JP2009161532A - Fluoroether carboxylic acid, surfactant, production method of fluorine-containing polymer using the same and aqueous dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound which shows a low bioaccumulation potential and can be suitably used as a surfactant, a production method of a fluorine-containing polymer using the new compound, a surfactant, and an aqueous dispersion of the fluorine-containing polymer. <P>SOLUTION: The new compound is a fluoroether carboxylic acid represented by formula (I): CF<SB>3</SB>(CF<SB>2</SB>)<SB>n</SB>OCH<SB>2</SB>CF<SB>2</SB>CF<SB>2</SB>ORfCOOM (wherein Rf is a partially or completely fluorine-substituted 2C alkylene group; n is 0 or 1; and M is a monovalent alkali metal, NH<SB>4</SB>or H). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a fluoroethercarboxylic acid, a surfactant, and a fluorine-containing polymer and an aqueous dispersion using the same.

As a compound obtained by the ring-opening reaction of tetrafluorooxetane, XCH ₂ CF ₂ COY (wherein X is R ¹ O— or R ² CH ₂ CF ₂ CF ₂ O—, R ¹ and R ² is a saturated aliphatic group having 1 to 3 carbon atoms or a halogenated saturated aliphatic group, etc. Y is —OR ³ , and R ³ is a saturated aliphatic group having 1 to 3 carbon atoms or a halogenated group. 2,2-difluoropropionic acid derivatives represented by a saturated aliphatic group or the like) (see, for example, Patent Document 1).

Moreover, it is a carboxylate obtained by utilizing the ring-opening reaction of tetrafluorooxetane, and has excellent surface activity,
Rf ¹ (OCH ₂ CF ₂ CF ₂ ) _n1 OCX ¹ X ² CF ₂ (Rf ² ) _n2 COOM
(In the formula, Rf ¹ represents a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, and the fluoroalkyl group contains 1 to 5 oxygen atoms in the main chain; Rf ² represents a linear or branched fluoroalkylene group having 1 to 25 carbon atoms, and the fluoroalkylene group may contain 1 to 5 oxygen atoms in the main chain. N1 represents an integer of 0 to 3, and n2 represents an integer of 0 or 1. X ¹ and X ² are the same or different and represent a hydrogen atom or a fluorine atom, and M represents NH ₄ or Represents a monovalent metal element) (see, for example, Patent Document 2). However, there is no specific description of a specific compound having excellent surface activity and low bioaccumulation.

JP-A-2-223538 (Claim 1) International Publication No. 2005/003075 Pamphlet

An object of the present invention is to provide a novel compound with low bioaccumulation, a method for producing a fluoropolymer using the novel compound, a surfactant, which can be suitably used as a surfactant in view of the above-mentioned present situation. And providing a fluoropolymer aqueous dispersion.

The present invention relates to the following general formula (I)
_{CF 3 (CF 2) n OCH} 2 CF 2 CF 2 ORfCOOM (I)
Wherein Rf is a partially or entirely fluorine-substituted alkylene group having 2 carbon atoms, n is 0 or 1, and M is a monovalent alkali metal, NH ₄ or H. A fluoroethercarboxylic acid.

The present invention provides the following general formula (II) by contacting the fluoroethercarboxylic acid with fluorine.
CF ₃ (CF ₂ ) _n OCFXCF ₂ CF ₂ ORfCOOM (II)
(Wherein Rf is a partially or entirely fluorine-substituted C 2 alkylene group, n is 0 or 1, M is a monovalent alkali metal, NH ₄ or H, and X is H or F). It is a manufacturing method characterized by manufacturing the fluoro ether carboxylic acid manufactured.

The present invention is a surfactant comprising the above fluoroethercarboxylic acid.

The present invention is a polymerization surfactant comprising the above fluoroethercarboxylic acid.

The present invention is a method for producing a fluorine-containing polymer, comprising a step of polymerizing a fluorine-containing monomer in an aqueous medium containing the fluoroethercarboxylic acid.

The present invention is an aqueous dispersion containing a fluoropolymer, comprising the fluoroethercarboxylic acid, wherein the fluoropolymer has an average particle size of 50 to 500 nm. is there.

The present invention relates to the step (A) of bringing the aqueous dispersion into contact with an anion exchange resin in the presence of a nonionic surfactant and the aqueous dispersion obtained in the step (A) in the aqueous dispersion. It is a manufacturing method of the refinement | purification aqueous dispersion characterized by including the process (B) concentrated so that solid content concentration may be 30-70 mass% with respect to 100 mass% of aqueous dispersion.

The present invention is a fine powder produced by coagulating the aqueous dispersion.

