US20120296040A1 - Fluoroolefin/vinyl alcohol copolymer and process for its production - Google Patents

Fluoroolefin/vinyl alcohol copolymer and process for its production Download PDF

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US20120296040A1
US20120296040A1 US13/564,128 US201213564128A US2012296040A1 US 20120296040 A1 US20120296040 A1 US 20120296040A1 US 201213564128 A US201213564128 A US 201213564128A US 2012296040 A1 US2012296040 A1 US 2012296040A1
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fluoroolefin
copolymer
vinyl ether
vinyl alcohol
group
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Shunichi Kodama
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AGC Inc
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Asahi Glass Co Ltd
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Assigned to ASAHI GLASS COMPANY, LIMITED reassignment ASAHI GLASS COMPANY, LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KODAMA, SHUNICHI
Publication of US20120296040A1 publication Critical patent/US20120296040A1/en
Priority to US14/246,791 priority Critical patent/US9290595B2/en
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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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • 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
    • C08F214/267—Tetrafluoroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
    • 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
    • C08F216/02—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 alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • 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
    • C08F214/24—Trifluorochloroethene
    • C08F214/245—Trifluorochloroethene with non-fluorinated comonomers
    • C08F214/247—Trifluorochloroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
    • 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
    • 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
    • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
    • 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
    • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
    • 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
    • C08F216/18—Acyclic compounds
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
    • 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
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority

Definitions

  • the present invention relates to a fluoroolefin/vinyl alcohol copolymer and a process for its production.
  • a fluoroolefin/vinyl alcohol copolymer i.e. a copolymer of a fluoroolefin and vinyl alcohol, is used as a raw material for coating resins, a material for gas/liquid separation membranes, a gas barrier material, a sealing material for solar cells, a material for various surface protective sheets, a hydrophilic porous material, etc. (Patent documents 1 and 2).
  • Patent Documents 1 and 2 As a method for producing a fluoroolefin/vinyl alcohol copolymer, a method has already been known wherein a fluoroolefin and vinyl acetate are copolymerized, followed by hydrolysis under an acidic or basic condition (Patent Documents 1 and 2, and Non-Patent Document 3).
  • a fluoroolefin and vinyl acetate are used as raw materials, and they are copolymerized to obtain a fluoroolefin/vinyl acetate copolymer, and in such a copolymer, an ester moiety in polymerized units based on vinyl acetate is hydrolyzed to form a hydroxy group thereby to convert the polymerized units to ones based on vinyl alcohol.
  • an ester moiety in polymerized units based on vinyl acetate is hydrolyzed to form a hydroxy group thereby to convert the polymerized units to ones based on vinyl alcohol.
  • the reaction rate is low, and the productivity is low.
  • the obtained fluoroolefin/vinyl alcohol copolymer usually has a low thermal decomposition starting temperature and thus has a problem in thermal stability.
  • the present invention provides a process for producing a fluoroolefin/vinyl alcohol copolymer, and a fluoroolefin/vinyl alcohol copolymer, having the following constructions.
  • a process for producing a fluoroolefin/vinyl alcohol copolymer which comprises a polymerization step of copolymerizing a fluoroolefin represented by the following formula (1) and a vinyl ether represented by the following formula (2), and a deprotection step of substituting R 1 in polymerized units based on the vinyl ether in the copolymer obtained in the polymerization step, with a hydrogen atom to form a hydroxy group:
  • X is a fluorine atom, a chlorine atom, a trifluoromethyl group or —OC a F 2a+1 (wherein a is an integer of from 1 to 3), and R 1 is a protective group to be substituted with a hydrogen atom by a deprotection reaction.
  • R 1 in the formula (2) is —CR 2 R 3 R 4 (wherein each of R 2 , R 3 and R 4 which are independent of one another, is a C 1-3 alkyl group), a C 1-6 alkoxymethyl group, a tetrahydrofuryl group, a tetrahydropyranyl group or a trialkylsilyl group (—Si(R 5 ) 3 wherein R 5 is a C 1-6 alkyl group or an aryl group).
  • R 6 is a group which is not susceptible to a deprotection reaction in the deprotection step.
