WO2002079274A1 - Process for producing fluoropolymer and derivative thereof, and use of fluoropolymer derivative - Google Patents

Abstract

A process for industrially advantageously producing at low cost fluoropolymers of various structures having a fluorine content regulated to a desired value and derivatives of the polymers; and a useful use of the fluoropolymer derivatives. The process comprises the following polymerization step and the following fluorination step which follows the polymerization step. Polymerization step: the step of polymerizing a monomer β having one or more carbon-bonded fluorine atoms and one or more carbon-bonded hydrogen atoms or the step of copolymerizing the monomer β with a comonomer (j) coplymerizable with the monomer β. Fluorination step: a step in which a partially fluorinated polymer having carbon-bonded fluorine atoms and carbon-bonded hydrogen atoms is dissolved in a solvent for fluorination and then fluorinated in the liquid phase to replace one or more of the carbon-bonded hydrogen atoms of the partially fluorinated polymer with fluorine atoms.

Description

 Specification

 Fluoropolymers and their i ^ method, and uses of fluoropolymer derivatives

 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. >

 »From the formula in which a hydrogen atom is bonded to a carbon atom, and the chemical formula containing chloro (CH) is contained, the method is to fluorinate all of the C-H moiety into C-F using fluorine gas. There are known ways to do this.

 As a method for fluorinating a C-H-containing polymer, such a polymer compound is usually a solid or a liquid at room temperature, and it is difficult to perform mochi glueing.

(1) Fluorination by detoxification with fluorine gas as it is (La Mar method), and

(2) C ~ H containing high polymerized ^ # 1 in the middle of A L,? A male that introduces fluorine gas into the male and fluorinates in the liquid phase is known.

 In the method described in (1) above, only the highly solidified solid surface is fluorinated, so it is difficult to obtain a fluorinated product having the desired structure, or adjust the fluorination key. Unfortunately, there was a problem.

In the above method (2), a perfluorinated organic solvent is usually used as an inexhaustible solvent. However, 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,口 ホ ル 等 等 、 励 励 励 励 励. 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.

 In addition, even if you visit the Sudanada, in fact, it is difficult to improve the conversion of the perfluorinated organic to anyone who has a good taste. Therefore, after (2), there was a problem in that it became difficult to obtain a polymerized “^” which was difficult to fluorinate, which became non-uniform in the β-system. However, there are problems with low efficiency and high manufacturing cost.

 On the other hand, as an application to obtain a polymerized ^ J having C-F, it is conceivable to polymerize a fluorine-based monomer in which all of the C-H portions have been pre-fluorinated, but generally available fluorine-based monomers Is difficult to synthesize; (There is a problem that ft is limited. Also, depending on the fluoromonomer, the combination of polymerizable compounds is limited. There were limited issues.

 From the above observations, it was reported that tetrafluoroethylene, a fluorine-based monomer, and propylene, a non-fluorine-based monomer, were copolymerized and then fluorinated in the liquid phase to obtain a fluorine-containing polymer. (Tokuhyo Heihei 4-50000520). However, such a copolymer S of a fluorine-based monomer and a non-fluorine-based monomer has a problem in that a copolymer having an arbitrary structure cannot be obtained for $ S because the combination thereof is limited. In addition, the fluoropolymer obtained by fluorinating a copolymer of tetrafluoroethylene and propylene has a problem that further chemical conversion cannot be performed because the 05-acid is not available.

In addition, 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). However, in order to produce a polymer obtained by the above process, an additional polymerization step is required, and the number of steps required to obtain the polymer is increased. Therefore, 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). The production of a fluorine-containing polymer capable of reducing the amount of fluorine is also carried out.Furthermore, the fluorine-containing polymer produced by the present invention (a useful derivative obtained from the book is also referred to as “r» T.

<Disclosure of the Invention>

 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.

 1. 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 (β) and a comonomer (j) copolymerizable with the monomer β).

 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

 2. The male production method according to claim 1, wherein the partially fluorine-containing polymer is a product in a polymerization step.

 3. The polymerization reaction in the polymerization process is a forced D polymerization reaction.

 4. The monomer according to claim 1, 2, or 3, which is a monomer obtained through the following monomer synthesis.

Monomer synthesis step: A monomer having a hydrogen atom bonded to a carbon atom and an optional (Y ² ) — (α) 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 claim that the average molecular weight of the partial fluorine b≤coalescing is 100 or more; ~ 4 of! / TS m listed on either side

6. partially fluorinated fluorine content of I匕重coalescence is 3 0-7 0 weight _^0/0, and a full Tsu餘有kinematic 3 5 mass _^0/0 or more of the fluoropolymer, force, partially fluorinated ί 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.

 7. The weight of all of the fluorine atoms in the union of partial fluorine converted to hydrogen atoms (the weight of the book is strictly insoluble according to the fluorine i R ^^ Φ). ^^

8. partially fluorinated I kfi coalescence of claims 1-7 Les performing fluorination step until 4 0 mole _^0/0 or more atom that carbon atom is a fluorine atom, Zurekani B¾) | ¾ m

 9. 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.

 10 0. Monomer (β) 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. In claim 9, ^ 言 of the word B¾

 1 1. 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 "|| and having a heavy COF group in the side chain

1 2. In the polymer obtained by the method of claim 11, a hydroxylated compound having a fluorine-free monovalent と and a water に in one C〇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

13. —Repeating unit represented by jl-wiping [CX ¹⁰ X ²⁰ -C (R ¹⁰ ) C〇OR ^H ] — (where X ¹⁰ and X ² ° each independently represent a hydrogen atom or a fluorine atom, R ^{1 ()} represents a hydrogen atom, a fluorine atom or a fluorinated methyl group, forces, X ^1Q, 1 or more selected from X ^2G and R ^1Q is a group of the fluorine atom as an essential. R ^H Represents fluorine or a monovalent organic group.), And the ratio of fluorine atoms is 35 mass / ⁰ . To 86 weight _^0/0 and polymers, organic super certain ^ tf dark product can dissolve the Gen鍾coalescence.

 14. The thread according to claim 13 wherein the curable substance is a coating The best mode for carrying out the invention>

 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 Γ (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.

—は、 ァクリロイル基 またはメタクリロイル¾ ^の一部であってもよレ、。 (1) Monomers that polymerize by unsaturated chain opening include CH2 CR ¹ — and CH ₂ = CC 1-(where R ¹ ^) as polymerizable groups (also referred to as non-sticky groups of addition polymerization ft). * indicates a hydrogen atom or a methyl group.) or one or more hydrogen atoms in these groups monomer force ^s with substitution radicals fluorine atom. here,

— May be part of an acryloyl group or methacryloyl ¾ ^.

 Examples of the monomers polymerized in the two rows S in (2) include cyclic ethers, cyclic lacquers, lactams, ratatone, and cycloparaffins.

(3) 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.

 In the present specification, 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 重合). Les ,. The number of repeating units in the polymer may be one, or two or more.

 In the present specification, the term “increase” refers to a group that essentially requires a carbon atom, and may be a saturated group or an unsaturated group. As the halogen atom, a fluorine atom or an atom is preferable. The monovalent! Β 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 τ Examples of 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 ,.

 In the present specification, 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 V¾. The same applies to other compounds.

 The monomer forming step, the polymerization step, and the fluorinating step in the present invention will be described in order.

 [Monomer

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 (γ) and a fluorine atom bonded to a carbon atom. .

