10
  • g is an integer of 0 to 3
  • h is an integer of 0 to 3
  • g + h 1 to 3
  • at least 1 of b, e, and h Is preferably 1 or more.).
  • the amount of the compound represented by the general formula (4) varies depending on the number of hydroxyl groups in the molecule of the fluorine-containing monomer / vinyl alcohol copolymer. What is necessary is just to use the quantity sufficient for one compound represented by General formula (4) to react with respect to one hydroxyl group.
  • the amount of the compound represented by the general formula (4) is usually 0.5 to 100 moles with respect to 1 mole of hydroxyl groups in the molecule of the fluorine-containing monomer / vinyl alcohol copolymer. Preferably, 0.67 to 10 mol, more preferably 0.83 to 2 mol may be used.
  • the hydroxyl group in the molecule of the fluorine-containing monomer / vinyl alcohol copolymer and the isocyanate group of the compound represented by the general formula (4) are subjected to a urethanation reaction (addition). Reaction) to form urethane bonds.
  • the hydrolyzable metal alkoxide present in the compound represented by the general formula (4) does not substantially react and becomes a curing site of the fluoropolymer of the present invention.
  • the unreacted OH group is a site for improving the compatibility and solubility of the fluoropolymer of the present invention. Acts as
  • the urethanization reaction easily proceeds by mixing the fluorine-containing monomer / vinyl alcohol copolymer and the compound represented by the general formula (4) or heating the mixture.
  • the heating temperature (reaction temperature) of the urethanization reaction is usually about 5 to 90 ° C, preferably about 10 to 90 ° C, more preferably about 20 to 80 ° C.
  • the fluorine-containing monomer / vinyl alcohol copolymer and the compound represented by the general formula (4) may be reacted in the presence of a catalyst. It does not specifically limit as said catalyst, What is necessary is just to use the conventionally well-known thing used for a urethanation reaction, and a commercial item can be obtained easily.
  • the catalyst examples include organic titanium compounds such as tetraethyl titanate and tetrabutyl titanate, organotin compounds such as tin octylate, dibutyltin oxide, and dibutyltin dilaurate, and halogen compounds such as stannous chloride and stannous bromide. Examples include stannous. Among these, organotin compounds are preferable.
  • Examples of the catalyst also include amine catalysts.
  • examples include ethanolamine, N-methylethanolamine, triethanolamine, N, N-dimethylethanolamine, n-butylamine, diethylamine, triethylenediamine, triethylamine, tetramethylenediamine, and cyclohexylamine.
  • triethylenediamine or triethylamine is used.
  • triethylamine is more preferable.
  • the urethanization reaction proceeds in a shorter time, and the intended fluoropolymer is obtained.
  • the amount of the catalyst used for the urethanization reaction is not particularly limited and may be appropriately adjusted.
  • the amount is usually 0.00001-3 mass per 100 mass parts of the compound represented by the general formula (4). Part, preferably about 0.0001 to 1 part by mass.
  • a solvent may be further used.
  • a solvent that does not interfere with the progress of the urethanization reaction and that is generally used may be used.
  • the solvent examples include ketone solvents such as methyl isobutyl ketone (MIBK) and methyl ethyl ketone (MEK); ester solvents such as ethyl acetate and butyl acetate; ether solvents such as THF, HCFC225 (CF 3 CF 2 CHCl 2 / A fluorine-based solvent such as a CClF 2 CF 2 CHClF mixture), an amide solvent such as N, N-dimethylformamide (DMF), or the like may be used.
  • An alcohol solvent having an OH group is not preferable because it prevents the urethanization reaction from proceeding. In addition, even if water is present in the system, the progress of the urethanization reaction is hindered, so that each solvent is more preferably dehydrated before use.
  • other components may be added as necessary.
  • other components include an antioxidant, a leveling agent, an inorganic filler, and an organic filler.
  • the amount used is preferably 0.01 to 10 parts by mass, and 0.1 to 2 parts by mass with respect to 100 parts by mass of the compound represented by the general formula (4). More preferably. More preferably, it is 0.5 to 1 part by mass.
  • the fluorine-containing polymer of the present invention is obtained by copolymerizing a fluorine-containing monomer and a vinyl ester monomer to obtain a fluorine-containing monomer / vinyl ester copolymer.
  • an olefin-containing fluoropolymer by reacting a compound represented by step
  • hydrolyzable metal alkoxide was contained by further alkoxylating reaction with aliphatic alcohol. It can also be produced by a production method comprising a step of obtaining a fluoropolymer. This manufacturing method is sometimes referred to as a second manufacturing method of the present invention.