The present invention provides the following general formula (I) from at least one component selected from waste water generated by coagulation of the aqueous dispersion, waste water generated by washing, and / or off-gas generated in the drying step.
_{CF 3 (CF 2) n OCH} 2 CF 2 CF 2 ORfCOOM (I)
(Wherein Rf is a partially or entirely fluorine-substituted alkylene group having 2 carbon atoms, n is 0 or 1, M represents a monovalent alkali metal, NH ₄ or H). Or the following general formula (II)
CF ₃ (CF ₂ ) _n OCFXCF ₂ CF ₂ ORfCOOM (II)
(Wherein Rf is a partially or entirely fluorine-substituted C 2 alkylene group, n is 0 or 1, M is a monovalent alkali metal, NH ₄ or H, and X is H or F). A method for producing regenerated fluoroethercarboxylic acid, comprising a step of recovering and purifying the fluoroethercarboxylic acid to be purified.
The present invention is described in detail below.

The fluoroethercarboxylic acid of the present invention has the following general formula (I)
_{CF 3 (CF 2) n OCH} 2 CF 2 CF 2 ORfCOOM (I)
(Wherein Rf is a partially or entirely fluorine-substituted C2 alkylene group, n is 0 or 1, M represents a monovalent alkali metal, NH ₄ or H). .

The inventors of the present invention are useful for emulsion polymerization of fluoroolefins even though the fluoroethercarboxylic acid having the structure CF ₃ (CF ₂ ) _n OCH ₂ CF ₂ CF ₂ ORfCOOM has a hydrogen atom in the structure, Furthermore, the inventors have found that it can be easily separated and recovered from the polymer after the polymerization, thereby completing the present invention.

That is, when the fluoroethercarboxylic acid of the present invention is used as a surfactant for emulsion polymerization of fluoroolefins, it exhibits excellent surface activity and can stably obtain a high molecular weight fluoropolymer. When a conventional washing method is performed, it can be easily separated and recovered from the polymer.

Furthermore, the fluoroethercarboxylic acid of the present invention has an extremely excellent effect of low bioaccumulation. In general, in the case of a surfactant having a fluoroalkyl group as a hydrophobic group, bioaccumulation tends to be low when the number of carbons is small and high when the number of carbons is large. In contrast, the surface activity is low when the number of carbon atoms is small, and is high when the number of carbon atoms is large. The fluoroethercarboxylic acid of the present invention is contrary to such technical common sense and has a low bioaccumulation property despite its excellent surface activity. The reason for this is presumed to be that it is difficult to be taken into the living body due to having a specific structure partially containing a hydrogen atom in the structure, or it is quickly discharged even if it is taken in.

Rf in the general formula (I) is preferably —CH ₂ CF ₂ —, —CHFCF ₂ —, —CF ₂ CF ₂ —, or —CF (CF ₃ ) —. Of these, from the viewpoint of excellent surface _{activity, -CF 2 CF 2 -, -} CF (CF 3) - is preferably.

M in the general formula (I) represents a monovalent alkali metal, NH ₄ or H, and examples of the monovalent alkali metal include Li, Na, and K. The M is preferably NH _{4 in} that it can be easily removed by heat treatment.

As the fluoroethercarboxylic acid of the present invention,
CF ₃ OCH ₂ CF ₂ CF ₂ OCH ₂ CF ₂ COONH ₄ ,
CF ₃ OCH ₂ CF ₂ CF ₂ OCHFCF ₂ COONH ₄ ,
CF ₃ OCH ₂ CF ₂ CF ₂ OCF ₂ CF ₂ COONH ₄ ,
CF ₃ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) COONH ₄ ,
CF ₃ CF ₂ OCH ₂ CF ₂ CF ₂ OCH ₂ CF ₂ COONH ₄ ,
CF ₃ CF ₂ OCH ₂ CF ₂ CF ₂ OCHFCF ₂ COONH ₄ ,
CF ₃ CF ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ CF ₂ COONH ₄
Etc.

The fluoroethercarboxylic acid of the present invention is, for example,
(1) (CF ₃ ) _n COF _2-n is subjected to a ring-opening addition reaction with tetrafluorooxetane or hexafluoroepoxypropane, and fluorinated as necessary, to obtain the following general formula (3)
CF ₃ (CF ₂ ) _n OCH ₂ CF ₂ CF ₂ ORfCOF (3)
(Wherein Rf and n are the same as above), a step of synthesizing the fluorocarboxylic acid fluoride (3), and
(2) The fluorocarboxylic acid fluoride (3) can be produced by a method including a step of converting the terminal —COF of the fluorocarboxylic acid fluoride (3) into —COOM.

The fluoroethercarboxylic acid of the present invention also has
(CF ₃ ) _n COF _2-n is subjected to a ring-opening addition reaction of tetrafluorooxetane, and the following general formula (α)
CF ₃ (CF ₂ ) _n OCH ₂ CF ₂ COF (α)
(Wherein n is the same as above), a step of synthesizing a fluorocarboxylic acid fluoride (α) represented by:
The above fluorocarboxylic acid fluoride (α) is further subjected to a ring-opening addition reaction of tetrafluorooxetane, and fluorinated as necessary, whereby the following general formula (3-1)
CF ₃ (CF ₂ ) _n OCH ₂ CF ₂ CF ₂ ORf′COF (3-1)
(Wherein Rf ′ represents —CH ₂ CF ₂ —, —CHFCF ₂ — or —CF ₂ CF ₂ —, and n is the same as described above). And the process of
The terminal-COF of the fluorocarboxylic acid fluoride (3-1) can be produced by a method including a step of converting it to -COOM.