(γ ¹ ) and (γ ² ) in the monomer (H) are each other; ^^ Also forms a 〖¾i bond.

The bond formed by (γ ¹ ) and the combination of (γ ² ) and force include a single bond, a double bond, and a triple bond, and the ϋ ^ group includes a 結 bond, a ο—, S— and the like. The valence of the keyed link is not particularly ρ knee, and the valency of more than two valleys can be fought. As the germ-free group, ^one of Υ ¹ and Υ 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. ) And fe ^ is one OH: one COO— formed in ^, one of Y ¹ and Y ² is -SO3X ¹ (where X ¹ has the same meaning as the knitting). include the one so ₂ 〇 first prize Ru form to a guard OH. In addition, the following B® group formed at an age where one of Y ¹ and Y ² is c ¹ = o and iifc ^ is HOC ² — (where ¹ and ² in C ¹ and C 2 are ¾ indicates a carbon atom.) Force S

; C

 The ο—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). In particular, the monomer () is a non-fluorine-based monomer that does not contain a fluorine atom in † ¾t.

Monomers (α) 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. However, in the following formula, R〗 represents a hydrogen atom or a methyl group, X ¹ has the same meaning as that of the self, and 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, and r represents a fiber of 1 to 4.

CH ₂ = C (R ¹ ) one Q ¹ — COX ¹ ; formula ")

(Eg CH ₂ = C (R ¹ ) — COOH, CH ₂ = C (R ¹ ) _C〇C 1, CH ₂ = C (R ¹ ) one (CH ₂ ) _ra — COOH, CH ₂ = C (R ¹ ) one (CH ₂ ) _m -COC1, etc. ) CH ₂ = C (R ¹ ) one Q ² —OH; formula (α ¹² )

(For example, CH ₂ = C (R ¹ )-(CH ₂ ) _r OH, CH ₂ = C (R ¹ ) one (CH ₂ CH (CH ₃ )) _p OH, CH ₂ = C (R ¹ ) COOCH ₂ CH (OH) CH ₂ C1, etc.)

When the monomer () is CH ₂ CHC (a monomer having a part of R), it is preferable to use a monomer in which R ¹ is a hydrogen atom because the yield of the fluorination step is high. 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 fluorinated compounds which ®S the monomer ( "), especially R ^F Mashi monovalent Employed (R ^F) and both of an Y ¹ of ^) force child essentially containing fluorine atoms bonded to carbon atoms - Y ¹ 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.

Specific examples of R ^1F include the following example S. In addition, in the following specific examples, groups corresponding to the groups having the respective structural isomers are also included.

C ₄ F ₉ — {where F (CF ₂ ) ₄ —, (CF ₃ ) ₂ CFCF ₂ —, (CF ₃ ) ₃ C—, or CF ₃ CF ₂ CF (CF ₃ ) first class. }, C ₅ F _n- {where, F (CF ₂ ) ₅ —, (CF ₃ ) ₂ CF (CF ₂ ) ₂ —, (CF ₃ ) ₃ CCF ₂ —, or F (CF ₂ ) ₃ CF (CF ₃ ) First class. }, C ₆ F ₁₃ — {however, F (CF ₂ ) ₃ C (CF ₃ ) ₂ — etc. _{}, C 8 F 17 -,} C 10 F 21 -, C 12 F 25 - C 14 F 29 -, C 16 F 33 -, C 18 F 37 -, C 20 F 41 -, (CF 3) 2 CF ( CF ₂ ) _s One (s is 3 or more fibers), CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) One, CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) ―. An example of 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 ¾T: is 1¾ notice.

For example, the monomer (ratio) of Upsilon ² Gar COX ¹ (X ¹ is ΙίίΙ the same meaning as Yuki) (such as to TO a monomer represented by the ftjf yourself formula (alpha ^11).) If it is, the Y ^{1 of the} fluorinated ^ is preferably 1 OH. As the fluorinated compound, R ^1F (CH ₂ ) _n OH or R ^1F COF (R ^1F has the same meaning as disgust. N represents n from！ to 5, and preferably from 2 to 5. , 2 or 3 are particularly preferred.)) Represented by) is preferred.

For example, 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.

Specific examples of the fluorinated ^ # ¹ in which Y ^{1 is} -OH and 1 COX ¹ include the following S). Here, n has the same meaning as described above.

R ^1F COF (for example, CF ₃ CF ₂ COF, CF ₃ CF ₂ CF ₂ 〇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.).

It is a compound that can be easily synthesized from fluorinated or of course. For example, 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.

Monomer) and KJ¾ with the fluorine-containing compound: W removed by the applied according to the combination of Y ¹ and Y ² Can be renewed. For example, (meth) Atari / and R ^1F (CH ₂ ) _π R R ¾ R エ ス テ ル エ ス テ ル エ ス テ ル エ ス テ ル エ ス テ ル エ ス テ ル。。。 。.

Examples of the monomer (hereinafter referred to as monomer (β ′)) 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.

CH ₂ = C (R ¹ ) COO (CH ₂ ) _n R ^1F

CH ₂ = C (R ¹ ) OCOR ^1F

CH ₂ = C (R ¹ ) COO (CH ₂ ) _k OCO (CH ₂ ) _n R ^1F ,

G- (CH ₂ ) _ra OCOR ^1F .

 The monomer (β ') can be obtained from the product of the monomer synthesis step by performing ordinary purification. Obtaining the monomer (β) used in the subsequent polymerization step: The removal is not limited, but the monomer (β,) 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 (| 3) in a subsequent polymerization step. Further, a monomer (β ′) obtained by chemically converting the monomer (β ′) produced in the monomer synthesis step may be used.

 The monomer (β) in the polymerization step in the present invention is preferably a monomer obtained via a monomer synthesis step. The reason is that both monomers (ο and fluorinated compounds) can be obtained inexpensively and inexpensively by using compounds having various structures. This is because various types of monomers (β) can be synthesized by obtaining β ′) and, if necessary, performing chemical conversion on the monomer (β ′).

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. In addition, the fluorine atom bonded to the carbon atom in the monomer (β,) is very powerful before and after the ヒ ichological transformation. In the monomer (β ') 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 (β) 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 (β) is preferably a monomer (β ¹ ) which is a monomer (β ¹ ) linked by an unsaturated group in addition polymerization and a divalent group which requires a force esterification. As the monomer (β ¹ ) which essentially contains the ester ^, a monomer represented by the following formula (β ^ι -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. However, U represents an unsaturated group in addition polymerization, and 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.

U— Qi—COO— Q ² — R ^F · · · ( ¹ 1 1)

U— Q ¹ — OCO— Q ² — R ^F · · · (β'-Ζ)

〇Η ₂ = 〇Ι ^ one C〇〇 one Q ² — R ^F · · · (β'-10)

CH ₂ = CRi— Q ¹ — OCO—Q ² — R ^F · '· ( ¹ — 20)

CHs ^ CR ¹ COO— (CH ₂ ) _P R ^1F (jS'-l 1)

CH ^ CR! OCO— (CH ₂ ) _k R ^1F · '· · (ー 21) 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 ¾¾ and easily Polymerization is a monomer capable of producing a heavy ^ (book having various structures. Further, the monomers

Since a polymer obtained by polymerizing (β ¹ ) is a heavy polymer having an ester / polymer in a side chain, there is also an advantage that the ester bond can be chemically converted to be derivatized. Particularly mono mer and expression of the formula ¹ one 1) (beta ¹ - In the monomers represented by 2), formula (J3 ¹ - monomer represented by 1), leads to雜a by derivatization Replying to @Dragon

In particular, 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 ) _ΠOH (wherein, R ^1F and n have the same meaning as in Kagome).