  • the method described in detail in the first production method is used for the method of copolymerizing the fluorine-containing monomer and the vinyl ester monomer and the method of hydrolyzing the fluorine-containing monomer / vinyl ester copolymer. it can.
  • Vinyl ester monomers do not contain fluorine atoms.
  • Examples of the vinyl ester monomer include vinyl acetate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and the like.
  • vinyl ester monomer vinyl acetate and vinyl stearate are preferable. More preferred is vinyl acetate.
  • R c is “an organic group having at least one olefin”.
  • the compound represented by the general formula (6) is represented by the following general formula (7): X b —R 13 — (R 14 —CH ⁇ CH 2 ) c (7) (Wherein X b is Cl, Br or I, R 13 is the same or different and is a (c + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and R 14 is the same or different; —O—, —O—C ( ⁇ O) —, a single bond, and c is an integer of 1 to 10) are preferred.
  • Xb is preferably Br from the viewpoint of easy control of the reaction.
  • the hydroxyl group of the fluorine-containing monomer / vinyl alcohol copolymer and the X b -group of the compound represented by the general formula (6) undergo an etherification reaction to form an ether bond.
  • the olefin present in the compound represented by the general formula (6) does not substantially react and becomes a reaction point of the next hydrosilylation reaction, and finally, an introduction point of the hydrolyzable metal alkoxide. Thus, it becomes a cured site of the fluoropolymer of the present invention.
  • the unreacted OH group is a site for improving the compatibility and solubility of the fluoropolymer of the present invention. Acts as
  • the etherification reaction can be carried out by reacting the fluorine-containing monomer / vinyl alcohol copolymer with a compound represented by the general formula (6) under alkaline conditions. Preferably, the reaction is carried out under conditions where the pH is 8-12. It is preferable to use 1.0 to 1.1 moles of the compound represented by the general formula (6) with respect to 1 mole of hydroxyl groups in the molecule of the fluorine-containing monomer / vinyl alcohol copolymer.
  • the etherification reaction can be carried out at room temperature to a temperature at which the solvent is refluxed for 1 to 24 hours.
  • aromatic hydrocarbons such as benzene and toluene, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide and the like can be used.
  • the fluorinated monomer / vinyl alcohol copolymer and the compound represented by the general formula (6) are reacted to obtain an olefin-containing fluoropolymer, followed by hydrolysis.
  • trichlorosilane or trialkoxysilane and the olefin of the olefin-containing fluoropolymer are hydrosilylated with each other to obtain a functional metal alkoxide, and when trichlorosilane is used, an aliphatic alcohol and alkoxylation reaction are then performed.
  • the fluorine-containing copolymer containing the target hydrolysable metal alkoxide can be obtained.
  • An example of this process is represented by the chemical reaction formula shown below.
  • x and y are the number of repeating polymer units.
  • X b , R 13 , R 14 and c are the same as those in the general formula (7).
  • trialkoxysilane examples include trimethoxysilane, triethoxysilane, and tripropoxysilane. Of these, trimethoxysilane and triethoxysilane are preferable.
  • trimethoxysilane and triethoxysilane are preferable.
  • the hydrosilylation reaction can be carried out by reacting the olefin-containing fluoropolymer with trichlorosilane or trialkoxysilane. It is preferable to use 1.05 to 10 moles of trichlorosilane or trialkoxysilane with respect to 1 mole of olefin in the molecule of the olefin-containing fluoropolymer.
  • Examples of the aliphatic alcohol include alcohols having 1 to 12 carbon atoms. From the viewpoint of reactivity, secondary alcohols are more preferable than tertiary alcohols, and primary alcohols are more preferable.
  • the number of carbon atoms is preferably 1 to 4, more preferably 1 or 2. Examples of such are methanol and ethanol.
  • the alkoxylation reaction can be carried out by reacting the polymer obtained by the hydrosilylation reaction with trichlorosilane described above and an aliphatic alcohol.
  • the hydrosilylation reaction may be performed.
  • the hydrolyzable metal alkoxide obtained by the hydrosilylation reaction with trialkoxysilane may be used. It becomes possible to change the carbon chain length of the alkoxide moiety.
  • the amount of aliphatic alcohol used in the alkoxylation reaction is preferably 1 to 2 moles of aliphatic alcohol per 1 mole of silyl groups in the molecule of the polymer obtained by the hydrosilylation reaction. .
  • aprotic solvent such as diethyl ether, toluene, tetrahydrofuran, or acetonitrile
  • the solvent it is preferable to use an aprotic solvent such as diethyl ether, toluene, tetrahydrofuran, or acetonitrile as the solvent.
