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WO2002079274A1 - Procede de production de fluoropolymere et son derive, et utilisation d'un derive de fluoropolymere - Google Patents

Procede de production de fluoropolymere et son derive, et utilisation d'un derive de fluoropolymere Download PDF

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Publication number
WO2002079274A1
WO2002079274A1 PCT/JP2002/003213 JP0203213W WO02079274A1 WO 2002079274 A1 WO2002079274 A1 WO 2002079274A1 JP 0203213 W JP0203213 W JP 0203213W WO 02079274 A1 WO02079274 A1 WO 02079274A1
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Prior art keywords
fluorine
polymer
monomer
atom
group
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English (en)
Japanese (ja)
Inventor
Daisuke Shirakawa
Takashi Okazoe
Takashige Maekawa
Kazuya Oharu
Masao Unoki
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2002577897A priority Critical patent/JP4214378B2/ja
Publication of WO2002079274A1 publication Critical patent/WO2002079274A1/fr
Anticipated expiration legal-status Critical
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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
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/22—Esters containing halogen
    • 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
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/24—Haloalkylation

Definitions

  • the present invention relates to the production of an industrially useful fluorine-containing compound and a derivative thereof, and the use of the fluorine-containing compound obtained by using the same.
  • the method is to fluorinate all of the C-H moiety into C-F using fluorine gas. There are known ways to do this.
  • such a polymer compound is usually a solid or a liquid at room temperature, and it is difficult to perform mochi glueing.
  • a perfluorinated organic solvent is usually used as an inexhaustible solvent.
  • the solubility of the polymerized polymer in the perfluorinated organic solvent is low, and the Of course, the organic matter is insoluble. Therefore, as an auxiliary IJ for dissolving the C-H-containing polymer, it is possible to dissolve the C-H-containing polymerized ⁇ ), and to use a powerful, perfluorinated, male-soluble auxiliary sickle (for example, ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ .
  • Males also use fluorine gas Since it is consumed and fluorinated, the fluorinated polymer has an insufficient $ ⁇ power ratio, which is not economical. Also, when the boiling point of the forehead lj was low, the auxiliary solvent fluorine MS occurred in the eyes, and there was a problem that control of S ⁇ was difficult.
  • the ISA of the present invention has previously shared the process (1) to (4) involving liquid-phase fluorine bKiS as a method for inexpensively and efficiently producing a polymerizable fluorine-based monomer (WO O0 / 5 6 6 9 4).
  • a fluoropolymer is produced at a lower production cost.
  • Manufacture is required.
  • the present invention provides a method for economically converting a fluorine-containing polymer having various nuclei into a lj (e.g., an IJ method for industrial implementation).
  • fluorine-containing polymer capable of reducing the amount of fluorine is also carried out.
  • fluorine-containing polymer produced by the present invention a useful derivative obtained from the book is also referred to as “r» T.
  • the present inventors have found that the above-mentioned liS can be solved by a method including a polymerization step involving a partially fluorinated monomer and a fluorination step performed after the polymerization step, leading to the present invention. . That is, the present invention provides the following.
  • Fluorine-containing polymerization step including the following Sfi synthesis step and the following fluorination step performed after the polymerization step: a monomer () having a fluorine atom as a carbon atom and a hydrogen atom as a carbon atom is obtained. Polymerizing the tflt monomer ( ⁇ ) and a comonomer (j) copolymerizable with the monomer ⁇ ).
  • Fluorination step A partial fluorine-tfi union having a carbon atom and a fluorine atom bonded to a carbon atom and having an element atom is dissolved in a solvent of fluorine and then subjected to liquid-phase fluorination to obtain an understanding. Replacing one or more of the hydrogen atoms bonded to carbon atoms in the fluorinated polymer with fluorine atoms; m
  • the polymerization reaction in the polymerization process is a forced D polymerization reaction.
  • Monomer synthesis step A monomer having a hydrogen atom bonded to a carbon atom and an optional (Y 2 ) — ( ⁇ ) is reacted with the optional (Y 2 ) to form a linkage or a linking group (Y 1 ) and a fluorine-containing compound having a fluorine atom bonded to a carbon atom. 5.
  • the average molecular weight of the partial fluorine b ⁇ coalescing is 100 or more; ⁇ 4 of! / TS m listed on either side
  • partially fluorinated fluorine content of I ⁇ coalescence is 3 0-7 0 weight 0/0, and a full Tsu ⁇ kinematic 3 5 mass 0/0 or more of the fluoropolymer, force, partially fluorinated ⁇
  • the male product i * fe according to any one of claims 1 to 5, wherein the amount is larger than the volume of the imaginary unit.
  • a partially fluorinated polymer is a polymer that essentially has 1 fluorine bonded to the polymer side chain with an ester ⁇ , and the fluorinated polymer is partially fluorinated heavy ⁇ (hydrogen bonded to the carbon atom).
  • the 3t ⁇ according to any one of claims 1 to 8, wherein at least one of the atoms is a fluorine-containing polymer which is difficult to be a fluorine atom and which has an ester ⁇ in a polymer side chain.
  • Monomer ( ⁇ ) force A monomer having s (meth) acryloyloxy group and i-plane fluorinated; Fiber, and partially fluorinated heavy is required to have a repeating unit of the monomer. It is a polymer in which the fluorine-containing polymer has a fluorine atom bonded to a carbon atom in a double ill, and has a monovalent fluorine-containing organic group linked to the side chain of the polymer by an ester bond.
  • the fluorine-containing heavy obtained by the process of claim 10 (in the present invention, the heavy-weight (the conversion of a side chain ester into a single COF group is referred to as a heavy-weight, A polymer having a fluorine atom bonded to a carbon atom in the "
  • a hydroxylated compound having a fluorine-free monovalent ⁇ and a water ⁇ in one C ⁇ F group of the polymer side chain is provided.
  • the polymer odor has a fluorine atom bonded to a carbon atom. Fluorine-free polymers bonded by a bond
  • the monomer in the present specification refers to a compound having a polymerizable group (S-compatible monomer).
  • the number of polymerizable groups in the monomer is one or more, and one is preferable.
  • Examples of the monomer include ⁇ (1) a monomer polymerized by the opening of an inedible bond (so-called addition polymerization I. raw monomer) ”and“ (2) a monomer polymerized by both bonds of the bond (so-called ring-opening polymerization) And (3) a monomer polymerized by the movement or movement of an atom or an atomic group.
  • Examples of the monomers polymerized in the two rows S in (2) include cyclic ethers, cyclic lacquers, lactams, ratatone, and cycloparaffins.