Specific examples of the monomer (β 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 ) „F.

Further, the specific u of the monomer (β) is a monomer other than the above is CF ₂ = C

_{HCF 3, CF 3 CF 2 CF} 2 CF 2 CH = CH 2, CF 3 CF 2 CF 2 CF 2 CF = CH 2 Hitoshigakyo up 'is.

 The polymerization step is a step of polymerizing the monomer (β) or a step of copolymerizing the monomer (j3) with the comonomer (j). The polymerization of only the monomer (β) may be used, and only one type of the monomer (β) 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.

In the present invention, 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, polyoxyalkylene di (Meta) Acrylate, (meth) acrylate having polysiloxane, 2-dimethylaminoethyl (meth) acrylate, alkyl (meth) acrylate having an alkyl group having 8 to 20 carbon atoms, cycloanoreky (meth) acrylate, (Meth) acrylates such as hydroxyethyl (meth) acrylate; (halogenated alkyl) butyl ethers having a halogen atom of fluorine atom; cyclic olefins such as norbornylene; bier alkyl ketone, triaryl cyanide Nurate, aryl glycidyl ether, vinyl, vinyl, N-vinylcarbazole, maleimide, N-methylimide, and the like.

 Among these, as 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. In addition, the monomer (j), which is a monomer (β) -force S (meth) acrylate, is preferably selected from (meth) acrylates or butyl chloride in terms of yield, especially Scaling force from acrylates is preferred.

In the polymerization in the polymerization step, the monomer (β) is preferably used in an amount of 50 to 100 mol% based on the monomer 4 to carry out the polymerization. Here, the polymerization method of the monomer (β) is In other words, ^^ mouth polymerization SJ¾ method can be applied as it is. For example, a monomer (^ -ιοο) having a (meth) atalyloxy group can be easily polymerized according to the conditions and methods of milky mouth.

 In the polymerization step in the polymerization step, 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. Further, 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.

 In the polymerization step: The following polymer contains a repeating unit of the monomer (j3). Further, in the polymerization step, the comonomer (j) was copolymerized: ¾ ^ 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. For example, 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. However, Even at the age of chemical conversion, 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.

 [Fluorinated @]

 In the fluorination step, 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. As described above, even if the polymer is formed in the polymerization step, 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. In other words, 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.

In the fluorination step, 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. Here, to dissolve in Fluoride-t®S Nada, fluoridity conditions! This means that 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. In addition, 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.

Further, 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餘有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.

Further, 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 (τ _ε ) force s, and the like, and it is difficult to obtain the physical property force s required for the polymer. Perform liquid phase fluoropolymerization of a partially fluorinated polymer in a liquid phase, which requires a certain amount of fluorine. As a method of this type, a cobalt fluoride ECF method is known, but the present invention performs fluorination by a liquid phase fluorination method which can reduce the production cost of the fluoropolymer. According to the method, as described above, the fluorine-containing polymer in a uniform state can be obtained, so that the fluorine-containing polymer desired by JF can be reliably obtained at a high yield.

 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. 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. In addition, when the carbon-carbon unsaturated bond grows in the partially fluorine-containing polymer, a fluorine atom may be added in some cases.

In the present invention, fluorine is obtained by fluorinating all of the hydrogen atoms bonded to carbon atoms in the partially fluorinated polymer (that is, completely fluorinated). Have difficulty. Fluorine is the fluorination rate (the fluorination rate is the partial fluorination weight Preferably, 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. With 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.

 In 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.

In the fluorine reaction of the present invention, in order to further increase the fluorination rate, it is necessary to heat the fluorination at a low temperature and then heat the fluorination.

After the addition, the force of performing further fluorine kKJ ^ at +10 to 150 ° C is preferable. In addition, 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. .

 As the spirit of 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. Certain is preferable, and furthermore, ぺ norehnorero alka ^ !, perfluoroeeg, perfluoropolyethers (trade names: cittotus, fomblin, gano, n, demnum, etc.) (Trade name: Hunloop), Black phenolic polyethers, Perfunoleoalkylamine

(For example, perfluorotrialkylamine, etc.) and inert fluids (trade name: Florinato).

 Further, 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.

Anyone who uses fluorine at least 5 times the mass of the partially fluorinated polymer is preferable, and particularly preferably uses 100 to 100 times the mass of the partially fluorinated polymer. Fluoropolymers are also used Moti [^ Roh? Rice Uranaido of intense night that males? To Yokai has to a ^{5 X 1 0- 4 ~0. L} P a 's, for reasons that can be smoothly carried out the liquid phase fluorine I preferably in particular ^{5 X 1 0- 4 ~5 X 1} 0- 3 P a · s to the power ¾ | desirable #.

 As 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. As the 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,

(1.5 times or more mol) is preferable in terms of S selectivity. In addition, 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®¾, from the viewpoints of ¾yield, 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. Force, preferably 0, 0 1 to 5MPa (gauge £, especially the age at which no fiber is shown indicates gauge pressure). The power of removing HF, such as ¾ ^, 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. As the fluorine gas, either in the batch mode or in the continuous yarn, it is possible to use an inert gas such as nitrogen gas.

In 1¾1], charge the partially fluorinated polymer and Fluorine Nada, and start the marsh. Next, at a predetermined pressure of ^ S ^ Jt and pressure, fluorine gas is continuously supplied to the liquid phase in the vessel ^: ^ ^ 2] ® Sees 雄 of フ ッ 素 in ¾. Next, at a given temperature and Si ^ pressure, fluorine gas and a partially fluorinated polymer which has been fluorinated with fluorine are continuously and simultaneously supplied to the liquid phase at a given molar ratio at a given molar ratio. Method. According to this method, 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. In addition, it is preferable that 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.

としては、 N a F 子ましい。 In fluorine, hydrogen atoms are replaced by fluorine atoms, and HF force S is by-produced. In order to remove the by-product HF, 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 (¾¾) 1, and (j) cooler (between 178 ° C and + 10 ° C) Listen to (h) — (i) one (j)

A liquid return line 辯 g is also available to return the ben- gin of β-fluoride from the vessel to ϋ. 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 ¾ system from increasing.

Further, in order to efficiently increase the fluorination rate in liquid-phase fluorine, C-! ■ ¾ ^^ compounds must be added Q to the reaction system, or irradiation with ultraviolet spring must be performed. Is preferred. Thereby, the partially fluorinated polymer in the system can be efficiently fluorinated. The UV irradiation time is preferably 0.1 to 3 hours. As C—H¾5 ^ substantiated 棚), 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. In addition, 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.

 In 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.

For example, 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.) In the age of 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. In addition, as the fluorine-containing polymer, 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.

 From the ¾ ^ ¾ substances produced by the fluorination process, for ordinary ages, 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.

 For example, in a fluorine-containing polymer having an ester bond in a side chain, various polymers can be derived by utilizing the properties of the ester bond. For example, by performing an ester bond ^ 军, 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. When 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. When 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.

 Further, the polymer having one C 有 す る F group in the side chain can be subjected to esterification of the —COF group to obtain fluorine-containing polymers having various esterified groups. Examples of the hydroxylated ^ include fluorine-containing compounds, hydroxylated compounds having monovalent β and water M¾, 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. For example, 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.