  • a catalyst may be used, and the catalyst is preferably a tertiary amine.
  • tertiary amines include triethylamine, pyridine, tri-n-butylamine, di-n-butyloctylamine, tri-n-pentylamine, tri-n-hexylamine and tri-n-octylamine. It is done.
  • the amount of the catalyst used is preferably 1 to 2 moles of catalyst per mole of silyl group in order to carry out the reaction efficiently. There is no problem as long as the reaction temperature is not higher than the boiling point of the solvent. Alternatively, it is preferably refluxed at the boiling point of the solvent.
  • a method for copolymerizing a fluorinated monomer and a vinyl ether monomer and a method for deprotecting a fluorinated monomer / vinyl ether copolymer have been well known in the past.
  • the invention can also be performed.
  • By deprotecting the fluorine-containing monomer / vinyl ether copolymer —OR is converted to a hydroxyl group, and a fluorine-containing monomer / vinyl alcohol copolymer is obtained.
  • the fluorine-containing monomer / vinyl ether copolymer obtained by copolymerizing a fluorine-containing monomer and a vinyl ether monomer has a molar ratio of the fluorine-containing monomer to the vinyl ether monomer (fluorine-containing monomer).
  • (Mer) / (vinyl ether monomer) is preferably (40 to 60) / (60 to 40), more preferably (45 to 55) / (55 to 45).
  • the deprotection of the fluorine-containing monomer / vinyl ether copolymer is preferably performed so that the degree of deprotection is 1 to 100%, and more preferably 30 to 100%.
  • the degree of deprotection is determined by 1 H-NMR, the integral value of protons derived from a tertiary butyl group (—C (C H 3 ) 3 ) around 1.0 to 1.3 ppm before and after the deprotection reaction, It can be measured by quantifying the integral value of protons derived from a main chain methylene group (—C H 2 —CH—) of 2.2 to 2.7 ppm.
  • 1 H-NMR GEMINI-300 manufactured by VARIAN
  • R in the general formula (8) is not particularly limited as long as it is deprotected, but —CR 1 R 2 R 3 (R 1 , R 2 and R 3 each independently has 1 to 3 carbon atoms) An alkyl group), an alkoxymethyl group having 1 to 6 carbon atoms, a tetrahydrolfuryl group, a tetrahydrolpyranyl group, or a trialkylsilyl group (—Si (R 4 ) 3 , R 4 has 1 carbon atom) An alkyl group or an aryl group of ⁇ 6), and —CR 1 R 2 R 3 is more preferable.
  • the vinyl ether monomer tertiary butyl vinyl ether (t-butyl vinyl ether) is preferable because of its availability.
  • the preferable details of the compound represented by the general formula (4), the preferable addition amount, and the like can apply the contents detailed in the first production method.
  • an olefin-containing fluoropolymer by reacting a compound represented by step
  • hydrolyzable metal alkoxide was contained by further alkoxylating reaction with aliphatic alcohol. It can also be produced by a production method comprising a step of obtaining a fluoropolymer. This manufacturing method may be referred to as a fourth manufacturing method of the present invention.
  • the preferable details of the compound represented by the general formula (6), the preferable addition amount, and the like can apply the contents detailed in the second production method.
  • the preferable details of the vinyl ether monomer represented by the general formula (8), the preferable addition amount, and the like can apply the contents described in detail in the third production method.
  • cured material The curable composition containing the fluoropolymer of this invention is also one of this invention.
  • the aspect which uses a solvent is mentioned, for example.
  • various substrates can be coated to form a coating film. Further, after the coating film is formed, it can be cured efficiently by heating to obtain a cured coating film. This is preferable.
  • the solvent examples include fluorine-containing organic solvents such as perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and HCFC225; monovalent alcohols having 1 to 8 carbon atoms, ethylene glycol, glycerin, etc. Alcohols such as polyhydric alcohols; ketones such as methyl isobutyl ketone (MIBK); esters, halogenated hydrocarbons excluding fluorine, and the like. Among these, HCFC225, alcohols, and ketones are preferable because the fluorine-containing polymer can be easily dissolved and is easily available. Of the alcohols, monohydric alcohols having 1 to 4 carbon atoms are more preferred, and isopropanol is even more preferred.
  • fluorine-containing organic solvents such as perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexan
  • the curable composition of the present invention may contain a silane compound.
  • the silane compound include the following general formula (9): Si (OR I ) 4 (9) (Wherein R I represents an aliphatic hydrocarbon group, the number of carbon atoms of which is not particularly limited), and a partial hydrolysis-condensation product of the compound represented by the general formula (9) Such as things.