  • Examples of monomers that polymerize by the recitation or transfer of atoms or atomic groups include compounds that polymerize by polycondensation reaction, polyaddition, acid tat formation, transfer polymerization, or swelling. And diamines, dicarboxylic acids, diisocyanates, phenols, diazomethanes and the like.
  • the polymer refers to a polymer composed of two or more thighs (also referred to as repeating units) formed by polymerization, and is synthesized by polymerization ⁇ S.
  • the polymer may be a compound which is difficult to obtain by polymerization, or a compound obtained by performing chemical conversion on the part of the key formed by polymerization 0 & then polymerization ⁇ ). Les ,.
  • the number of repeating units in the polymer may be one, or two or more.
  • the term “increase” refers to a group that essentially requires a carbon atom, and may be a saturated group or an unsaturated group.
  • a fluorine atom or an atom is preferable. The monovalent!
  • ⁇ may be an alkyl group, an ether I "alkyl group containing a hydrogen atom, a cycloalkyl group, an ether (a cycloalkyl group containing a natural atom, or one or more of the ⁇
  • the divalent s include an alkylene group, an alkylene group containing an aethenole atom (for example, an oxyalkylene group, a polyoxyalkylene group, and a 7-alkyleneoxy group).
  • Noreqylene or a group in which at least one hydrogen atom in these groups is substituted with a halogen atom is preferred, and the number of occupied carbon atoms is preferably 1 to 20 S, particularly:! S preferred ,.
  • the (acryl) / le group and the methacryloyl / le group are referred to as (meth) atalyloyl group, and acrylic acid and methacrylo are collectively referred to as (meth) acrylino V3 ⁇ 4.
  • (meth) atalyloyl group acrylic acid and methacrylo are collectively referred to as (meth) acrylino V3 ⁇ 4.
  • acrylic acid and methacrylo are collectively referred to as (meth) acrylino V3 ⁇ 4.
  • the monomer forming step, the polymerization step, and the fluorinating step in the present invention will be described in order.
  • the monomer formation step is a step in which a specific fluorinated / is added to the monomer (().
  • the specific fluorine-containing compound is a compound having both a reaction (Y 1 ) capable of forming a chain, a male bond or a linking group as 4 ( ⁇ ) and a fluorine atom bonded to a carbon atom. .
  • the bond formed by ( ⁇ 1 ) and the combination of ( ⁇ 2 ) and force include a single bond, a double bond, and a triple bond, and the ⁇ ⁇ group includes a ⁇ bond, a ⁇ —, S— and the like.
  • the valence of the keyed link is not particularly ⁇ knee, and the valency of more than two valleys can be fought.
  • one of ⁇ 1 and ⁇ 2 is CO X 1 (X 1 is a halogen atom or a water atom, preferably a halogen atom, more preferably a special atom or a fluorine atom, particularly preferably a fluorine atom.
  • the ⁇ —c 3 monomer () is preferably a monomer S which is classified as an unfavorable S (1) or an unpleasant (2), and is particularly preferably an addition-polymerized monomer classified as a sui (1).
  • the monomer () is a non-fluorine-based monomer that does not contain a fluorine atom in ⁇ 3 ⁇ 4t.
  • Monomers ( ⁇ ) classified as disgusting (1) include one addition-polymerizable group, one ⁇ S ⁇ 4S (Y 2 ), and one or more hydrogen atoms bonded to carbon atoms. Having compound power S preferred.
  • Specific examples of the monomer () include the following compound power S.
  • R ⁇ represents a hydrogen atom or a methyl group
  • X 1 has the same meaning as that of the self
  • Q 1 and Q 2 each represent a single ⁇ or divalent linking group (2 As the valence linking group, an alkylene group is preferable.)
  • M represents a continuation of 2 to
  • p represents a difficulty of 2 to 5
  • r represents a fiber of 1 to 4.
  • the monomer () is CH 2 CHC (a monomer having a part of R)
  • R 1 is a hydrogen atom
  • examples of the monomer (H) classified into mm (2) include unreacted monomers, and specific examples thereof include a monomer having a glycidyl group, preferably Y 2.
  • -OH is G— (CH,) k kH, etc. (however, G represents a glycidyl group, and k is a discipline of 0 to 5).
  • the compound power represented by S is preferred L,.
  • Fluorine-containing compound has an R F group after Te Contact V, and the fluorination step of, may be an important group the R F group is improve the solubility in a solvent of the fluorine I partially fluorinated I coalesce.
  • R F is a monovalent organic group having one or more fluorine atoms bonded to a carbon atom, and is particularly preferably a group having a perfluorinated 1-radical (R 1F ).
  • R IF is preferably a perfluoroalkyl group or a Perf / Leo port (ether I "alkyl containing a hydrogen atom) group.
  • R 1F examples include the following example S.
  • groups corresponding to the groups having the respective structural isomers are also included.
  • R F other than R 1F is HC t F 2t — (t is 1 or more) force S.
  • Y 1 is set if the Y 2: more suitable 3 ⁇ 4T: is 13 ⁇ 4 notice.
  • the monomer (ratio) of Upsilon 2 Gar COX 1 (X 1 is ⁇ the same meaning as Yuki) (such as to TO a monomer represented by the ftjf yourself formula (alpha 11).)
  • the Y 1 of the fluorinated ⁇ is preferably 1 OH.
  • N represents n from! to 5, and preferably from 2 to 5. , 2 or 3 are particularly preferred.)) Represented by) is preferred.
  • the monomers in the (de) is the Y 2 gar OH ⁇ (Fuji oneself equation ( ⁇ using a model Nomar represented by the ratio 12) ⁇ like.), Gamma or one fluorinated compound CO X 1 ( X 1 has the same meaning as the restaurant itself.
  • fluorinated ⁇ # 1 in which Y 1 is -OH and 1 COX 1 include the following S).
  • n has the same meaning as described above.
  • R 1F COF for example, CF 3 CF 2 COF, CF 3 CF 2 CF 2 ⁇ CF (CF 3 ) COF, CF 3 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COF, etc.
  • R 1F COOH eg, CF 3 CF 2 COOH, CF 3 CF 2 CF 2 OCF (CF 3 ) CO OH, CF 3 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COOH, etc.
  • R 1F (CH 2 ) n OH for example, CF 3 CF 2 CH 2 OH, F (CF 2 ) 4 CH 2 CH 2 OH, F (CF 2 ) 6 CH 2 CH 2 OH, F (CF 2 ) 8 CH 2 CH 2 OH etc.).
  • a fluorine-containing compound in which Y 1 is —CO F can be obtained from a commercially available product, produced by a method described in WO 00/56694 by the present applicant, or obtained by ester bonding described below. ) Can be obtained.