  • X is a fluorine atom, a chlorine atom, a trifluoromethyl group or —OC a F 2a+1 (wherein a is an integer of from 1 to 3).
  • the fluoroolefin/vinyl alcohol copolymer of the present invention has a quality loss due to coloration prevented and has excellent heat resistance.
  • FIGS. 1(A) and (B) are 13 C NMR charts of copolymer B1 (upper chart) and copolymer A1 (lower chart) in Example 1.
  • FIGS. 2(A) and (B) are IR charts of copolymer B1 and copolymer A1 in Example 1, respectively.
  • the process for producing a fluoroolefin/vinyl alcohol copolymer of the present invention comprises the following steps.
  • Polymerization step a step of copolymerizing a fluoroolefin represented by the following formula (1) (hereinafter referred to as “the fluoroolefin (a)”) and a vinyl ether represented by the following formula (2) (hereinafter referred to as “the vinyl ether (b)”).
  • the fluoroolefin (a) a fluoroolefin represented by the following formula (1)
  • the vinyl ether (b) a vinyl ether represented by the following formula (2)
  • Deprotection step a step of substituting R 1 in polymerized units based on the vinyl ether (b) in the copolymer obtained in the polymerization step, with a hydrogen atom to form a hydroxy group.
  • X is a fluorine atom, a chlorine atom, a trifluoromethyl group or —OC a F 2a+1 (wherein a is an integer of from 1 to 3), and R 1 is a protective group to be substituted with a hydrogen atom by a deprotection reaction.
  • the process of the present invention is a process wherein in the polymerization step, a fluoroolefin/vinyl ether copolymer (hereinafter referred to as “the copolymer (B)”) having polymerized units based on the fluoroolefin (a) and polymerized units based on the vinyl ether (b) is obtained, and then, R 1 in polymerized units based on the vinyl ether (b) in the copolymer (B) is substituted with a hydrogen atom by a deprotection reaction, to obtain the copolymer (A) having polymerized units based on the fluoroolefin and polymerized units based on vinyl alcohol.
  • the copolymer (B) a fluoroolefin/vinyl ether copolymer having polymerized units based on the fluoroolefin (a) and polymerized units based on the vinyl ether (b)
  • the fluoroolefin (a) represented by the above formula (1) and the vinyl ether (b) represented by the above formula (2) are copolymerized to obtain the copolymer (B) having polymerized units based on the fluoroolefin (a) and polymerized units based on the vinyl ether (b).
  • fluoroolefin (a) may, for example, be tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene or a perfluoro(alkyl vinyl ether).
  • the perfluoro(alkyl vinyl ether) may, for example, be perfluoro(propyl vinyl ether).
  • the fluoroolefin (a) is preferably tetrafluoroethylene or chlorotrifluoroethylene, particularly preferably tetrafluoroethylene, whereby the heat resistance will be excellent.
  • fluoroolefin (a) one type may be used alone, or two or more types may be used in combination.
  • the vinyl ether (b) is a vinyl ether having a hydrogen atom of a hydroxy group of vinyl alcohol substituted with a protective group which can be deprotected.
  • R 1 is a protective group which protects a hydroxy group in the form of an ether and which is substituted with a hydrogen atom by a deprotection reaction to form a hydroxy group, and a protective group which is commonly used in the organic chemical field may be used.
  • —CR 2 R 3 R 4 (wherein each of R 2 , R 3 and R 4 which are independent of one another, is a C 1-3 alkyl group), a C 1-6 alkoxymethyl group, a tetrahydrofuryl group, a tetrahydropyranyl group or a trialkylsilyl group (—Si(R 5 ) 3 wherein R 5 is a C 1-6 alkyl group or an aryl group) is preferred, and —CR 2 R 3 R 4 is more preferred.
  • vinyl ether (b) t-butyl vinyl ether, 1,1-dimethylpropyl vinyl ether, methoxymethyl vinyl ether, tetrahydrofuryl vinyl ether, tetrahydropyranyl vinyl ether, vinyloxytrimethylsilane or vinyloxydimethylphenylsilane is preferred, and from the viewpoint of availability, t-butyl vinyl ether is particularly preferred.