  • R I represents an aliphatic hydrocarbon group, the number of carbon atoms of which is not particularly limited
  • a partial hydrolysis-condensation product of the compound represented by the general formula (9) Such as things.
  • the silane compound tetraethoxysilane is preferable because it is easily available.
  • the curable composition of the present invention preferably contains a hydrolyzable metal alkoxide group-containing compound (silane coupling agent) other than the fluoropolymer of the present invention.
  • silane coupling agent a hydrolyzable metal alkoxide group-containing compound
  • ESi (R II) 3-r D r (10) ESi (R II) 3-r D r (10) Wherein E is an organic residue capable of reacting with an organic compound such as a polymer, D is a halogen atom or an alkoxyl group, R II is an alkyl group, and r is It is an integer of 1 to 3).
  • silane coupling agent examples include tetraalkoxysilanes (eg, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane), trialkoxysilanes (eg, Methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyl Triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxys
  • silane coupling agents work as a crosslinking agent for the curable composition and contribute to the improvement of the strength and heat resistance of the cured product.
  • tetramethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, and condensates thereof are preferable.
  • the blending amount of the silane coupling agent in the curable composition of the present invention can be adjusted in the range of 0 to 99% by mass with respect to 100% by mass of the fluoropolymer of the present invention.
  • the curable composition of this invention may contain the filler as a structural component as needed.
  • a metal oxide, a metal, a polymer, a mineral, etc. are mentioned, for example, These may be used individually by 1 type and may use 2 or more types together.
  • a filler is used for the functional improvement and functional provision of the cured film obtained from the curable composition of this invention. Specific functions include surface hardness, anti-blocking, heat resistance, barrier properties, electrical conductivity, antistatic properties, electromagnetic wave absorption, ultraviolet cut, toughening, impact resistance, low heat linear expansion, and the like.
  • Examples of the metal oxide include silicon oxide, titanium oxide, zirconium oxide, zinc oxide, tin oxide, indium oxide, aluminum oxide, antimony oxide, cerium oxide, magnesium oxide, iron oxide, tin-doped indium oxide (ITO), and antimony-doped oxide. Examples thereof include tin and fluorine-doped tin oxide. Examples of the metal include gold, silver, copper, aluminum, nickel, iron, zinc, and stainless steel. Examples of the polymer include fluororesin, liquid crystal polymer, acrylic resin, styrene resin, polyurethane resin, epoxy resin, polycarbonate resin, melamine resin, polyolefin resin, and rubber.
  • the mineral examples include clay minerals such as montmorillonite, talc, mica, boehmite, kaolin, smectite, zonolite, verculite, and sericite.
  • carbon compounds such as carbon fiber, carbon black, acetylene black, ketjen black and carbon nanotubes; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; glass fibers, glass beads, glass flakes, glass balloons, etc. And various glasses.
  • the size of the filler is not particularly limited and can be, for example, about 1 nm to 10 ⁇ m, and any of spherical, needle-like, plate-like, fiber-like, balloon-like, hollow-like, etc.
  • the shape may also be In the case of the above polymer, powder, crosslinked particles, beads and the like are used.
  • powder may be used as it is, or a filler dispersed in a solvent like sol or colloid may be used.
  • a filler surface-treated with a coupling agent or the like may be further used for the purpose of improving dispersibility and interface affinity.
  • the curable composition of this invention may contain the other component in the range which does not impair the effect of this invention other than the component mentioned above.
  • Other components include, for example, hardness adjusters, extenders, mold release agents, surface treatment agents, flame retardants, antibacterial agents, leveling agents, antifoaming agents, thixotropic agents, heat stabilizers, light stabilizers, and UV absorption. Agents, colorants, coupling agents, metal alkoxides and the like.
  • the curable composition of the present invention is purified by a reprecipitation method or the like from the system in which the step of obtaining the fluoropolymer of the present invention in any one of the first to fourth production methods is performed.
  • a silane coupling agent, filler, hardness adjuster, extender or other additive as a crosslinking agent, and adjusting the viscosity by adding a solvent as appropriate according to the final mode, Can be prepared.
  • Curing of the curable composition of the present invention is basically a sol-gel reaction, and curing proceeds by a condensation reaction following hydrolysis.
  • the sol-gel curing reaction can be carried out under known reaction conditions.
  • the sol-gel curing reaction may be carried out by the following method. First, after pouring the curable composition of the present invention containing a solvent into a container, the solvent is distilled off and sol-gel curing is performed. Subsequently, the temperature is further raised and the solvent is completely distilled off and sol-gel curing is performed to obtain a desired hybrid cured product.