  • Examples of the monomer (hereinafter referred to as monomer ( ⁇ ′)) in the reaction in the monomer synthesis step include the following formulas. However, RR 1F , G, n and k in the following formula have the same meaning as above.
  • the monomer ( ⁇ ') can be obtained from the product of the monomer synthesis step by performing ordinary purification. Obtaining the monomer ( ⁇ ) used in the subsequent polymerization step: The removal is not limited, but the monomer ( ⁇ ,) that is used in the monomer formation step is composed of a fluorine atom bonded to a carbon atom and a carbon atom A monomer having a bonded hydrogen atom and can be used as a monomer (
  • the monomer ( ⁇ ) in the polymerization step in the present invention is preferably a monomer obtained via a monomer synthesis step.
  • the reason is that both monomers ( ⁇ and fluorinated compounds) can be obtained inexpensively and inexpensively by using compounds having various structures. This is because various types of monomers ( ⁇ ) can be synthesized by obtaining ⁇ ′) and, if necessary, performing chemical conversion on the monomer ( ⁇ ′).
  • the age at which the monomer (13 ') undergoes a chemical transformation is likely to be affected by the chemical transformation at a portion other than the polymerization I "showing raw".
  • Linking group or a communication is formed from Upsilon 1 and Upsilon 2 Metropolitan monomer (beta '), it may be changed by the chemical transformation.
  • the fluorine atom bonded to the carbon atom in the monomer ( ⁇ ,) is very powerful before and after the ⁇ ichological transformation.
  • Examples of such chemical transformations include the alkylation of a hydrogen atom to a nitrogen atom, and the protection of Mizuto's water.
  • the polymerization step is a step of polymerizing a monomer (or a step of copolymerizing a monomer (j3) and a copolymerizable comonomer (j).
  • the monomer ( ⁇ ) is preferably 14 polymerizable in addition polymerization, and i is particularly preferably an addition polymerizable monomer having a fluorine organic group (R F ). Further, the monomer ( ⁇ ) is preferably a monomer ( ⁇ 1 ) which is a monomer ( ⁇ 1 ) linked by an unsaturated group in addition polymerization and a divalent group which requires a force esterification. As the monomer ( ⁇ 1 ) which essentially contains the ester ⁇ , a monomer represented by the following formula ( ⁇ ⁇ -1) or a monomer represented by the following formula (/ 3 1 -2) is preferable.
  • Examples of the monomer represented by - (1 ⁇ ), (meth) ⁇ methacryloyl Ruo alkoxy group and force S preferably of are monomers having a monovalent fluorine-containing organic s, the following formula wherein - in (I3 1 10)
  • the monomer power represented by S is particularly preferred, and a monomer represented by the following formula ( ⁇ -11) is particularly preferred.
  • Examples of the monomer represented by the following formula (i 3 1 -2), a monomer represented by the following formula (J 8 1 -20) are preferred, particularly the formula - Mashi monomer force child represented by ( ⁇ 21) No.
  • U represents an unsaturated group in addition polymerization
  • Q 1 and Q 2 may be the same or different, may represent a single bond or a divalent linking group, and may represent R 1 hydrogen atom or Represents a methyl group
  • R F and R 1 F have the same meanings as described above
  • p represents a fiber of:! To 5, preferably 2 to 5, and particularly preferably 2 or 3.
  • k indicates a key female of 0 or more, and a fiber of 1 to 5 is preferred.
  • ⁇ 2 ⁇ ⁇ one C ⁇ one Q 2 — R F ⁇ ⁇ ⁇ ( ⁇ '-10)
  • the monomer () having an ester bond is a monomer that can be copolymerized with various comonomers (j). Further, the monomer (J3 1) is of the polymerization method, since it 3 ⁇ 43 ⁇ 4 and easily Polymerization is a monomer capable of producing a heavy ⁇ (book having various structures. Further, the monomers
  • a monomer represented by the formula (J3 1 — 11) is a compound represented by CH 2 CC (R 1 ) COX 1 (where R 1 X 1 has the same meaning as leakage) and R It is preferable to obtain the compound represented by 1F— (CH 2 ) ⁇ OH (wherein, R 1F and n have the same meaning as in Kagome).
  • the monomer ( ⁇ 1 ) include the following compounds. However, in the following formula, m indicates 1-12, and R 1 , p, and k have the same meaning as above.
  • CH 2 C (R 1 ) COO (CH 2 ) P (CF 2 ) MF ,
  • CH 2 C (R COO (CH 2 ) M OCO (CH 2 ) K (CF 2 ) M F,
  • CH 2 C (R 1 ) OCO (CH 2 ) K (CF 2 ) expectF.
  • the polymerization step is a step of polymerizing the monomer ( ⁇ ) or a step of copolymerizing the monomer (j3) with the comonomer (j).
  • the polymerization of only the monomer ( ⁇ ) may be used, and only one type of the monomer ( ⁇ ) may be used, or two or more types may be used.
  • the monomer (/ 3) and the comonomer (j) are copolymerized.
  • the monomer (j3) may use only one kind or two or more kinds, and the comonomer (j) uses only one kind. Also, two or more kinds may be used.
  • the comonomer (j) may or may not be covered by the C-H portion. It is preferable to use a force that is not covered by fluorine atoms.
  • Examples of the comonomer (j) include ethylene, vinylidene chloride, biel chloride, styrene, dimethinolestyrene, p-methynolestyrene, butadiene, isoprene, and olefins such as chloroprene; Daricidyl (meth) acrylate, (meth) acrylamide , N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, N-methylol (meth) acrylamide, aziridinyl ethyl (meth) acrylate, benzyl (meth) acrylate, Aziridinyl (meth) acrylate, polyoxyethylene mono (meth) acrylate, methyl polyoxyalkylene (meth) acrylate, 2-ethylhexyl polyoxyanoxylene (meth) acrylate
  • the comonomer (j) vinyl chloride and an alkyl having 8 to 20 carbon atoms and an alkyl.
  • (Meth) acrylate are preferable. Particularly, biel chloride, stearyl (meth) acrylate and dioctyl are preferred. Maleate or 2-ethynolehexinole (meth) atarylate is preferred.
  • the monomer (j), which is a monomer ( ⁇ ) -force S (meth) acrylate is preferably selected from (meth) acrylates or butyl chloride in terms of yield, especially Scaling force from acrylates is preferred.
  • the monomer ( ⁇ ) is preferably used in an amount of 50 to 100 mol% based on the monomer 4 to carry out the polymerization.