  • vinyl ether (b) one type may be used alone, or two or more types may be used in combination.
  • the fluoroolefin (a) and the vinyl ether (b) have high alternating copolymerizability, and therefore, the alternating copolymerization rate of the obtainable copolymer (B) becomes at least 95% as calculated by probability calculation from the copolymerization reactivity ratio of the two monomers.
  • the alternating copolymerization rate is the percentage of the number of combinations where polymerized units based on different monomers are adjacent to each other, based on the total number of combinations of adjacent two polymerized units.
  • the copolymer (B) is a copolymer represented by ababbababab (wherein a is a polymerized unit based on the fluoroolefin (a), and b is a polymerized unit based on the vinyl ether (b))
  • the total number of combinations of adjacent two polymerized units is 10
  • the number of combinations where polymerized units based on different monomers are adjacent to each other is 9, and therefore, the alternating copolymerization rate is 90%.
  • the copolymer (A) obtainable from the copolymer (B) will have an alternating copolymerization rate of the fluoroolefin (a) and vinyl alcohol being at least 95%.
  • the copolymer (A) having such a high alternating copolymerization rate polymerized units based on the fluoroolefin (a) and polymerized units based on vinyl alcohol are uniformly arranged, whereby the weather resistance and water resistance are improved.
  • the reactivity of hydroxy groups is more stabilized, since the hydroxy groups are uniformly distributed.
  • a vinyl ether (c) represented by the following formula (3) may further be copolymerized.
  • R 6 is a group which is not susceptible to a deprotection reaction in the deprotection step.
  • the vinyl ether (c) is a vinyl ether wherein R 6 is not susceptible to a deprotection reaction in the deprotection step.
  • R 6 is not susceptible to a deprotection reaction in the deprotection step means that R 6 is not susceptible to a deprotection reaction under the reaction conditions where R 1 in the vinyl ether (b) is substituted with a hydrogen atom by the deprotection reaction. That is, R 6 may be a group which is susceptible to a deprotection reaction under conditions other than the reaction conditions where R 1 is substituted with a hydrogen atom by the deprotection reaction.
  • R 6 in the vinyl ether (c) is preferably a C 1-6 primary or secondary alkyl group, or a group having at least one of hydrogen atoms in such an alkyl group substituted by a substituent.
  • the substituent may, for example, be a functional group such as a hydroxy group, an amino group or a glycidyl group, a fluorine atom, or the like.
  • a specific example of the vinyl ether (c) may, for example, be an alkyl vinyl ether such as methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether or cyclohexyl vinyl ether; a functional group-containing vinyl ether such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, aminopropyl vinyl ether or glycidyl vinyl ether; or a fluorinated vinyl ether such as heptafluoropentyl vinyl ether.
  • alkyl vinyl ether such as methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether or cyclohexyl vinyl ether
  • a functional group-containing vinyl ether such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, aminopropyl vinyl ether or glycidyl vinyl ether
  • a vinyl ether of either one of the vinyl ether (b) and the vinyl ether (c), and the fluoroolefin (a) are alternately copolymerized to obtain the copolymer (B).
  • the vinyl ether (b) and the vinyl ether (c) are substantially equal in the polymerization reactivity, and therefore, it is a question of probability that both sides of a polymerized unit based on the fluoroolefin (a) in the copolymer (B) become either a polymerized unit based on the vinyl ether (b) or a polymerized unit based on the vinyl ether (c).
  • the copolymer (B) is obtainable.
  • a monomer having a vinyl ether group (the vinyl ether (b) or the vinyl ether (c)) is likely to undergo isomerization, decomposition or cationic homopolymerization under an acidic condition. Therefore, with a view to carrying out the polymerization stably, it is preferred to carry out the radical polymerization under a basic condition, and it is more preferred to adjust the pH to be from 8 to 9.
  • a method of adjusting the pH to be under a basic condition in the polymerization a method of adding e.g. potassium carbonate or ammonium carbonate to the polymerization medium, is preferred.
  • the molar ratio (a/b) of the fluoroolefin (a) to the vinyl ether (b) to be used for the copolymerization is preferably from 40/60 to 60 / 40 , more preferably from 45/55 to 55/45, particularly preferably 50/50.