In particular, a polymer having a fluorine atom converted to a carbon atom in the polymerized f * ¾i 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. Is the polymer and

? An impregnated material can be used as a coating. 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肅己^ 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.

According to the production of 3 f fluorine-containing heavy powders according to the present invention, 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.麵 row

Hereinafter, the present invention will be described in detail with reference to male examples, but the present invention is not limited thereto. In addition, tetramethyl / lesilane was described as TMS, and dichloropentaf / leopropane was described as R-225, and the product name was AK-225. CC 1 ₂ FCC 1 F ₂ is written as R—1 13. Further, NMR data / data were shown as an apparent chemical shift range, and expressed by an integral value. Pressure ¾ examples referred in thread "pressure. ¹³ C-straight of S¾¾ quality CDC 13 is in NMR, it was a 76. 9 p pm. ¹⁹ F- NMR to the fluorine content of quantification by hexa Furuorobenzen (C ₆ F ₆ ) Was used for the interior.

 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. In the measurement of GPC, a solution in which 1-Vo 1% hexafenoleoloisopropinole alcohol was dissolved in R-225 was used as Togai night. In addition, PL g e1 5 μM i — ed—C was used for the GPC column.

 [Example 1]

(Example 11) Example of synthesis of F (CF ₂ ) ₄ CH ₂ CH ₂ OCOCH = CH ₂

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. Thereafter, the pressure was adjusted to normal pressure, and the temperature was raised to room temperature to collect a crude liquid. After recovery, the crude liquid was separated into two layers of distilled water (60 _g ) -i to recover an organic phase. After repeating the washing operation four times, Filtered. The filtrate was subjected to E distillation to obtain a fraction (34.1 g) having a temperature of 55 ° C / 0.6 kPa (a stringy pressure). GC boats accounted for 99%. The NMR spectrum of the fraction was measured and β was determined that the fraction was title.

- NMR (300. 40MHz, Nada CDC 1 _3, unto: TMS) δ (ppm): 2. 52 (2H), 4. 47 (2H), 5. 8 (1H), 6. 1 (1H), 6 4 (1H).

^{19 F-NMR (282. 65MH z} , solvent CD C 1 _{3, reference: CFC 1 3) δ (ppm} ):.. -81 1 (3F), -113 6 (2F), one 124. 2 (2F) , One 125.

8 (2F).

(Example 1-2) Example of polymerization of F (CF ₂ ) ₄ CH ₂ CH ₂ OCOCH CH ₂

 Worked on a 50 mL round bottom flask that had been fully converted to nitrogen. Here, F obtained in Example 1-1

(CF ₂ ) ₄ CH ₂ CH ₂ OC〇CH = CH ₂ (25.0 g) and 2,2′-azobisisobutymouth-tolyl (0.5 g) as a polymerization initiator were added to R—225 (53 7 g) was injected. While violently », the polymerization H ^ was started by 1 显 to 60 ° C. After 15 hours from the start of lfl, the mixture was cooled to room temperature, and the solution was recovered.

(300 g), and a solid content was recovered. Further, »operation was performed twice by dissolving the collected solid content in acetone (100 g) and dropping it in hexane (500 g). Thereafter, the mixture was heated (100 ° C, 24 hours) to obtain a solid (17.5 g) at room temperature. iH- NMR, ¹⁹ F- result of NMR, the resulting solid is repeating unit ¾ that _{[- CH (C OOCH 2 CH} 2 (CF 2) 4 F) one - CH _2] is the force et made heavy present ,did. The average molecular weight of the polymer was measured by GPC and found to be 43,000.

iH-NMR (300. 4MHz, Nada: CDC 1 _3,挪: TMS) δ (ppm): ... 1. 3 ~ 2 1, 2. 2~2 6, 4. 2~4 5.

^{19 F-NMR (282. 7MH z} , solvent: CD C 1 _{3, reference: CFC 1 3) δ (ρ} ρ m):.. -80 9 (3F), -113 2 (2F), one 123.8 (2F), -125.

9 (2F). (Example 1-3) Example of fluorination of the polymer obtained in Example 1-2

 5 OOmL of Hastelloy; ^ The R-113 (312 g) was added to the toclave and maintained at 25 ° C. : ^ "At the outlet of the gas to the clave, the time at 20 ° C, the NaF pellet, and the time at 120 ° C (fibre 1). The time at 20 ° C , A liquid line for returning the collected liquid to the autoclave was illuminated. ^^ After injecting nitrogen gas into the toclave for 1.0 days, the nitrogen gas was reduced to 20% with nitrogen gas (hereinafter referred to as “fluorine gas”). Fluorine gas was blown at 27 L / h for 1 hour, and then the polymer (2.3 g) obtained in Example 1-2 was added to the ^^ crepe while blowing fluorine gas into the crepe. — Introduced the Nada, which was reverted to 113 (114 g) over 3.33 hours, while injecting 6 mL of R-113 transmutation while blowing the fluorine gas with the same magnet. After that, the phase solution was collected and dried (60 ° C, 6.0 hours) to distill off R-113, producing a viscous liquid at room temperature. To give an object (2. 7 g).

 As a result of analyzing the product, it was confirmed that 66 mol% of the hydrogen atoms in the polymer obtained in Example 1-2 were converted to fluorine atoms in the polymer. The average value measured by GPC was 3500.

¹ H-NMR (300. 4 MHz, Nada: R-113, 挪: TMS, Uchikijo jun: Nitoguchi benzene) δ (p pm): 2.8-3.7, 3.8-5. 0, 5.1 to 6.3, 6.6

¹⁹ F- NMR (282. 7MHz, Nada: R- 113, reference: CDC 1 _3, the inner _{semi-: C 6 F 6) δ (} p pm):. -57 5~ one 59.0 One 76. 0 18.7, 1 89.0 to 1105.0, 1113.5 to 1: L14.0, 1120.0 to 1131.0, -141.0 150.0, -165.0 to One 180.0, One 205.0 215.0.

 [Example 2]

(Example 2-1) Synthesis example of F (CF ₂ ), CH ₂ CI-LOCOC (CH ₃ ) = CH ₂ 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). E-distillate the filtrate to 60 ° C / 0.6 kPa

A fraction of (in pressure) (35.6 g) was obtained. GC fraction of the fraction was 99%. The NMR spectrum of the fraction was measured and the fraction was marked ^! Β, then o

^J H-NMR (300. 40MHz, Nada CDC 1 _3,辨: TMS) δ (pm): 1. 98 (3H), 2. 45 (2Η), 4. 45 (2Η), 5. 6 (1Η) , 6.1 (m, 1Η).

^{19 F-NMR (282. 65ΜΗ ζ} , solvent CD C 1 _{3, reference: CFC 1 3) δ (ρ} ρ m):. -81 0 (3 F), one 113. 7 (2F), one 124.3 (2F), —125.8 (2F).

(Example 2-2) Example of polymerization of F (CF ₂ ) ₄ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂

F (CF ₂ ) ₄ CH ₂ CH ₂ OCOCH = CH ₂ obtained in Example 1-2, F (CF ₂ ) ₄ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ obtained in Example 2-1 (25.9 g )), And polymerization was carried out in the same manner as in Example 1-2, to obtain a solid product at room temperature (18 g).

^{As a result of 1} H-NMR and ¹⁹ F-NMR analysis, 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.