  • the polymerization method of the monomer ( ⁇ ) is In other words, ⁇ mouth polymerization SJ3 ⁇ 4 method can be applied as it is.
  • a monomer ( ⁇ - ⁇ ) having a (meth) atalyloxy group can be easily polymerized according to the conditions and methods of milky mouth.
  • a polymer corresponding to the used monomer is obtained.
  • the number of repeating units in the m book is two or more.
  • the manner of connecting the intertwined units of ⁇ is not particularly limited, and examples thereof include block-like, random-like, and graft-like connecting methods.
  • the molecular weight of the polymer to be subjected to the polymerization in the polymerization step is preferably 1000 or more, more preferably 100 to 100,000.
  • the polymer contained in the product of the polymerization step may be purified according to the purpose, or may be used as it is in the next step, etc., but it may be used in the next fluorination step. From the standpoint of performing stable purification, the power of purification is preferred.
  • As a refinement method it is desirable to separate the polymer in the product and the polymerization nada by a vehicle or the like. Furthermore, after dissolving all of the 'M product, it is possible to dissolve the monomer used in the polymerization step and the sulfide, and to precipitate the polymer obtained in the polymerization step. ⁇ After dripping the lumps of material and letting the polymer regenerate,? It is preferable to purify the polymer by filtering off the product, returning the product, and removing the nada from the product by drying.
  • the following polymer contains a repeating unit of the monomer (j3). Further, in the polymerization step, the comonomer (j) was copolymerized: 3 ⁇ 4 ⁇ includes a polymerized unit of the comonomer (j) in the polymer.
  • the polymer obtained in the polymerization step may be used as it is as a partially fluorinated idi combination in the fluorination step, or may be used as a partially fluorinated polymer in the fluorination step after chemical conversion.
  • the polymer obtained in the polymerization step contains a repeating unit of a comonomer (j 2 ) having a functional group: ⁇ protects the origin of the comonomer (j 2 ) in the polymer obtained in the polymerization step.
  • the compound protected with a group may be used as a partially fluorinated polymer in the fluorination step.
  • the window guard can be deprotected after the subsequent fluorination step, if desired.
  • the partial fluorine-S union needs to have a hydrogen atom aged to a carbon atom and a fluorine atom bonded to a carbon atom, and the chemical conversion is caused by polymerization H ⁇ . It is a transformation that does not change the formed.
  • the partial fluorine I around coalescence is preferably a polymer having repeating units of Iyaonore monomer (beta, in particular (meth) polymer having a Repetition rate units of monomer (1 one 1 0) having an Atari Roy Ruo alkoxy group Les, especially preferred.
  • the partially fluorinated polymer obtained through the polymerization process is dissolved in a fluorinating agent and then fluorinated in a liquid phase to bind to the carbon atoms in the partially fluorinated kfi polymer.
  • This is a step of converting one or more of the hydrogen atoms thus obtained into fluorine atoms.
  • a partially fluorine-fi-union is a double bond having a fluorine atom bonded to a carbon atom and a hydrogen atom converted to a carbon atom.
  • the polymer obtained by chemical conversion may be used.
  • Such a book has a fluorine atom, and since it has fluorine atoms, it dissolves in the form of fluorine b®, so it is not necessary to shelf a submarine that consumes fluorine gas. Without fluorination in a uniform state.
  • the partial fluorine ikfi coalescence in the present invention has a fluorine content that is adjusted as desired, and the fluorine-containing heavy ⁇ (the fluorine-containing heavy ⁇ (which can be converted into a book at the cost of manufacturing the book). It is a book.
  • the partially fluorinated polymer is dissolved in the fluorinated bSjS, which forms a liquid phase at the time of fluorination, to perform liquid phase fluorination.
  • fluoride-t®S Nada fluoridity conditions!
  • the partially fluorinated polymer is dissolved in the fiber of fluorine by 0.1% by mass or more, and in particular, the dissolution is preferably by 0.5% by mass or more.
  • the upper limit of the melting I "of the partial fluorine-bfi coalescence over the sea is 50 mass for anyone. It is preferable to be / 0. The sickle of fluorine is later.
  • the fluorine content of the partially fluorinated polymer is 35 mass 0 /.
  • the force is more than S preferred, 5 0 mass 0 /. That's the power of S preferred.
  • Fluoride ⁇ amount Shi preferable not less 6 5 mass 0/0 following les. If the amount of fluorine is too small, the solubility of fluorine in water becomes very low, and the fluorination system becomes non-uniform. There is no upper limit on the amount of fluorine, but if it is too high, it is not economical.
  • the partially fluorinated heavy ⁇ (the molecular weight of the book is preferably 100,000 or more s, more preferably 100,000 to 500,000, particularly 100,000 to 100,000. Partial fluorine merging has the advantage that it can not be entrained in the rice cake, has a large amount in the SS, and can reduce the amount of the fluorine in the forehead. If the amount is too large, dissolution of fluorinated slag in a certain amount is likely to occur. On the other hand, if the molecular weight is too small, the resulting fluoropolymer tends to have a lower glass transition ( ⁇ ⁇ ) force s, and the like, and it is difficult to obtain the physical property force s required for the polymer.
  • Partial fluorine merging has the advantage that it can not be entrained in the rice cake, has a large amount in the SS, and can reduce the amount of the fluorine in the forehead. If the amount is too large, dissolution of fluorinated slag in a certain amount is likely to
  • Liquid-phase fluorine itSi ⁇ is carried out by allowing a partial fluorine-containing compound to exist in the liquid phase formed by the fluorine-containing spirit and introducing fluorine gas into the liquid fluorine-containing compound.
  • a partial fluorine-containing compound By the liquid phase fluorine, one or more of the hydrogen atoms converted to carbon atoms in the partial fluorine are replaced with fluorine atoms, and the fluorinated polymer is formed.
  • a fluorine atom may be added in some cases.
  • fluorine is obtained by fluorinating all of the hydrogen atoms bonded to carbon atoms in the partially fluorinated polymer (that is, completely fluorinated).
  • Fluorine is the fluorination rate (the fluorination rate is the partial fluorination weight
  • the force S is such that the elimination of fluorine atoms introduced by fluorine based on the number of hydrogen atoms in the coalescence is 40 mol% or more.
  • the upper limit of the fluorination rate is 100%.
  • the fluorination ratio is particularly preferably 4 0-9 5 mol 0/0.
  • hydrofluoric ⁇ ⁇ Yuryou of the fluoropolymer is a amount greater than the fluorine content of the partially fluorinated Kakasane ⁇ f present, 3 5 preferably has a weight of 0/0 or more, 7 0 wt% or more It is particularly preferred that the content be 86% by mass or less.