  • the molar ratio (a/b) is within the above range, it is possible to readily obtain an alternate copolymer having the fluoroolefin (a) and the vinyl ether (b) alternately copolymerized.
  • the molar ratio (a/(b+c)) of the fluoroolefin (a) to the total of the vinyl ether (b) and the vinyl ether (c) to be used for the copolymerization is preferably from 40/60 to 60/40, more preferably from 45/55 to 55/45, particularly preferably 50/50.
  • the molar ratio (a/(b+c)) is within the above range, it is possible to readily obtain an alternate copolymer having the fluoroolefin (a) and the vinyl ether (b) or the vinyl ether (c) alternately copolymerized.
  • the molar ratio (b/c) of the vinyl ether (b) to the vinyl ether (c) is preferably 45/5 to 10/40, particularly preferably from 40/10 to 25/25.
  • radical polymerization initiation source a radical polymerization initiator or an ionizing radiation may be mentioned.
  • a water-soluble initiator or an oil-soluble initiator may suitably be used depending upon the polymerization type or the polymerization medium.
  • the water-soluble initiator may, for example, be a redox initiator composed of a combination of a persulfate such as ammonium persulfate, and a reducing agent such as hydrogen peroxide, sodium hydrogen sulfite or sodium thiosulfate; an inorganic initiator having a small amount of iron, a ferrous salt or silver nitrate incorporated to the above redox initiator; or an organic initiator, such as a dibasic acid peroxide such as disuccinic acid peroxide or diglutaric acid peroxide, or a dibasic acid salt such as azobisisobutylamidine.
  • a persulfate such as ammonium persulfate
  • a reducing agent such as hydrogen peroxide, sodium hydrogen sulfite or sodium thiosulfate
  • an inorganic initiator having a small amount of iron, a ferrous salt or silver nitrate incorporated to the above redox initiator
  • the oil-soluble initiator may, for example be a peroxyester type peroxide such as t-butyl peroxyacetate or t-butyl peroxypivalate; a dialkylperoxydicarbonate such as diisopropylperoxydicarbonate; benzoyl peroxide; or azobisisobutylnitrile.
  • a peroxyester type peroxide such as t-butyl peroxyacetate or t-butyl peroxypivalate
  • a dialkylperoxydicarbonate such as diisopropylperoxydicarbonate
  • benzoyl peroxide benzoyl peroxide
  • azobisisobutylnitrile azobisisobutylnitrile
  • t-butyl peroxypivalate may, for example, be preferred, from the viewpoint of handling efficiency, etc.
  • radical polymerization initiator one type may be used alone, or two or more types may be used in combination.
  • the amount of the radical polymerization initiator may be suitably changed depending upon the type, polymerization conditions, etc., and it is preferably from 0.005 to 5 mass %, particularly preferably from 0.05 to 0.5 mass %, based on the total amount of monomers to be used for the copolymerization.
  • the copolymerization type is not particularly limited, and bulk polymerization, suspension polymerization, emulsion polymerization or solution polymerization may, for example, be employed.
  • solution polymerization is preferred wherein an aromatic compound such as xylene or toluene, an alcohol such as t-butyl alcohol, an ester, a fluorochlorocarbon or the like is used as the polymerization medium.
  • the amount of the polymerization medium is preferably from 10 to 200 mass %, particularly preferably from 50 to 100 mass %, based on the total amount of monomers to be used for the copolymerization.
  • the copolymerization system may be any one of a batch system, a continuous system and a semicontinuous system.
  • the optimum value may suitably be selected depending upon the polymerization initiation source, the polymerization medium, etc., and it is preferably from ⁇ 30° C. to 150° C., more preferably from 0° C. to 100° C., most preferably from 20° C. to 70° C.
  • the polymerization pressure may suitably be selected depending upon the polymerization initiation source, the polymerization medium, etc., and it is preferably from 0.1 to 10 MPa, particularly preferably from 0.2 to 2 MPa.
  • the copolymerization time is preferably from 4 to 24 hours, more preferably from 6 to 12 hours.