  • the solvent evaporation and sol-gel curing step is preferably performed through two or more stages as described above in order to control foaming and curing shrinkage due to rapid scattering of volatile components such as the solvent.
  • the first stage is usually cured and dried to such an extent that the surface tack of the cured product is eliminated. Therefore, the condition is usually about 20 to 150 ° C. for about 1 minute to 2 hours. Is preferred.
  • heating is performed at about 130 ° C. to 280 ° C., preferably 200 ° C. or higher and lower than 250 ° C. for about 1 minute to 6 hours, thereby completely removing the residual solvent and completing the dealcoholization condensation reaction of the alkoxysilyl group. be able to.
  • the cured product (cured film) thus obtained is characterized by excellent heat resistance, mechanical properties, chemical resistance, water resistance, and durability due to the effect of compounding.
  • the viscosity at 30 ° C. is too low when the viscosity is too low.
  • the viewpoint that s or more is preferable and that the thin film formability is good 5 mPa ⁇ s or more is more preferable, and from the viewpoint that curing shrinkage during curing is small, 10 mPa ⁇ s or more is more preferable.
  • 20000 mPa ⁇ s or less is preferable, and from the viewpoint that the curable composition spreads over the details during molding, 5000 mPa ⁇ s or less is more preferable, and when a thin film is formed.
  • From the viewpoint of good leveling (surface smoothness) 2000 mPa ⁇ s or less is more preferable.
  • the curable composition of the present invention can be cured to form a cured film and used for various applications.
  • a method of forming the film a known method suitable for the application can be employed. For example, when it is necessary to control the film thickness, roll coating, gravure coating, micro gravure coating, flow coating, bar coating, spray coating, die coating, spin coating, dip coating, etc. are used. it can.
  • the curable composition of the present invention may be used for film formation, but is particularly useful as a molding material for various molded products.
  • As the molding method extrusion molding, injection molding, compression molding, blow molding, transfer molding, stereolithography, nanoimprinting, vacuum molding and the like can be adopted.
  • the curable composition of this invention can use as a material of a sealing member, an optical member, a photoelectronic imaging tube, various sensors, an antireflection film, for example.
  • cured material obtained from the curable composition of this invention is excellent in transparency, it can utilize suitably as an optical material which forms an optical member.
  • it can also be used as a sealing member material for electronic semiconductors, a water and moisture resistant adhesive, an adhesive for optical components and elements, and a paint.
  • a package for example, a package (encapsulation) of an optical functional element such as a light emitting element such as a light emitting diode (LED), an EL element or a nonlinear optical element, or a light receiving element such as a CCD, CMOS or PD, An example of this is mounting.
  • an optical functional element such as a light emitting element such as a light emitting diode (LED), an EL element or a nonlinear optical element, or a light receiving element such as a CCD, CMOS or PD
  • sealing members or fillers for optical members such as lenses for deep ultraviolet microscopes are also included.
  • the cured product of the present invention is excellent in transparency, it can be suitably used as a sealing material for optical elements.
  • the sealed optical element is used in various places. Although it does not specifically limit as an optical element, For example, in addition to light emitting elements, such as a light emitting diode (LED), EL element, and a nonlinear optical element, light receiving elements, such as CCD, CMOS, and PD, a high mount stop lamp and a meter Light emitting elements such as a panel, a backlight of a mobile phone, a light source of a remote control device of various electric products; a camera autofocus, a light receiving element for an optical pickup for CD / DVD, and the like.
  • the curable composition of this invention is suitable as a material which forms an optical member. Since the curable composition of the present invention contains fluorine, the obtained cured product becomes an optical member having a low refractive index, and is useful as an optical transmission medium, for example.
  • the curable composition of the present invention includes, in particular, a plastic clad material whose core material is quartz or optical glass, an optical fiber clad material, an all plastic optical fiber clad material whose core material is plastic, an antireflection coating material, and a lens. It can be used for materials, optical waveguide materials, prism materials, optical window materials, optical storage disk materials, nonlinear optical element materials, hologram materials, photolithographic materials, light emitting element sealing materials, and the like.
  • optical devices such as optical waveguides, OADMs, optical switches, optical filters, optical connectors, multiplexers / demultiplexers, and other optical devices are known and useful for forming these devices.
  • Material various functional compounds (non-linear optical materials, fluorescent light-emitting functional dyes, photorefractive materials, etc.) are contained and used for functional devices for optical devices such as modulators, wavelength conversion elements, and optical amplifiers. Is suitable.
  • As a sensor application there is an effect such as an improvement in sensitivity of an optical sensor or a pressure sensor, and protection of the sensor by water / oil repellency characteristics, which is useful.