  • the fluorine of the present invention it is preferable to carry out the fluorine at a low temperature in order to reduce the number of carbon atoms which form heavy f atoms between the carbon atoms S as small as possible. Especially — 50 ° C to 0 ° C. It's better to do it in C.
  • the force of performing further fluorine kKJ ⁇ at +10 to 150 ° C is preferable.
  • the power of the system to make the system more calorie when the impeachment is heated S is preferable, and the system is preferably made to be +0.1 to +0.3 MPa calo pressure. .
  • kRiS it is possible to dissolve the coalescence of partial fluorine, and of the males, it can melt fluorine gas, but it does not contain C-H bond.
  • ⁇ norehnorero alka ⁇ ! perfluoroeeg, perfluoropolyethers (trade names: cittotus, fomblin, gano, n, demnum, etc.) (Trade name: Hunloop), Black phenolic polyethers, Perfunoleoalkylamine
  • the fluorine-containing polymer itself formed by the liquid-phase fluorine is capable of forming a liquid phase under the conditions of the liquid-phase fluorine ⁇ ): tj ⁇ includes the fluorine-containing polymer of fluorine ? It may be used as fiber.
  • the fluorine gas in the liquid-phase fluorine gas it is possible to use the fluorine gas as it is or to use the fluorine gas that has been deactivated by inert gas.
  • inert gas nitrogen gas, helium gas power S is preferable.
  • Nitrogen gas power S is particularly preferable for economic reasons.
  • the amount of fluorine gas in the gas is not particularly limited, and is preferred from the viewpoint of power S efficiency of not less than 10%, and power S of not less than 20% is particularly preferable.
  • the amount of fluorine to be used for fluorine is preferably such that the amount of fluorine is always equal to the hydrogen atom in the partial fluorine ibS union (the force to make it equivalent to J s is preferable, especially 1.5 times equivalent or more (that is,
  • the fluorine gas is continuously introduced into the system so that i! Ft ⁇ is maintained.
  • the RJ ⁇ ag of fluorinated kRi ⁇ is usually preferably in the range of 16 ° C or higher and not more than the boiling point of fluorinated k®3 ⁇ 4, from the viewpoints of 3 ⁇ 4yield, selectivity, and low industrial practice.
  • One hundred and fifty degrees ( ⁇ + 200 ° C is particularly preferable, and one hundred and twenty degrees to one hundred and ten degrees is particularly preferable.
  • the power of removing HF, such as 3 ⁇ 4 ⁇ , which contains the atoms of S is preferred: ⁇ In the initial stage of fluorine, the pressure is large near ⁇ E, and the force of removing HF quickly is reduced, .
  • the form of fluorine ifcR ⁇ is preferably:
  • the type is preferably wipe 2 described below in terms of yield and scale.
  • an inert gas such as nitrogen gas.
  • the amount of male of the fluorine which dissolves the partially fluorinated bfi coalescence is preferably 5% by mass or more with respect to the partial fluorine and bfi coalescence, and more preferably at least 10 times the mass.
  • Force S preferred.
  • the fluorine of bR ⁇ is preliminarily filled with fluorine of * in advance so that the fluorine becomes nada ij amount even at the start of the reaction.
  • HF In fluorine, hydrogen atoms are replaced by fluorine atoms, and HF force S is by-produced.
  • HF can be introduced into the system, or HF cat IJ and the exit gas can be wormed at the gas outlet. As a Na F child.
  • the amount of the HF withdrawal I in the system is preferably 220 ⁇ & l, preferably 1-5 l, with respect to the partial fluorine 1 ⁇ (the atomic weight of ⁇ k element covered in the book).
  • ⁇ To remove the gas from the gas outlet, remove the ⁇ by (h) Allow time to cool off (10. Power of C to room temperature S is preferable, especially power of about 20 ° C) S is preferred.) (I) N a F pellet (3 ⁇ 43 ⁇ 4) 1, and (j) cooler (between 178 ° C and + 10 ° C) Listen to (h) — (i) one (j)
  • a liquid return line ⁇ g is also available to return the ben- gin of ⁇ -fluoride from the vessel to ⁇ . It is particularly preferable that the liquid line be ⁇ s-, because it can suppress the rise of viscosity at night due to the effect of fluorine. It is desirable to supply fluorine-containing rosin to the inside to prevent the viscosity of the 3 ⁇ 4 system from increasing.
  • C-! ⁇ 3 ⁇ 4 ⁇ compounds must be added Q to the reaction system, or irradiation with ultraviolet spring must be performed. Is preferred.
  • the UV irradiation time is preferably 0.1 to 3 hours.
  • C—H3 ⁇ 45 ⁇ substantiated ⁇ it is measured from tandems ⁇ ) other than partially fluorinated polymers, and is preferably aromatic, particularly preferably benzene, toluene or the like.
  • the added amount of the C-H bond is preferably 0.1 to 10 mol /% with respect to the total number of hydrogen atoms in the partially fluorine bm ⁇ f, particularly preferably 0.1 :!
  • a preferred force S is ⁇ 5 mol%.
  • the C—H bond ⁇ enrichment ⁇ ) is the preferred force of the gas when it is exposed to the fluorine gas force S in the system.
  • the force of pressing the system is preferably S.
  • the pressure at the time of the calo pressure is preferably in the range of 0.01 to 5 MPa force S, whereby fluorine can be increased.
  • fluorinated ros at least partially fluorinated ⁇ (One or more of the hydrogen atoms bonded to the carbon atoms in the book are woven into fluorine atoms to form a fluoropolymer.
  • a partially fluorinated polymer may be a monomer ( 1 1 1 1) that is a repeating unit of 1 (CH 2 — C (R (COO (CH 2 ) p R 1 F ))-(where R p, and R 1 F has the same meaning as disgust.)
  • a polymer containing a repeating unit represented by at least one hydrogen atom bonded to a carbon atom in the unit is a fluorine atom
  • the partially fluorinated polymer is a polymer containing a repeating unit of a comonomer (j), and a hydrogen atom converted to a carbon atom in the repeating unit of the comonomer is a carbon atom!
  • At least some of the fluorinated atoms in the fluoridation process are partially or completely fluorinated.
  • a heavy compound in which a fluorinated compound is essentially composed of a 1-fluorinated group linked to a polymer side chain by an ester bond (depending on the age of the book, One or more of the hydrogen atoms bonded to the carbon atoms of the partially fluorinated polymer are replaced by fluorine atoms, and the fluorinated polymer is a fluorinated polymer that requires an esteno bond in the polymer side chain.