  • the molecular weight of the copolymer (B) may be adjusted by controlling the ratio of the monomers and the polymerization medium or by employing a chain transfer agent.
  • the number average molecular weight (Mn) of the copolymer (B) is preferably from 3,000 to 300,000, more preferably from 10,000 to 300,000.
  • Mn of the copolymer (B) is at least 3,000, the toughness of a coating film may easily be maintained.
  • Mn of the copolymer (B) is at most 300,000, formation of a film or sheet becomes easy.
  • Mn of the copolymer (B) is preferably from 3,000 to 30,000. In a case where it is used as a film or sheet, Mn of the copolymer (B) is more preferably from 10,000 to 100,000.
  • the molecular weight distribution (Mw/Mn) of the copolymer (B) is preferably from 1 to 3, more preferably from 1 to 2. When Mw/Mn of the copolymer (B) is at most 3, an improvement in the coating productivity or an improvement in the film strength can be expected.
  • R 1 in polymerized units based on the vinyl ether (b) in the copolymer (B) obtained in the above polymerization step is substituted with a hydrogen atom by a deprotection reaction to form a hydroxy group, whereby the polymerized units based on the vinyl ether (b) are converted to polymerized units based on vinyl alcohol, to obtain the copolymer (A) having polymerized units based on the fluoroolefin (a) and polymerized units based on vinyl alcohol.
  • R 1 in polymerized units based on the vinyl ether (b) in the copolymer (B) may be substituted with a hydrogen atom by the deprotection reaction.
  • a deprotection reaction of a protected alcohol by an acid, heat or light which is commonly carried out, may be employed.
  • the acid to be used for the deprotection reaction may, for example, be an inorganic acid such as sulfuric acid, hydrochloric acid or nitric acid, or an organic acid such as acetic acid, butyric acid or trifluoroacetic acid.
  • an inorganic acid such as sulfuric acid, hydrochloric acid or nitric acid
  • an organic acid such as acetic acid, butyric acid or trifluoroacetic acid.
  • the deprotection reaction by an acid is preferably (1) a deprotection reaction in a mixed solution of sulfuric acid/ethanol/water, (2) a deprotection reaction in a mixed solution of hydrochloric acid/dioxane or (3) a deprotection reaction in a mixed solution of trifluoroacetic acid/methylene chloride.
  • the deprotection reaction by an acid is not particularly limited to the reaction system of the above (1) to (3) and may be carried out in an aqueous system or in a non-aqueous system.
  • the deprotection reaction by an acid may be carried out by using a photo-acid-generator which generates an acid under irradiation with light.
  • a photo-acid-generator may, for example, be an onium salt, a halogenated compound, a diazoketone compound, a sulfone compound or a sulfonic acid compound.
  • a specific example may, for example, be diphenyl iodonium triflate, triphenyl sulfonium triflate, phenyl-bis(trichlorimethyl)-s-triazine, methoxyphenyl-bis(trichloromethyl)-s-triazine, 4-trisphenancyl sulfone or 1,8-naphthalenedicarboxylic acid imide triflate.
  • the deprotection reaction may be terminated halfway before all of protective groups in the copolymer (B) are deprotected, to obtain the copolymer (A) having polymerized units based on the fluoroolefin (a), polymerized units based on the vinyl ether (b) and polymerized units based on vinyl alcohol.
  • the ratio of polymerized units based on the vinyl ether (b) to polymerized units based on vinyl alcohol by terminating the deprotection reaction halfway, it is possible to adjust the hydrophilicity, crystallinity, etc. of the obtainable copolymer (A).
  • a factor whereby the deprotection by an acid proceeds at a sufficient reaction rate is considered to be such that the etheric oxygen atom of the vinyl ether (b) is likely to more readily undergo protonation than the acetic acid group of vinyl acetate.
  • the fluoroolefin and vinyl acetate are randomly copolymerized, whereby the alternating copolymerizability of the two monomers is low. And, the positions of hydroxy groups in the fluoroolefin/vinyl alcohol copolymer obtainable from such a fluoroolefin/vinyl acetate copolymer, are also random.