  • a cured product obtained by curing the curable composition can be suitably used as an optical member in terms of excellent transparency.
  • the cured product of the present invention preferably has a light transmittance of 80% or more. More preferably, it is 85% or more, and still more preferably 90% or more.
  • the light transmittance of the cured product can be measured at a wavelength of 550 nm using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.).
  • the cured product of the present invention is not only excellent in transparency but also exhibits special performance as a sealing member as described above, and is particularly suitable as a sealing member for optical elements. .
  • the curable composition of this invention is excellent in adhesiveness with glass, a metal, etc., it can be used suitably also as coating agents, antifouling agents, etc., such as glass or a metal surface. That is, a curable composition that is a coating agent or an antifouling agent is also one preferred embodiment of the present invention.
  • coating the curable composition of this invention to the surface of a base material is employable. Examples of the coating method include brush coating, spray coating, spin coating, dip coating, roll coating, gravure coating, and curtain flow coating.
  • the base material examples include ornaments such as tie pins, necklaces, and earrings; metal or plated products such as water faucets, brass instruments, woodwind instruments, golf clubs, door handles, dumbbells, and blades; insulators, tiles, and hygiene Ceramic materials such as pottery, tableware and roof tiles; stone materials such as tombstones, meteorites and marble; paper products such as wallpaper, bran paper, books, posters and photographs; leather such as wallets, shoes, bags, watch bands and baseball gloves Products: Household appliances such as fan blades, microwave doors, refrigerator surfaces, etc .; Contact glass for copiers, OHP mirrors, OHP sheets, keyboards, telephones, office desks and other office-related products; Glasses, cupboards Household items such as doors, mirrors, window glass, electric lamp umbrellas, chandeliers; building materials such as show windows, telephone boxes, aquarium glass; vehicle glass, painted surfaces of car bodies, etc. Both parts; accessories such as glasses frames, glasses for underwater glasses, goggles, helmets, cover glasses for watch dials; play equipment such as pachinko
  • GPC HLC-8020 manufactured by Tosoh Corporation was used, one column manufactured by Shodex (one GPC KF-801 and one GPC KF-802 were used). From the data measured by using tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated using the following GPC KF-806M in series. calculate.
  • THF tetrahydrofuran
  • Tg Glass transition temperature
  • Tm Melting point
  • Synthesis example 1 Into a 3 L stainless steel autoclave, 1200 g of butyl acetate as a solvent and 140 g of vinyl acetate as a vinyl ester monomer were added, 7.2 g of perbutyl PV (product name, manufactured by NOF Corporation) was added as a polymerization initiator, and the flange was tightened. The autoclave was vacuum-substituted, 200 g of tetrafluoroethylene was enclosed as a fluorine olefin gas, and the reaction was started by placing it in a shaking thermostat at 60 ° C. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed, the shaking was stopped in 6 hours, and the remaining gas was blown to complete the reaction.
  • perbutyl PV product name, manufactured by NOF Corporation
  • composition of the polymer A1 was determined from elemental analysis of fluorine, the alternating ratio of fluorine olefin and vinyl ester was calculated from 1 H-NMR, and the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined from GPC. The glass transition temperature was measured from DSC. The results are shown in Table 2.
  • Synthesis example 2 Polymer A2 was obtained in the same manner as in Synthesis Example 1 except that the monomer charge ratio, scale, reaction time, etc. were changed.
  • the reaction conditions are summarized in Table 1, and the physical properties of the obtained polymer are summarized in Table 2.
  • Synthesis example 3 A 3 L stainless steel autoclave was charged with 1000 g of pure water, 23.2 g of vinyl acetate, Neocor P (76.4 mass% isopropyl alcohol solution of sodium dioctylsulfosuccinate: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), nitrogen-substituted, and tetrafluoro Ethylene 37g was added and the inside of a tank was heated up to 80 degreeC. Thereafter, 30 g of tetrafluoroethylene was added. At this time, the pressure in the tank was 0.809 MPa. Under stirring, 22 g of a 1% by mass aqueous solution of ammonium persulfate (APS) was added to initiate the reaction.
  • APS ammonium persulfate
  • the solenoid valve when tetrafluoroethylene is consumed and the inside of the tank reaches 0.800 MPa, the solenoid valve is automatically opened to supply tetrafluoroethylene, and when 0.775 MPa is reached, the solenoid valve is automatically closed and tetrafluoroethylene is closed. While controlling the supply and pressure of tetrafluoroethylene in a cycle in which the supply of ethylene was stopped, vinyl acetate was added in accordance with the consumption of tetrafluoroethylene.