  • a partially fluorinated polymer is a compound having a repeating unit of a monomer having a (meth) acryloyloxy group and one fluorine atom, and is a heavy-f-unit.
  • the fluorine-containing polymer is a heavy chain having a fluorine atom having a carbon atom in the main chain of the polymer and having a 1-fluorine atom which is connected to the side chain of the polymer by an ester bond. Is particularly preferred.
  • the ability to remove the fluorinated Nada to obtain a polymer is preferable.
  • the compound can be used as it is or by derivatization to another chemical compound to obtain a useful polymer having properties in ffi.
  • various polymers can be derived by utilizing the properties of the ester bond. For example, by performing an ester bond ⁇ ⁇ , a polymer having one COF group in the polymer side chain can be derived.
  • the polymer having one COF group in the side chain of the Xiaolong body is preferably a polymer having a fluorine atom bonded to a carbon atom in the polymer main chain.
  • the ⁇ S condition of the ester bond can be adopted.
  • the fluorine-containing polymer is liquid under the && conditions for ester bond »S, heat it under NaF, CsF, KF, etc. Due to the strength of the ester, it is preferred.
  • the fluoropolymer is solid under the conditions of S ⁇ and solid ⁇ , the polymer is dissolved in Nada, where the polymer can be dissolved, and then dissolved in a solvent such as NaF, CsF, or KF. It is preferred that the ester bond be formed by heating under heating. As a reminder, it is necessary to reverse the fluoropolymer and to intercept from the male whose boiling point is higher than the key.
  • the polymer having one C ⁇ ⁇ ⁇ F group in the side chain can be subjected to esterification of the —COF group to obtain fluorine-containing polymers having various esterified groups.
  • the hydroxylated ⁇ include fluorine-containing compounds, hydroxylated compounds having monovalent ⁇ and water M3 ⁇ 4, and examples of so-called alcohols such as alcohols.
  • the conditions for the esterification can be applied to the conditions of the mouth, and examples include various hydroxylations ⁇ ) being converted to one COF group.
  • the polymer having one COF group in the side chain and the hydroquine compound are liquid under the condition of esthetic / ray fc®, and the liquid is preferable: ⁇ is the power of performing acetic acid in Nada. It also acts as a solvent for the hydroxy compound.
  • ⁇ Polymers with COF groups in the side chain and / or alcohol Being solid: ⁇ ? Fiber S (for example, dichloropentafluoropropane (R-225)) or the like is suitable for the force S to be applied. It is preferable that the fluorinated polymer and the alcono be dissolved and the boiling point be selected from those having a higher boiling point than the S-male of Esteroi.
  • the fluorine-containing polymer produced by the method of the present invention, or the fluorine-containing polymer (the polymer derivatized from the book contains a surfactant (J, wki oil repellent, coating j, lubricant, and It is a polymer useful as an agent.
  • a surfactant J, wki oil repellent, coating j, lubricant, and It is a polymer useful as an agent.
  • a polymer having a fluorine atom converted to a carbon atom in the polymerized f * 3 ⁇ 4i odor and having a monovalent organic group (R H ) containing no fluorine in the side chain of the polymer is bonded by an ester bond.
  • An impregnated material can be used as a coating.
  • the coating agent By applying the coating agent to the surface of the substrate after it is applied, excellent water and oil repellency can be exhibited, and a surface having a high strength and strength can be obtained.
  • the polymer is preferably a polymer produced by the method of the present invention when the monomer (] 3) is CH 2 CC (R 1 ) COO (CH 2 ) n R 1F . Furthermore, a repeating unit represented by the general formula [CX 10 X 20 — C (R 10 ) COORH] — (where X 10 and X 20 are each; M represents a hydrogen atom or a fluorine atom) , R 1 represents a hydrogen atom, a fluorine atom, or a fluorinated methyl group, and one or more groups selected from force, X 1 , X 2, and R 1Q are groups in which a fluorine atom is essential. is.
  • R H is a meaning same as ⁇ f.) force S preferred is heavy ⁇ (present essentially containing. the percentage of kindness units in the heavy ⁇ book 20-00 Monore 0/0 Further, it is preferable that the ratio of the fluorine atoms is 15 to 86% by mass, and it is particularly preferable that the ratio of the fluorine atoms be 35 to 86% by mass. It is preferably from 100,000 to 100,000, and especially from 1000 to 50,000.
  • fluorine-containing polymers having various structures and various amounts of fluorine can be easily produced.
  • the method of the present invention has a low production cost, Fluorine-containing polymerization is possible. ⁇ row
  • the average molecular weight is a number average molecular weight (H), which was measured by gel permeation chromatography (hereinafter referred to as GPC) and converted from a polymethylmetharylate sample.
  • GPC gel permeation chromatography
  • a solution in which 1-Vo 1% hexafenoleoloisopropinole alcohol was dissolved in R-225 was used as Togai night.
  • PL g e1 5 ⁇ M i — ed—C was used for the GPC column.
  • a 10 OmL flask having a dropping funnel at the top and having the inside preliminarily nitrided was considered.
  • F (CF 2 ) 4 CH 2 CH 2 OH (26.4 g), hydroquinone (0.1 g), and p-toluenesulfonic acid (1.72 g) were charged into the flask, and the pressure inside the system was reduced. (2 OkPa pressure)), and heated to 70 ° C. Subsequently, the water was violently kept while maintaining the internal pressure, and acrylic acid (12.9 g) was added dropwise from the upper dropping funnel. After the completion of the dropping, the mixture was stirred for 2 hours, and the water generated by the distillation was distilled off from the distilling device which was formed at the top.
  • the reaction, washing and filtration were carried out in the same manner as in Example 1-1, except that the acrylonitrile used in Example 1-1 was changed to methacrylic acid (15.4 g).
  • the obtained solid was composed of a repeating unit [one CH 2 — C (CH 3 ) (COOCH 2 CH 2 (CF 2 ) 4 F) —] Being coalesced.
  • the average amount determined by GPC was 26,000.
  • Example 2-3 Example of fluorination of the polymer obtained in Example 2-2
  • Example 1-3 As in Example 1-3, except that the polymer obtained in Example 1-2 was changed to the polymer obtained in Example 2-2 (1.8 g), the fluorination was performed in the same manner as in Example 1-3. «Processing and processing of rice liquid at room temperature Wisteria (2.4 g) was obtained.
  • Example 2-2 As a result of analyzing the product, it was found that 69 monoles of hydrogen atoms in the polymer obtained in Example 2-2. The value of the polymer whose / 0 was hardly affected by a fluorine atom was determined. The average molecular weight measured by GPC was 900.