¹ H-NMR (300.4 MHz, Nada: CDC, Summary: TMS) δ (p pm): 1.0-1.6, 1.9-2.4, 2.5-2.8, 4.2 ~ 4.6.

^{1 9 F-NMR (282. 7MH} z, solvent: CDC 1 _{3, reference: CF C 1 3) δ (} p pm): one 80. 9 (3F), one 114. 0 (2F), one 123.8 (2F), one 126.5 (2F).

 (Example 2-3) Example of fluorination of the polymer obtained in Example 2-2

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.

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.

¹ H-NMR (300.4ΜΗζ, Nada: R-113, Summary: TMS, Nichio: Nitoguchi benzene) δ (p pm): 2.6-3.8, 5.0-5.6, 5 7-6.8.

^{19 F-NMR (282. 7 MHz} , away: R- 113, fireman's standard: CDC 1 _3, the inner semi-:

C ₆ F ₆ ) δ (p pm): -80 82, 1 85 to 1 87, — 110 to 1 126, 1 14

5.0 to 1 150. 0, -205. 0 215.0.

 [Example 3]

(Example 3-1) Example of synthesis of F (CF ₂ ) ₈ CH ₂ CH ₂ OCOCH = CH ₂

Example 1 F (CF ₂ ) ₄ CH ₂ CH ₂ 〇H used in 1 to F (CF ₂ ) ₈ CH ₂ CH ₂ OH (46.

^ S and filtration were carried out as in Example 1-1, except changing to 4 g). The filtrate was β-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.

^ -NMR (300. 40MHz, Nada CDC 1 _3, noodles: TMS) 5 (p pm) : 2.

52 (2H), 4.47 (2H), 5.8 (1H), 6.1 (1H), 6.4 (1H).

^{1 9 F-NMR (282. 65MH} z, solvent CD C 1 have _{reference: CFC 1 3) δ (ρ} ρ m):.. One 81. 1 (3F), -113 6 (2F), -121 5 ( 6F), one 122.5 (2F), -123.3 (2F), -125.8 (2F).

(Example 3-2) F (CF ₂ ) ₈ CH ₂ CH ₂ 〇COCH = CH ₂ weight ^

Example 1 F (CF ₂ ) ₄ CH ₂ CH ₂ OCOCH 2 CH ₂ CH ₂ in Example 1 was changed to F (CF ₂ ) ₈ CH ₂ CH ₂ OCOCH = CH ₂ (40.0 g) obtained in Example 3-1 Except for the above, polymerization and wheat treatment were carried out in the same manner as in Example 12 to obtain a solid (32.1 g) at room temperature. ^ -NMR, ¹⁹ F— As a result of NMR analysis, the solid obtained was a repeating unit [— CH ₂ — CH

(CO〇CH ₂ CH ₂ (CF ₂ ) _S F) I] Powerful weight ^ (I told you this was a book. The average molecular weight determined by GPC was 8200.

^X H-NMR (300. 4MHz, Nada: CDC 1 _3, Lecture: TMS) δ (ppm): .. 1. 0~2 2 (2H), 2. 3~2 8 (3H), 4. 4~ 4.6 (2H).

¹⁹ F-NMR (282. 7MHz, solvent: CDC 1 _{3, reference: CFC 1 3) δ (ρ} ρ m):. -80 3 (3F), one 112. 7 (2F), one 120.8 (6 F), —121.7 (2F), -122.4 (2F), and 15.2 (2F).

 (Example 3-3) Example of fluorination of the polymer obtained in Example 3-2

 In Examples 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.

 As a result of analyzing the product, it was confirmed that the polymer obtained by substituting 19.4 mol% of the hydrogen atoms in the polymer obtained in Example 3-2 with a fluorine atom was ^^. The average favorable weight determined by GPC was 2100.

 -NMR (300.4 MHz, solvent: R-l13, standard: TMS, internal standard: benzene at the mouth) δ (ppm): 2.6 to 3.5, 4.0 to 6.0, 6.5 ~ 7.0.

^{19 F-NMR (282. 7 MHz} , Nada: R-l 13, reference: CFC 1 _3, inner Makoto votes quasi:

C ₆ F ₆ ) δ (ppm): -73.0 87.0, -105.0- -136.0, -21

0.0 to one 215.0.

 [Example 4]

(Example 4-1) Synthesis example of F (CF ₂ ) ₈ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂

Example 1 Change the acrylic acid used in 1-1 to methacrylic acid (15.4 g) and change F (CF) ₄ 〇1〇01¾0 to (CF ₂ ) ₈ CH ₂ CH ₂ OH (46.8 g) Except for the same procedure as in Example 1-1 and filtration.蒸 留 蒸 留, 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 ^).

H-NMR (300. 40MHz, Nada CDC 1 _3,挪: TMS) δ (p pm) : 1. 98 (3H), 2. 45 (2H), 4. 45 (2Η), 5. 6 (1Η) , 6.1 (1Η).

^{19 F-NMR (282. 65MH z} , solvent CDC 1 _{3, reference: CFC 1 3) δ (ppm} ):. -81 0 (3F), one 113. 4 (2F), one 121. 5 (6 F) , One 122.6 (2F), -123.3 (2F), -125.8 (2F).

(Example 4-1-2) F (CF ₂ ) ₈ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ double ^ ί

Example 1 F (CF ₂ ) ₄ CH ₂ CH ₂ 〇 COCH = CH ₂ in Example ₂ F (CF ₂ ) ₈ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (40.5 Polymerization and wheat treatment were performed in the same manner as in Example 1-2 except that g) was changed to g) to obtain a solid ^^ product (31.2 g) at room temperature.

¹ H-NMR ¹⁹ F—As a result of NMR analysis, the obtained solid is a polymer having repeating units [1-CH ₂ —C (CH ₃ ) (COOCH CH ₂ (CF ₂ ) ₈ F)-] Did. The average molecular weight measured by GPC was 15,000.

^J H-NMR (300. 4MHz,鵷: CDC 1 _3, noodles: TMS) δ (p pm) :.. 1. 0~1 8 (3H), 1. 9~2 4 (2H) '2. 5 ~ 2.8 (2H), 4.2 ~ 4.6 (2H).

^{19 F-NMR (282. 7MH z} , solvent: CD C 1 _{3, reference: CFC 1 3) δ (ppm} ):. -81 3 (3F), one 113. 6 (2F), one 121. 7 (6F ), —122.5 (2F), -123.4 (2F), 126.1 (2F).

 (Example 4-3) Example 4

 In 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.

Analysis of the goods, 70.0 mol _^0/0 fluorine hydrogen atom in the polymer obtained in Example 4 one 2 The atom of the polymer was added to the atom. The average molecular weight measured by GPC was 1200.

¹ H-NMR (300. 4 MHz, Nada: R-113, fresh: TMS, internal standard: nitrobenzene) δ (p pm): 1.4, 2.6-3.6, 5.0- 5.8, 5.8 to 7.0.

^{19 F-NMR (282. 7 MHz} , Nada: R- 113, fireman's standard: CDC 1 _3, inner _{廳準: C 6 F 6) δ (} p pm):. -58 0~ one 85.0, -112～ 1 128. 0, 1 147.0 to 1 149.0, -209.5 to 1 211.0.