  • the properties are non-uniform as between portions where the proportion of polymerized units based on the fluoroolefin is high and portions where the proportion of polymerized units based on vinyl alcohol is high, and accordingly, the water resistance and heat resistance tend to be low.
  • the fluoroolefin (a) and the vinyl ether (b) or vinyl ether (c) are substantially alternately polymerized, whereby hydroxy groups will be uniformly distributed in the polymer chain. Therefore, hydroxy groups are not concentrated at specific sites, and it is possible to prevent that hydrophilicity of specific portions of the polymer chain becomes extremely high, and the copolymer (A) will exhibit excellent water resistance. Further, in the copolymer (A), polymerized units based on vinyl alcohol are not concentrated at specific sites, whereby excellent heat resistance can readily be obtainable.
  • the heat resistance of the copolymer (A) can be evaluated by the later-described 10 mass % thermal decomposition starting temperature (hereinafter referred to also as “Td 10 [° C.]”).
  • the 10 mass % thermal decomposition starting temperature of the copolymer (A) obtainable by the present invention is preferably at least 340° C., more preferably from 360 to 400° C.
  • the copolymer (A) in a case where the copolymer (A) is used as a coating material, it is possible to form a coating film having hydroxy groups uniformly arranged. Further, from a composition comprising the copolymer (A) and a curing agent such as melamine or isocyanate reactive with hydroxy groups, it is possible to form a film or coating film made of a cured product having a crosslinked structure. In such a case, it is also possible to obtain such an effect that by uniformly distributing hydroxy groups without using the vinyl ether (c), the reactivity of hydroxy groups can be constantly obtained.
  • a curing agent such as melamine or isocyanate reactive with hydroxy groups
  • timing for carrying out the deprotection step is not particularly limited, and for example, a composition obtained by mixing the copolymer (B), a component such as an acid to be used for the deprotection reaction and a curing agent, etc. is formed into a film or sheet and then light or heat is applied to form hydroxy groups to obtain a film or sheet made of a cured product having a crosslinked structure. That is, in such a case, the vinyl ether moieties in the copolymer (B) may be used as potential curing moieties.
  • the number average molecular weight (Mn) and the molecular weight distribution (Mw/Mn) of a copolymer obtained in each Example were measured by gel permeation chromatography (GPC) using a high speed GPC apparatus “HLC-8220GPC” manufactured by Tosoh Corporation. Their values are calculated values using polystyrene as standard substance. As the eluent, tetrahydrofuran was used.
  • the glass transition temperature of a copolymer was measured by using “DSC Q-100” manufactured by TA Instruments Japan Inc., in a N 2 gas atmosphere at a temperature raising rate of 10° C./min.
  • the 10 mass % thermal decomposition starting temperature of a copolymer was measured by using TGA Q-500 manufactured by TA Instruments Japan Inc., in air at a temperature raising rate of 10° C./min.
  • copolymer composition of a copolymer was calculated from the fluorine mass analytical values of the copolymer. However, in Example 6, the calculation was made by further combining the results of 13 C-NMR measurement.
  • TFE tetrafluoroethylene
  • a fluoroolefin (hereinafter referred to as “TFE”)
  • TFE tetrafluoroethylene
  • the pressure at that time was 1.56 MPa.
  • polymerization was continued for 7 hours, and when the pressure decreased to 1.12 MPa, the autoclave was cooled with water, and non-reacted TFE was purged to terminate the polymerization.
  • the obtained polymer solution was put into methanol to precipitate the formed copolymer B1, followed by vacuum drying.
  • the yield of the copolymer B1 was 22.0 g, and the conversion of the monomers was 41%.
  • the 13 C-NMR spectrum of the copolymer B1 is shown in FIG. 1(A)
  • the IR spectrum is shown in FIG. 2(A) .
  • the copolymer B1 obtained in Example 1 was used.
  • the copolymer B1 obtained in Example 1 was used.
  • the deprotection step was carried out in the same manner as in Example 1 except that the copolymer B2 was used, to obtain copolymer A4.
  • the deprotection step was carried out in the same manner as in Example 1 except that the copolymer B3 was used, to obtain copolymer A5.
  • the deprotection step was carried out in the same manner as in Example 1 except that the copolymer B4 was used, to obtain copolymer A6.