  • Example 1-1 ⁇ S and filtration were carried out as in Example 1-1, except changing to 4 g).
  • the filtrate was ⁇ -distilled to obtain a fraction (54 g) of 90 to 95 ° C / 0.6 kPa pressure).
  • GC purity was 99%.
  • the NMR spectrum of the fraction was measured and it was determined that the fraction was the title compound.
  • Example 3-3 Example of fluorination of the polymer obtained in Example 3-2
  • Example 1-3 fluorination was carried out in the same manner as in Examples 1-3 except that the heavy ⁇ f obtained in Example 1-2 was changed to the polymer (3.6 g) obtained in Example 3-2. The reaction and treatment were carried out to obtain a solid product (3.27 g) at room temperature.
  • Example 1 Change the acrylic acid used in 1-1 to methacrylic acid (15.4 g) and change F (CF) 4 ⁇ 1 ⁇ 013 ⁇ 40 to (CF 2 ) 8 CH 2 CH 2 OH (46.8 g) Except for the same procedure as in Example 1-1 and filtration. ⁇ ⁇ ⁇ ⁇ , 60 ⁇ 70 ° C / 16 kP A fraction of a (55 g) was obtained. GC boats accounted for 93.4%. The NMR spectrum of the fraction was measured and it was determined that the fraction was labeled ⁇ ).
  • Example 13-3 the polymer obtained in Example 1-2 was replaced with the heavy ⁇ (book (3.0 g)) obtained in Example 4-2. To obtain a solid (3.32 g) at room temperature.
  • F (CF 2 ) 10 CH 2 CH 2 OCOCH co-weight of CH 2 and norbornene ⁇ ⁇ ⁇ ⁇ mL ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ 30 ⁇ ⁇ ⁇ ⁇ .
  • F (CF 2 ) 10 CH 2 CH 2 OCOCH CH 2 (19, 6 g) obtained in Example 5-1 and perbutyl viva as a polymerization initiator were added.
  • Rate (0.2 g) was dissolved in R-113 (22.5 g). The temperature was raised to 55 ° C with intense ⁇ , and polymerization ⁇ S was started.
  • the obtained solid was characterized as having a repeating unit derived from 2- (perfluoro (n-decyl)) ethyl acrylate and a repeating unit derived from norbornene.
  • the weight included in a molar ratio of 34: 1 (it was determined to be a book.
  • the average favorable weight measured by GPC was 1600.
  • Example 5-3 Example of fluorination of the double-stranded book obtained in Example 5-2
  • Example 13-3 the fluorine was obtained in the same manner as in Example 1-3 except that the heavy ⁇ f obtained in Example 1-2 was changed to the polymer (2.9 g) obtained in Example 5-2. And flame treatment to obtain solid
  • Example 5-2 As a result of analyzing the ⁇ product, it was found that the copolymer obtained in Example 5-2 had 27 monovalent hydrogen atoms. The polymer of which / 0 was substituted by a fluorine atom was used. The average good weight measured by GPC was 4000.
  • Example 6-3 Heavy ⁇ obtained in Example 6-2 (Example of fluorination of book)
  • Example 1-3 the blockage of fluorine gas was changed from 5.27 L / h to 5.16 L / h, and the polymerization f obtained in Example 1-2 was obtained in Example 6-2.
  • the same procedure as in columns f 1 to 3 was repeated, except that the polymer (3.58 g) dissolved in R-113 (179 g) was dissolved in R-113 (179 g) for an intense night, and the reaction was carried out for 3.25 hours.
  • the product 3.27 g was obtained.
  • ⁇ Analysis of the product, 19.4 mol 0/0 of the hydrogen atoms in the polymer obtained in Example 6-1 was knitted from polymers that are woven into a fluorine atom.
  • Example 7-2 was dissolved in R-113 (161.4 g), and the mixture was heated for 7.5 hours. I did & ⁇ . Then, while injecting 20% 3 ⁇ 4 fluorine gas at the same rate, inject 6 mL of R-113 intense night, further inject 20% 3 ⁇ 4 fluorine gas for 0.5 hour, then nitrogen gas for 1.0 hour I blew it.
  • Example 7 Fully dry the fluorinated polymer (8.3 g) obtained in _ 3 with KF powder (0.4 g) in a flask, heat to 120 ° C with vigorous » Heated. Thereafter, the sample recovered from the flask was filtered to recover a liquid substance (5.6 g). The product was determined by NMR to be a mixture of two or more types of compounds, each of which has the compound # # combined with esteno as the ⁇ it product. In addition, NMR confirmed that 69.7% of the ester synthesized in the fluorinated complex obtained in Example 7-3 was converted to one COF group by ⁇ .
  • Example 7-5 Example of esterification of ⁇ product obtained in Example 7-4
  • Example 7-4 While the methanol (5.8 g) was vigorously applied to the flask at ⁇ ⁇ and room temperature, the product obtained in Example 7-4 (5.1 g) was added dropwise over 0.5 B of the flask. After that, it was heated to 60 ° C for 4 hours. Subsequently, methanol was distilled off by distillation, followed by further E drying (100 ° C, 24 hours) to recover a liquid 4 ⁇ product (4.9 g). As a result of X H-NMR and 19 F-NMR, all of one COF group in the product obtained in Example 7-4 was esterified and converted to -COOCH 3 group ⁇ ! But I did what I did.
  • Example 8 Example of synthesis of F (CF 2 ) a OCF (CF 3 ) CF 2 ⁇ CF (CF 3 ) CH 2 OH
  • a 10 OmL flask with a dropping funnel at the top Was. NaBH 4 (19.9 g) and dioxane (250.1 g) were charged into the flask, and the system was vigorously closed for 1 hour while keeping the system at room temperature. »From the dropping funnel at the top, add F (CF 2 ) 3 OCF (CF 3 ) CF 2 OCF (CF 3 ) COF (l 72 g) from the upper dropping funnel, if the internal temperature exceeds 60 ° C, Carefully, it was dripped slowly.
  • the collected fresh phase was washed with 10% by mass of aqueous sodium bicarbonate (200 g) and separated into two layers. Furthermore, after having carried the carrier with fi-magnesium, it was filtered. The filtrate was subjected to distillation to obtain a fraction (51.5 g) of 45.5 ° C / 0.3 kPa (pressure). GC boats accounted for 99%. The NMR spectrum of the fraction was measured, and ⁇ was determined that the fraction was labeled ⁇ .
  • the collected crude liquid was dropped into methanol (300 g) to recover a solid content.
  • the recovered solid is converted to R-225 (100 g) and dropped twice into hexane (500 g), and the operation is performed twice.