 [Example 5]

(Example 5-1) Example of synthesis of F (CF ₂ ) ₁₀ CH ₂ CH ₂ OCOCH = CH ₂

Changing F (CF ₂ ) ₄ 〇 << ^ 〇1¾011 used in Example 1-1 to (CF ₂ ) ₁₀ CH ₂ CH ₂ OH (54.6 g) was performed in the same manner as in Example 1 _ 1 and filtration was performed. Was. The filtrate? By distillation, a fraction (52 g) of 95 to 105 ° C / 14 kPa (thread pressure) was obtained. GC boats accounted for 99 mol%. Measure the NMR spectrum of the fraction and confirm that the fraction is labeled ^).

'H-NMR (300. 40MHz,鵷CDC 1 _3, leash: TMS) δ (p pm) : 2. 52 (2H), 4. 47 (2Η), 5. 8 (1Η), 6. 1 (1Η ), 6.4 (1Η).

^{19 F-NMR (282. 65ΜΗ ζ} , solvent CD C 1 _{3, reference: CFC 1 3) δ (ρ} ρ m):. -81 1 (3 F), one 113. 6 (2F), one 121.5 (l OF), one 122.5 (2F), one 123.3 (2F), one 125.8 (2F).

(Example 5-2) F (CF ₂ ) ₁₀ CH ₂ CH ₂ OCOCH = co-weight of CH ₂ and norbornene ^ ί し た mL 職 た 職 し た し た 職 職 し た 30 し た 窒 素. Here, norbornene (3.0 g), 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. After 18 hours from the start, the mixture was cooled to room temperature to recover a crude liquid. Collected The crude solution was inverted by adding AK-225 (50 g), and then dropped into hexane (200 g) to recover a solid content. Furthermore, the recovered solid is dissolved in acetone (50 g) and hexane

(200 g). Then, it was dried (70 ° C, 19 hours) to obtain ^^ (10 g) as a solid at room temperature.

^{As a result of 1} H-NMR and ¹⁹ F-NMR analyses, 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.

Chromatography NMR (300. 4MHz,鵷: CDC 1 _3, fireman's standard: TMS) δ (p pm) :... 1. 0~2 4, 2. 4~3 0, 4. 2~4 7.

¹⁹ F- NMR (282. 7MH z, Nada: CD C 1 _{3, reference: CFC 1 3) S (p} pm): -8 1. 8 (3 F), -1 1 3. 8 (2 F), — 1 21.8 (10 F), — 1 22.5

(2F) '-1 23.5 (2F),-126.4 (2F).

 (Example 5-3) Example of fluorination of the double-stranded book obtained in Example 5-2

 According to 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

(3. O g) was obtained.

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.

¹ H-NMR (300. 4 MHz, 鵷: -l 13, fresh: TMS, standard: nitro benzene) δ (p pm): 2.6 to 4.4, 5.0 to 6.0, 6, 5—7.0.

^{19 F-NMR (282. 7 MHz} , Nada: R- 1 13, reference: CDC 1 _3, inner release form quasi:

C ₆ F ₆ ) δ (p pm): -81 to -1 83, -85 87, -120 to 1 127, 1 20

9 to 1 2 1 2. [Example 6]

(Example 6—1) CH ₂ = CHCOO (CH ₂ ) ₂ (CF ₂ ) ₈ F

^, A 200-ml 4-neck flask equipped with a thermometer and a distillation column was prepared. Here, F (CF ₂ ) ₈ CH ₂ CH ₂ OH (1492 g, 95.0% yarn coverage, 2.7 mol), paratoluene snolefonic acid (68.4 g), Atari / (330 g), hydroquinone (2 . 64 g). The temperature of the inside of the ¾ was raised to 90 ° C and the temperature was slowly increased to E (26.6 kPa (absolute pressure)).

0 & 1 hour after the start, the water that had passed through was distilled off from the top of the distillation column with a boat at 1 Oml / hour. 10 hours after the start, ® was terminated when the S conversion reached 99%. Water (700 ml) was added to ® ®, and the temperature was adjusted to 50 ° C to remove iJ's acrylic acid and paratoluenesnolefonic acid. Distillation gave CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ ) ₈ F (1100 g, bp. 87 ° C / 1. 6X 133. 322 Pa (舰 pressure)).

(Example 6-2) CH ₂ = CHCOO (CH ₂ ) ₂ (CF ₂ ) ₈ F <M ^ \ (Part 2)

F (CF ₂ ) ₈ CH ₂ CH ₂ CH ₂ OCOCH = CH ₂ (18 g), R—225 (42 g), and 2, 2′-azobisisobutyronitrino obtained in Example 6-1 Degassing (0.18 g) was repeated three times with 100 ml of glass ampoule by applying AL liquid to the sample, and then polymerized at 60 ° C for 15 days. Polymerization of f-sister was not detected from the GC of the liquid solution after the completion of the reaction. Monomer was not substantially detected, and the repeating unit [− CH ₂

— CH (COO (CH ₂ ) ₂ (CF ₂ ) ₈ F) 1] The weight average molecular weight of the obtained polymer was 48,000.

 (Example 6-3) Heavy ^ obtained in Example 6-2 (Example of fluorination of book)

In 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.

¹ H-NMR (300.4 MHz, Nada: R-113, Fresh: TMS, Internal standard: Nitoguchi benzene) δ (p pm): 2.6 ~ 3.5, 4.0 ~ 6.0, 6.5-7.0.

^{. 19 F-NMR (282. 7} MHz, Nada: R- 1 13, fireman's standard: CFC 1 _3, inner咅廳 _{quasi: C 6 F 6) 5 (} p pm): -73 0~ one 87.0, - 105.0--136.0,-21 0.0-1 215.0.

 [Example 7]

(Example 7-1) CF ₃ CF ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ synthesis example

Example 11 F (CF ₂ ) ₄ 〇1¾011 in 1-1. ? ₃ . ? Changing to ₂ 0 ^ ¾01¾ (15.0 g) and changing acri / to meth / also performed ^ &, », and filtration. The filtrate was subjected to E distillation to obtain a fraction (23.5 g) of 55 ° C / l 2 kPa pressure). The GC purity of the fraction was 99%. The NMR spectrum of the fraction was determined, and it was determined that the main component was the title compound.

^J H-NMR (300. 40MHz, Nada CDC 1 _3, fireman's standard: TMS) δ (p pm) : 1. 97 (3H), 4. 60 (2Η), 5. 7 (1Η), 6. 21 (1Η ).

^{19 F-NMR (282. 65MH z} , solvent CD C 1 have _{reference: CFC 1 3) δ (ppm} ):.. -81 8 (3F), -123 17 (2F).

(Example 7-2) CF ₃ CF ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ polymerization example

Example 1 Change F (CF ₂ ) CH ₂ CH ₂ OCO CH ₃ = CH ₂ 7-1 -C ^ CF ₃ CF ₂ CH ₂ OC〇C (CH ₃ ) = CH ₂ (12.9 g) , 2, 2'-azobisisobutyronitrile was changed to 0.25 g, and the amount of R-225 was changed to 28.6 g, as in Example 1-2. After further drying, a polymer (10.8 _g ) solid at room temperature was obtained. ^{As a result of 1} H—NMR and ¹⁹ F—N, it was determined that the polymer was a polymer composed of repeating units [one CH ₂ —C (CH ₃ ) (COOCH ₂ CF ₂ CF ₃ ) one] . Ma The average molecular weight measured by GPC was 19,800.

Ή-NMR (300. 4MHz, Nada: CDC 1 _3, male: TMS) δ (p pm) :... 0. 8~1 5, 1. 8~2 4, 4. 2~4 6.