  • the alternating copolymerization rate of the copolymer C1 was from 80 to 85% by a calculation from the copolymerization reactivity ratio of both monomers.
  • the copolymer C1 obtained in Comparative Example 1 was used.
  • the deprotection reaction was attempted under the same conditions as in Example 1 by using the copolymer C2. After heating and stirring for 48 hours, copolymer D3 was recovered and vacuum dried. The copolymer D3 was analyzed by the IR spectrum, whereby it was found that there was no change in the spectrum as between before and after the reaction, and the deprotection reaction did not proceed. That is, the copolymer D3 was the same copolymer as the copolymer C2.
  • TFE/TBVE 21600 1.67 34 341 19100 1.77 75-80 366 207 Nil Ex. 2
  • TFE/TBVE 21600 1.67 34 341 19500 1.91 75-80 365 206 Nil Ex. 4
  • the copolymers (A 1 to A 4 ) in Examples 1 to 4 produced by using the vinyl ether (b) had no coloration and had a high quality. Further, the copolymers (A 1 to A 6 ) obtained in Examples 1 to 6 had high 10 mass % thermal decomposition starting temperatures and were excellent in heat resistance.
  • the copolymers (D 1 and D 2 ) in Comparative Example 1 and 2 produced by using vinyl acetate had lower 10 mass % thermal decomposition starting temperatures as compared with the copolymers (A 1 to A 4 ) in Examples 1 to 4 and were inferior in heat resistance. This is considered to be such that since polymerized units based on vinyl acetate were consecutively arrayed, portions where polymerized units based on vinyl alcohol were consecutively arrayed, were formed, and such portions were likely to be broken by heat.
  • the deprotection step by an acid in Comparative Example 1 required 72 hours and thus was inferior in the productivity as compared with 12 hours as required in the deprotection step by an acid under the same conditions in Example 1.
  • copolymer D2 in Comparative Example 2 produced by hydrolyzing the copolymer C1 produced by using vinyl acetate, under a basic condition, was inferior in quality with coloration to yellow observed.
  • the copolymer (A) obtainable by the process of the present invention is useful as e.g. a raw material for coating material excellent in weather resistance and transparency, an optical material excellent in transparency, a gas/liquid separation film material excellent in water resistance, a gas barrier material, a sealing material for solar cells, a material for various surface protective sheets, a hydrophilic porous material, etc.

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US20140187699A1 (en) * 2011-10-05 2014-07-03 Asahi Glass Company, Limited Composition comprising fluorinated olefin/vinyl alcohol copolymer and alkoxysilane, compound, cured product formed from said composition, and film comprising said cured product
US20150021261A1 (en) * 2011-12-28 2015-01-22 Daikin Industries, Ltd. Porous polymer membrane
US20160145369A1 (en) * 2013-06-26 2016-05-26 Daikin Industries, Ltd. Composition, porous polymer membrane and hydrophilic agent
US9702837B2 (en) 2014-12-02 2017-07-11 Kuwait Institute For Scientific Research System for measuring glass transition temperature of a polymer

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US9624325B2 (en) * 2011-10-05 2017-04-18 Honeywell Intenational Inc. Curable fluorocopolymer formed from tetrafluoropropene
JP6127976B2 (ja) * 2011-10-05 2017-05-17 旭硝子株式会社 含フッ素オレフィン／ビニルアルコール共重合体の製造方法および該共重合体を含む組成物から成形してなるフィルムの製造方法
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JP6455507B2 (ja) 2014-03-10 2019-01-23 Ａｇｃ株式会社 塗料用組成物、溶剤系塗料、水系塗料、粉体塗料および塗装物品
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WO2018118493A1 (fr) * 2016-12-20 2018-06-28 3M Innovative Properties Company Copolymères partiellement fluorés dérivés d'allyléthers fluorés
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US20150021261A1 (en) * 2011-12-28 2015-01-22 Daikin Industries, Ltd. Porous polymer membrane
WO2014084356A1 (fr) * 2012-11-30 2014-06-05 旭硝子株式会社 Membrane de séparation comportant un copolymère contenant du fluor
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