  • the pressure-reduced grass 100 ° C, 24 hours
  • an elastomer-like solid 20.8 g
  • the obtained solid was composed of a repeating unit [one CH 2 — CH (C OOCH 2 CF (CF 3 ) OCF 2 CF (CF 3 ) ⁇ (CF 2 ) 3 F) [1].
  • the average molecular weight of the polymer was measured by GPC and found to be 21,000.
  • Example 8-4 Example of fluorination of the polymer obtained in Example 8-3
  • Example 8-3 obtained in heavy ⁇ (33 mole 0/0 of the hydrogen atoms in the fluorine atom in the isolated polymer in ⁇ ! Is wisteria. Also, GPC The average good weight measured in was 850,000.
  • Example 9-1 stimulation was Yuzuru nights examples 6-3 obtained in the polymer R- 225 on to 5 mass 0/0 dissolved.
  • the glass ® 1.5 cm X 7 cm was immersed in the inside of the lanyard to uniformly adhere ⁇ ⁇ on the glass surface.
  • the glass was further treated with 90 for 1.5 hours to form a female on the glass surface.
  • the angle of inversion (unit: degree) of the obtained glass surface was measured by means of X-ray and X-ray power (Tandou: Bawa Interface Chemistry SA-20S3 ⁇ 4 Insect angle meter).
  • the deworming angle in water was 114.2 degrees
  • the contact angle in hexadecane was 78.5 degrees.
  • the fall angle of hexadecane (IOL) was measured with the device on the shelf,
  • the surface of the glass was sharply shaved with a spatula. No change in the surface was observed, and it was leaked that a surface with an excellent abrasion durability of 3 ⁇ 49 was formed.
  • Example 9-2 The material obtained in Example 7-5 was used to form a support on the glass surface in the same manner as in Example 9-1.
  • the critical surface ⁇ of the glass surface was calculated by Zisman plot to be 19 mNZ m. This value was equal to or greater than the critical surface of polytetrafluoroethylene (18 mN / m). Difficulty availability>
  • the production method of the present invention it is possible to obtain a multi-view fluoropolymer by using a partially fluorinated polymer from which various types of t can be easily obtained.
  • the ⁇ method of the present invention can produce a fluorine-containing polymer whose fluorine content has been adjusted by an economical and industrially feasible method that does not require the addition of a male prosthesis or the like.
  • fluoropolymers having various Byeon medicaments produced according to the present invention and polymers derivatized therefrom are useful as coatings and functional agents such as J.
  • the ⁇ used as a coating can form a hard lake with excellent 3 ⁇ 4k oil repellency on the surface of the ⁇ .

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Abstract

L'invention concerne un procédé permettant la production industrielle avantageuse à faible coût de fluoropolymères de diverses structures ayant un contenu de fluor régulé à une valeur voulue ainsi que de dérivés des polymères, et un emploi utile des dérivés des fluoropolymères. Le procédé comprend une étape de polymérisation suivie d'une étape de fluoration. L'étape de polymérisation consiste en la polymérisation d'un monomère (β) ayant un ou plusieurs atomes de fluor liés par du carbone ainsi qu'un ou plusieurs atomes d'hydrogène liés par du carbone ou en la copolymérisation du monomère (β) avec un comonomère (j) copolymérisable avec le monomère (β). L'étape de fluoration consiste à dissoudre un polymère partiellement fluoré présentant des atomes de fluor liés par du carbone et des atomes d'hydrogène liés par du carbone dans un solvant de fluoration et ensuite à le fluorer dans la phase liquide afin de remplacer un ou plusieurs atomes d'hydrogène, liés par du carbone, du polymère partiellement fluoré, par des atomes de fluor.
PCT/JP2002/003213 2001-03-30 2002-03-29 Procede de production de fluoropolymere et son derive, et utilisation d'un derive de fluoropolymere Ceased WO2002079274A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006095790A1 (fr) * 2005-03-10 2006-09-14 Asahi Glass Company, Limited Nouveau polymere de structure fluorospirocetal
WO2010113864A1 (fr) * 2009-03-31 2010-10-07 ダイキン工業株式会社 Procédé de fabrication d'un polymère fluoré stabilisé
US9650639B2 (en) 2008-05-19 2017-05-16 Advaxis, Inc. Dual delivery system for heterologous antigens
US10016617B2 (en) 2009-11-11 2018-07-10 The Trustees Of The University Of Pennsylvania Combination immuno therapy and radiotherapy for the treatment of Her-2-positive cancers

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Publication number Priority date Publication date Assignee Title
US4948844A (en) * 1988-04-16 1990-08-14 Tokuyama Soda Kabushiki Kaisha Process for preparation of perfluorinated copolymer
JPH06128335A (ja) * 1992-09-02 1994-05-10 Tokuyama Soda Co Ltd 含フッ素共重合体の製造方法
WO2000056694A1 (fr) * 1999-03-23 2000-09-28 Asahi Glass Company, Limited Procede de production d'un compose de fluor au moyen d'une fluoration en phase liquide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4948844A (en) * 1988-04-16 1990-08-14 Tokuyama Soda Kabushiki Kaisha Process for preparation of perfluorinated copolymer
JPH06128335A (ja) * 1992-09-02 1994-05-10 Tokuyama Soda Co Ltd 含フッ素共重合体の製造方法
WO2000056694A1 (fr) * 1999-03-23 2000-09-28 Asahi Glass Company, Limited Procede de production d'un compose de fluor au moyen d'une fluoration en phase liquide

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006095790A1 (fr) * 2005-03-10 2006-09-14 Asahi Glass Company, Limited Nouveau polymere de structure fluorospirocetal
US9650639B2 (en) 2008-05-19 2017-05-16 Advaxis, Inc. Dual delivery system for heterologous antigens
WO2010113864A1 (fr) * 2009-03-31 2010-10-07 ダイキン工業株式会社 Procédé de fabrication d'un polymère fluoré stabilisé
CN102365299A (zh) * 2009-03-31 2012-02-29 大金工业株式会社 稳定化含氟聚合物的制造方法
JP5464210B2 (ja) * 2009-03-31 2014-04-09 ダイキン工業株式会社 安定化フルオロポリマーの製造方法
CN102365299B (zh) * 2009-03-31 2014-08-13 大金工业株式会社 稳定化含氟聚合物的制造方法
US9458255B2 (en) 2009-03-31 2016-10-04 Daikin Industries, Ltd. Method for producing stabilized fluoropolymer
US10016617B2 (en) 2009-11-11 2018-07-10 The Trustees Of The University Of Pennsylvania Combination immuno therapy and radiotherapy for the treatment of Her-2-positive cancers

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