  • the resulting vinyl acetate / tetrafluoroethylene copolymer had a glass transition temperature of 40 ° C. and a particle size of 116 nm.
  • the reaction conditions are summarized in Table 1, and the physical properties of the obtained polymer are summarized in Table 2.
  • Synthesis example 4 A 300 mL stainless steel autoclave is charged with 50 g of butyl acetate solvent and 10 g of vinyl stearate monomer, 0.4 g of perbutyl PV (product name, manufactured by NOF Corporation) is added as a polymerization initiator, the flange is tightened, and the autoclave is vacuum-substituted. Then, 8.0 g of tetrafluoroethylene was encapsulated as a fluorine olefin gas, and 2.6 g of hexafluoropropylene was subsequently encapsulated, and the mixture was placed in a shaking thermostat at 60 ° C. to initiate the reaction. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed, the shaking was stopped in 15 hours, and the remaining gas was blown to complete the reaction.
  • perbutyl PV product name, manufactured by NOF Corporation
  • Synthesis Examples 5-7 Polymers A5, B1, and B2 were obtained in the same manner as in Synthesis Example 1 except that the type of monomer and the charging ratio, scale, reaction time, and the like were changed.
  • the reaction conditions are summarized in Table 1, and the physical properties of the obtained polymer are summarized in Table 2.
  • Synthesis example 8 In a 300 mL stainless steel autoclave, 150.0 g of t-butanol, 26.7 g of t-butyl vinyl ether, and 0.48 g of potassium carbonate were added, 0.46 g of a 70% isooctane solution of perbutyl PV was added as a polymerization initiator, and the flange was tightened. The autoclave was replaced with vacuum, 26.7 g of tetrafluoroethylene (TFE) was sealed as a fluorine olefin gas, and the reaction was started in a shaking thermostat at 60 ° C. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed, the shaking was stopped in 3 hours, and the remaining gas was blown to complete the reaction.
  • TFE tetrafluoroethylene
  • Synthesis Example 9 (Saponification heterogeneous system) 4 g of TFE / vinyl acetate polymer A2 obtained in Synthesis Example 2 was stirred in 136 g of MeOH solvent, and a catalytic amount of NaOH particles (about 0.4 g) was added and gradually reacted to uniformly dissolve the polymer. Stirring was continued until The solution colored yellow with the reaction, and when the solution was stirred at room temperature for 3 days, the polymer was uniformly dissolved, so the reaction was terminated. The reaction solution was concentrated with an evaporator and dropped into water to purify the polymer by reprecipitation.
  • Synthesis example 10 (saponification homogeneous system)
  • the TFE / vinyl acetate polymer A1 obtained in Synthesis Example 1 was uniformly dissolved in 10 g THF solvent so as to have a concentration of 10% by mass. Thereafter, a 0.6N NaOH solution was added to give an equivalent amount of vinyl acetate in the polymer, and after 30 minutes the polymer was reprecipitated in a large amount of water. After washing with 1N HCl, it was thoroughly washed with ion-exchanged water, and the reprecipitated polymer was suction filtered and dried at 80 ° C. for 2 hours with a dryer. As a result of calculating the hydrolysis rate (degree of saponification) from the relative intensity of the carbonyl peak by IR, 34% of TFE / vinyl alcohol / vinyl acetate polymer A1-34 was obtained.
  • Synthesis Examples 11 to 13 (saponification uniform system) By changing the saponification time in Synthesis Example 10, TFE / vinyl alcohol / vinyl acetate polymers A1-45, A1-86, and A1-96 were obtained.
  • the saponification time and saponification degree are summarized in Table 3.
  • Synthesis Examples 14 to 18 (saponification homogeneous system) A saponified polymer was obtained in the same manner as in Synthesis Example 10 except that the saponification time of Synthesis Example 10 was 1 day and the polymers obtained in Synthesis Examples 3 to 7 were used. The results are summarized in Table 3.
  • Example 1 1.5 g of polymer A1-96 was uniformly dissolved in 20 g of N, N-dimethylformamide (DMF) solvent. 0.59 g of 3-isocyanatopropyltriethoxysilane ((C 2 H 5 O) 3 SiC 3 H 6 NCO) (KBE-9007) (corresponding to a 10 mol% modification amount of OH groups in the polymer), and as a catalyst After adding 42 ⁇ L of dibutyltin dilaurate, the mixture was stirred at room temperature for 24 hours.