^{19 F-NMR (282. 7MH z} , solvent: CD C 1 have _{reference: CFC 1 3) δ (ppm} ):. -83 9 (3F), one 125. 5 (2F).

 (Example 7-3) Example of fluorination of the heavy ^ (

 装置 The same equipment as in Rows 1-3 was ¾1;; ^ After injecting nitrogen gas into the clave for 1.0 hour, 赚 Fluorine gas was injected with ¾! SilO. 4LZh for 1 hour.

 Next, while blowing 20% fluorine gas at the same flow rate, the polymer (7.9 g) obtained in Example 7-2 was dissolved in R-113 (161.4 g), and the mixture was heated for 7.5 hours. I did & λ. Then, while injecting 20% ¾ fluorine gas at the same rate, inject 6 mL of R-113 intense night, further inject 20% ¾ fluorine gas for 0.5 hour, then nitrogen gas for 1.0 hour I blew it.

After completion, the crude liquid was recovered, and the solvent was distilled off under reduced pressure (60 ° C, 6. hours) to obtain a viscous liquid ripp (10.3 g) at room temperature. . - NMR, ¹⁹ F- result of NMR, raw Narubutsu fluorine I having the structure 78 mole _^0/0 of the hydrogen atoms in the polymer obtained in Example 7- 2 (average fit) is a fluorine atom [ ^ The power of being united S «was done. The average molecular weight measured by GPC was 1,400.

 Ή-NMR (300.4MHz, Nada: R-113, standard: TMS, including benzene) δ (p pm): 3.0-4.0, 4.0-5.0, 5 3-6.7, 6.7-7.3.

¹⁹ F- NMR (282. 7 MHz, Nada: R- 113, reference: CDC 1 _3, Uchiyujun: to hexa Full O b benzene) δ (p pm):. -56 5~ one 59.0 One 81.0 to -82.

0, -82.0 to 1 82.5, 186.0 to 187.5, 1106.0 115.0,

-127. 0 to 1 130.5, -147.5.0 148.5, 1 170.0 to 1 18 5.0.

 (Example 7-4) Ester bond of fluorinated polymer obtained in Example 7-3 Example

後、 フラスコより回収したサンプルを濾過し、 液状の^ ¾物 (5. 6 g) を回収した。 生 成物は、 エステノ 合が した化^ #1を^ it物とする 2種以上の化^ ¾の混 で あることを NMRにより β、した。 また、例 7— 3で得たフッ素ィ虚合体中に械するェ ステ 合の 69. 7%が^^されて一 COF基に変換されていることを NMRにより確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 ^^.

Ρ 7

¹ H-NMR (300.4ΜΗζ, Nada: R-l13, standard: TMS, standard: double-mouthed benzene) δ (ppm): 3.0-4.0, 4.0-5.0, 5 3-6.7, 6.7-7.3.

¹⁹ F- NMR (282. 7 MHz, solvent: R_L 13, reference: CDC 1 _3, the inner can Nishijun: to Kisafunoreo port benzene) δ (ppm):.. 48. 5~23 0, -56 5~ one 59.0,

-62. 0 to 1 74.0, 1 81.0 82.0, 1 82.0 to 1 82.5, 1 86.

0 87.5, 1 106.0 to 1115.0, 1127.0 to 1130.5, 1 147.

0 148.5, 1 170. 0 185.0.

 (Example 7-5) Example of esterification of ^^ product obtained in Example 7-4

While the methanol (5.8 g) was vigorously applied to the flask at λ ^ 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.

¹ H-NMR (300.4 MHz, Nada: R-113, Standard: TMS, Internal: Nito Benzene) δ (p pm): 3.0 to 3.5, 3.5 to 4.0, 4.0 to 5.0, 5.3 to 6.7, 6.7 to 7.3.

^{1 9 F-NMR (282. 7MHz} , Nada: R- 113,挪: CDC 1 _3, the inner semi-: to Kisafunoreo port benzene) δ (p pm):. -58 5 68. 0, one 70.0-1 80.

0, 1 81.0 82.0, 1 82.0-1 82.5, 1 86.0 87.5, 1 1

06.-1 to 115.0, 1127.0 to 130.5, 1147.0 to 148.5, 1170.0 to 185.0.

 [Example 8]

(Example 8—1) Example of synthesis of F (CF ₂ ) a OCF (CF ₃ ) CF ₂ 〇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. After the completion of the dropping, one hour was won, and the mixture was cooled to room temperature to recover a crude liquid. The collected broth was slowly dropped into distilled water (300 g), separated into two layers, and recovered. The operation of collecting the collected mochi was repeated intensely with a 5% by mass methanol aqueous solution (300 g), separated into two layers, and then recovered five times. Further, the dried rice cake was dried with magnesium and filtered. The filtrate was subjected to ^ Εdistillation to obtain a fraction (141.8 g) of 88.5 ° C / 9.3 kPa ii ±). The GCS was 95.9%: ^ The NMR spectrum of the fraction was measured, and ± ± minutes were marked ^!

¹ H-NMR (300. 40MHz ,? fireman's standard CDC 1 _3, male: TMS) 5 (ppm): 4. 13 (1H), 4. 18 (1H).

^{19 F-NMR (282. 65MH z} , solvent CD C 1 _{3, reference: CFC 1 3) δ (ρ} ρ m):.. -78 0 (IF), -79 9 (3F), one 81.2 ( 3F), -81.4 (2 F), -81.9 (IF), -82.2 (3F), -129.1 (2F), -135. 4 (IF), -144.5 (1 F).

(Example 8-2) F (CF ₂ ) 3 OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ 〇COCH = CH ₂

A 1 L flask having a dropping funnel at the top and having its interior sufficiently nitrogenated beforehand was broken. In the flask, F (CF ₂ ) 3 OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OH (88.3 g), methylene chloride (340.8 g), pyridine (13.7 g) and hydroquinone (0.12 g), and the water was violently winning. Then, at »! ^^ Atarino from the upper dropping funnel! ^ Chloride (19.1 g) was dripped slowly. After dropping, the internal temperature was adjusted to 40 ° C, and the temperature was lowered for 3 hours. Next, distilled water (150 g) was added dropwise, and the mixture was separated into two layers to recover an organic phase. 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 β was determined that the fraction was labeled ^.

^ -NMR (300. 40MHz,鵷_{CDC 1 3, ¾2p: TMS)} δ (p pm): 4. 13 (1H), 4. 1 8 (1Η), 6. 08 (1H), 6. 18 (1Η ), 6.52 (1Η).

^{19 F-NMR (282. 6 5ΜΗ} ζ, solvent CD C 1 _{3, reference: CFC 1 3) 5 (ρ} ρ m):.. -78 0 (IF), -79 9 (3F), -8 1. 2 (3 F), —81.4 (2 F), —81.9 (1 F), 1 82.2 (3F), -129. 1 (2F), 1 135.4

(IF), -144.5 (IF).

(Example 8-3) F (CF ₂ ) a OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OCOCH = CH ₂ weight

A 5 OmL round-bottomed flask whose inside was replaced in advance was crushed. Here, F (CF ₂ ) 3 OCF (CF ₃ ) CF ₂ 〇CF (CF ₃ ) CH ₂ OCOCH = CH ₂ (36. Og) and 2,2, -azobisisobutyronitrile (0.1 g) as the polymerization initiator were dissolved in R-225 (25.3 g). The operation of intensifying overnight with liquefied nitrogen, degassing with a vacuum pump, and inverting was performed three times. Then, the temperature was raised to 60 ° C using an oil bath while violently lightning the night, and Polymerization®S was started. After 15 hours from the start, the mixture was turned over to room temperature and the crude liquid was recovered. The collected crude liquid was dropped into methanol (300 g) to recover a solid content. In addition, the recovered solid is converted to R-225 (100 g) and dropped twice into hexane (500 g), and the operation is performed twice. Then, the pressure-reduced grass (100 ° C, 24 hours) Then, at room temperature, an elastomer-like solid (20.8 g) was obtained.

As a result of ¹ H-NMR and ¹⁹ F-NMR, the obtained solid was composed of a repeating unit [one CH ₂ — CH (C OOCH ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) 〇 (CF ₂ ) ₃ F) [1]. The average molecular weight of the polymer was measured by GPC and found to be 21,000.

^! H-NMR (300. 4MHz, Nada: CDC 1 _3, leash: TMS) δ (p pm) :.. 1. 3- 2. 1, 2. 2~2 6, 4. 4~4 9.

^{19 F-NMR (282. 7 MHz} , solvent: CDC 1 have _{reference: CFC 1 3) δ (ρ} ρ m):... -78 0 (IF), -79 9 (3F), -81 2 (3F ), —81.4 (2 F), —81.9 (IF), −82.2 (3F), —129.1 (2F), 135.4 (IF), 144.5 (IF) .

 (Example 8-4) Example of fluorination of the polymer obtained in Example 8-3

 The heavy ^ (this (2.3 g) obtained in Example 1-2 in Example 1-3 was dissolved in R-113 (114 g) and the polymer obtained in Example 8-3 (5.16 g) was dissolved. ) Was added to R-113 (260 g), and the solution was sprayed over 3 and 12 hours, followed by fluorine treatment.

After completion of the synthesis, the liquid was recovered, and R-113 was distilled off with a car (80 ° C, 10. OB Temple) to obtain a viscous liquid product (5.3 g) at room temperature. Was. As a result of analyzing the 4β¾ was 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.

¹ H-NMR (300.4MHz, Nada: R-113, Fresh: TMS, Inner court: Nitoguchi benzene) § (p pm): 2.8-3.7, 3.8-5.0, 5 1-6.6.

¹⁹ F- NMR (282. 7 MHz, Nada: R- 113, Agata: CDC 1 _{3, Uchiyujun: C 6 F 6) δ (} p pm):. -78 0~- 85. 5, -95. 0 to 1 109.0, -129.

0 131. 0, -134. 0 to 1 136.0, 1 144.0 to 1 150.0, 1 16

5.0 to one 205.0.

 [Example 9] Glass surface

(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 ί 夜 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-20S¾ Insect angle meter).

 As a result, the deworming angle in water was 114.2 degrees, and the contact angle in hexadecane was 78.5 degrees. In addition, when the fall angle of hexadecane (IOL) was measured with the device on the shelf,

 Furthermore, 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 ¾9 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>

 According to 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.

 In addition, the 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 ¾k oil repellency on the surface of the ^.

Claims

1. Including the following polymerization step and the following fluorination step performed after the consolidation step: ^ Fluorine polymerization step: a step of polymerizing a monomer (β) having a fluorine atom and a hydrogen atom converted into a carbon atom, or , A tijf monomer (β) and a comonomer (j) copolymerizable with the monomer (] 3)  Fugamadori process: A liquid fluorine is obtained by dissolving a partially fluorine-containing polymer having a fluorine atom as a carbon atom and a TK element atom as a carbon atom in a fluorine atom, followed by liquid-phase fluorination. Separation of at least one hydrogen atom bonded to a carbon atom into a fluorine atom 2. The method according to claim 1, wherein the partially fluorinated polymer is a secondary product of a polymerization step. 3. The i¾ ^ fe according to claim 1 or 2, wherein the polymerization in the polymerization step is an addition polymerization. 4. The monomer (j3) force S, which is a monomer obtained through the following monomer synthesis: Mi ^ ¾ described in claim 1, 2, or 3 Monomer Synthesis Step: 'the monomer one having隨and (Y ²⁾ (α), saying ¾¾¾' and hydrogen atoms to carbon atoms Awakening: (Upsilon ²⁾ and was capable of forming a continuous line诘合or linking groups' To form a fluorine-containing compound that has both (隨¹ ) and a fluorine atom bonded to a carbon atom. 5 · Partially fluorinated heavy ^ The average preferred weight of the book is 1000 or more, 6. partially fluorinated I匕重fluorine content 3 0 coalescence - a 7 0 wt _^0/0, off of the fluoropolymer Tsu * ^ Yes 4 ^ a 35 mass _^0/0 h, and, Claims 1 to 5 wherein the amount is greater than the amount of the partially fluorinated polymer. 7. The polymer in which all of the fluorine atoms of the partial fluorine-containing compound are converted to hydrogen atoms is not soluble in the fluorine-containing compound, and is heavy. ¾ 8. partially fluorinated polymers of claims 1-7 Les performing fluorination step until 4 0 mole _^0/0 or more ^ k atom bonded to a carbon atom is Mm fluorine atom, according to whether the deviation Made of ^ 9.Partially fluorinated (This is a polymer that has a monovalent fluorinated moiety and is linked to the side chain of the polymer by an esteno bond. One or more of the hydrogen atoms are converted to fluorine atoms, and the fluorine-containing heavy ^ which is essential for the ester ^^ in the polymer side chain (this is a book, claims 1 to 8 (7). Made 10. The monomer (j3) is a monomer having a (meth) atalyloyloxy group and 1-fluorinated haze, and the partially fluorinated polymer is a polymer having a repeating unit of the monomer as an essential component. 10. The process according to claim 9, wherein the fluoropolymer is a polymer having a fluorine atom attached to a carbon atom in the polymer and having a monovalent fluorine-containing organic group connected to the side chain of the polymer by an ester bond. 11. The fluorinated polymer obtained by the production according to claim 10, wherein an ester of the polymer side chain is converted to a COF group by ^^, and the polymer is converted into carbon atoms. Combined M ^ fe of a polymer having a fluorine atom and having one CO F group in the side chain of the polymer 1 2. The heavy compound obtained in claim 11 (in the present invention, the hydroxylated compound having a fluorine-free compound, a monovalent compound having a monovalent structure and a water-soluble compound in the —CO F group of the polymer side chain). A polymer having a fluorine atom as a carbon atom in the polymerization, having a force, a fluorine atom not bonded to the side chain of the polymer by an aesthetic, and having a monovalent property (the S5t of this book). ^ 1 3. —Repeating unit represented by the general formula [CX ¹⁰ X ²⁰ -C (R ¹⁰ ) COOR "] (where X ¹⁰ and X ²⁰ are each; each hydrogen atom or fluorine atom is And R ^{1 Q} represents a hydrogen atom, a fluorine atom, or a fluorinated methyl group, and X ^{1 D} , ² ° and 1 ^ ^{1 (} at least one selected from ³ requires a fluorine atom is to group. R ^H includes.) indicating the Rere monovalent organic group free of fluorine, and the polymer proportion of fluorine atoms is 35 mass ⁰ /.～ 8 6 mass _^0/0, m coalesce Organic destruction that can invigorate the atmosphere. 13. The extinct material according to claim 13, wherein 1 is a coating agent.