  • DMF N, N-dimethylformamide
  • Example 12 1.5 g of polymer A1-96 was uniformly dissolved in 15 g of THF solvent. Thereafter, 0.4 g of sodium hydroxide was added, and after uniform dissolution, 0.54 g of allyl bromide was added dropwise at room temperature from a dropping funnel and stirred at room temperature for 13 hours. The resulting reaction solution was re-precipitated in water, vacuum-dried, dissolved in a heavy DMSO solution, and analyzed by H-NMR. As a result, an allyl group was confirmed. The amount of allyl group introduced calculated from NMR was 100 mol%. The obtained polymer was 0.8 g and the yield was 53%. This process is represented by the chemical reaction formula as shown below.
  • Example 13 Preparation of curable composition 1.1 g of A1-96-KBE20 synthesized in Example 1 was dissolved in MIBK to a concentration of 10% by mass. Subsequently, the silicon wafer was spin-coated using a spin coater under conditions of 300 rpm ⁇ 5 seconds, 3000 rpm ⁇ 25 seconds, and then heated and formed on a hot stage at 250 ° C. for 5 minutes. The physical properties of the coating film after film formation were evaluated. The results are summarized in Table 5. The appearance after film formation was visually evaluated. The evaluation results are indicated by ⁇ (uniform), ⁇ (turbid), and ⁇ (white turbidity).
  • the solvent resistance was evaluated by visually observing the appearance by dropping one drop of butyl acetate solution onto the coating film and wiping with a Kimwipe one minute later.
  • the evaluation results are indicated by ⁇ (no change), ⁇ (partially changed), and ⁇ (peeling).
  • ⁇ (no change), ⁇ (partially changed), and ⁇ (peeling) For heat resistance, the silicon wafer after film formation was placed in an electric furnace at 100 ° C., and the appearance after 100 hours was visually evaluated. The evaluation results are indicated by ⁇ (no change), ⁇ (partially changed), and ⁇ (peeling).
  • the refractive index after film formation was measured with a spectroscopic ellipsometer.
  • Examples 14 and 15 A curable composition was prepared in the same manner as in Example 13, and the physical properties of the coating film were evaluated. Table 5 shows the types, amounts, and evaluation results of the polymers used.
  • Comparative Examples 1 and 2 A curable composition was prepared in the same manner as in Example 13 using A1 (Comparative Example 1) and A1-96 (Comparative Example 2) as polymers, and the physical properties of the coating film were evaluated. The evaluation results are shown in Table 5.

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Abstract

La présente invention a pour but de fournir un nouveau polymère contenant du fluor qui peut être facilement durci, tout en ayant une résistance aux solvants, des propriétés de barrière aux gaz, et une transparence et une résistance à la chaleur. La présente invention concerne un polymère contenant du fluor qui est caractérisé en ce qu'il comprend une unité de polymérisation à base d'un monomère contenant du fluor, et comme unités de polymérisation facultatives, une unité de polymérisation à base d'alcool vinylique et une unité de polymérisation représentée par la formule générale (1). -CH2-CH(-O-(L)l-Rb)- (1) (Dans la formule, Rb représente un groupe organique ayant au moins un alcoolate métallique hydrolysable ; L représente un groupe organique divalent ; et l est 0 ou 1).
PCT/JP2013/062941 2012-05-24 2013-05-08 Polymère contenant du fluor et son procédé de fabrication WO2013175962A1 (fr)

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CN113072654A (zh) * 2021-03-30 2021-07-06 天津日津科技股份有限公司 一种含氟聚乙烯醇缩醛防潮剂的制备方法
WO2022163503A1 (fr) * 2021-01-29 2022-08-04 Ａｇｃ株式会社 Électrode pour batterie secondaire, et dispositif électrochimique

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JP6323320B2 (ja) * 2014-12-15 2018-05-16 旭硝子株式会社 塗料用組成物および塗装物品
WO2016104602A1 (fr) * 2014-12-26 2016-06-30 ダイキン工業株式会社 Matériau antisalissures marin, revêtement antisalissures marin, panneau antisalissures marin, structure sous-marine et procédé pour empêcher l'adhérence de micro-organismes marins à une structure sous-marine
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WO2020195860A1 (fr) * 2019-03-27 2020-10-01 Ａｇｃ株式会社 Polymère, procédé de production associé, composition d'un agent résistant à l'eau et à l'huile, article, et papier résistant à l'eau et à l'huile

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CN113072654A (zh) * 2021-03-30 2021-07-06 天津日津科技股份有限公司 一种含氟聚乙烯醇缩醛防潮剂的制备方法
CN113072654B (zh) * 2021-03-30 2023-06-16 天津日津科技股份有限公司 一种含氟聚乙烯醇缩醛防潮剂的制备方法

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