The fluoroethercarboxylic acid of the present invention also has
(CF ₃ ) _n COF _2-n is subjected to a ring-opening addition reaction of tetrafluorooxetane, and the following general formula (α)
CF ₃ (CF ₂ ) _n OCH ₂ CF ₂ COF (α)
(Wherein n is the same as above), a step of synthesizing a fluorocarboxylic acid fluoride (α) represented by:
The fluorocarboxylic acid fluoride (α) is subjected to a ring-opening addition reaction of hexafluoroepoxypropane, and the following general formula (3-2)
_{CF 3 (CF 2) n OCH} 2 CF 2 CF 2 OCF (CF 3) COF (3-2)
(Wherein n is the same as above), a step of synthesizing the fluorocarboxylic acid fluoride (3-2), and
The terminal-COF of the fluorocarboxylic acid fluoride (3-2) can be produced by a method including a step of converting it to -COOM.

Examples of the fluorocarboxylic acid fluoride (3) include:
The following general formula (1)
CF ₃ (CF ₂ ) _n OCH ₂ CF ₂ CF ₂ OCH ₂ CF ₂ COF (1)
Fluorocarboxylic acid fluoride (1) represented by the following general formula (2a)
CF ₃ (CF ₂ ) _n OCH ₂ CF ₂ CF ₂ OCHFCF ₂ COF (2a)
And a fluorocarboxylic acid fluoride (2a) represented by the following general formula (2b)
CF ₃ (CF ₂ ) _n OCH ₂ CF ₂ CF ₂ OCF ₂ CF ₂ COF (2b)
Fluorocarboxylic acid fluoride represented by (2b)
Is mentioned.

The fluorocarboxylic acid fluoride (1) can be produced by a ring-opening addition reaction in which tetrafluorooxetane is subjected to ring-opening addition to (CF ₃ ) _n COF _2-n .

The fluorocarboxylic acid fluoride (2a) can be produced by monofluorination of the fluorocarboxylic acid fluoride (1), and the fluorocarboxylic acid fluoride (2b) is obtained by converting the fluorocarboxylic acid fluoride (1) to It can be produced by difluorination.

In the step (1), for example, (CF ₃ ) _n COF _2-n and tetrafluorooxetane or hexafluoroepoxypropane are reacted with each other using a fluorine ion as a catalyst in an aprotic polar solvent to obtain CF ₃ (CF ₂ ) _n (OCH ₂ CF ₂ CF ₂ ) _m ORfCOF (n is 0 or 1, m is 0 or an integer of 1 or more, and Rf is the same as above).

Examples of the fluorine ion source include alkali metal fluorides such as cesium fluoride, potassium fluoride, and sodium fluoride, and tetramethylurea.

Examples of the aprotic polar solvent include glymes such as tetraglyme, diglyme, triglyme and polyglyme, THF, dioxane, DMF, DMA, HMPT, acetonitrile and the like.

The reaction between the (CF ₃ ) _n COF _2-n and tetrafluorooxetane is usually performed with stirring for 1 to 24 hours under the conditions of a temperature of −50 to 50 ° C. and a pressure of 0 to 1 MPa. it can.
The progress of the reaction between the (CF ₃ ) _n COF _2-n and tetrafluorooxetane is observed by a gas chromatograph or the like.

The amount of the _{catalyst, (CF} 3) to n _{COF 2-n} total amount of, is preferably 1 to 100 mol% on a molar basis. A more preferred lower limit is 5 mol%, and a more preferred upper limit is 50 mol%.

The amount of the solvent is not particularly limited, but it can be used in a large amount when it is necessary to lower the pressure expected from the boiling point of (CF ₃ ) _n COF _2-n and the reaction temperature. However, if the amount is too large, separation and recovery of the product after the reaction becomes difficult. Therefore, the volume of (CF ₃ ) _n COF _2-n is set to 1 and is preferably 0.1 to 1000 times. A more preferred lower limit is 0.5 times, and a more preferred upper limit is 2 times.

The _{(CF 3)} n _{COF 2-n} and tetrafluoroethylene Oki to the total molar amount of the cetane _{(CF 3)} n _COF ratio of _2-n is preferably in the range of 9-95 mol%. From the viewpoint of yield, the ratio of (CF ₃ ) _n COF _2-n can have a more preferable lower limit of 15 mol% and a more preferable upper limit of 50 mol%. A more preferred lower limit is 30 mol%, and a more preferred upper limit is 40 mol%.

The reaction vessel used for the reaction between the (CF ₃ ) _n COF _2-n and tetrafluorooxetane is not particularly limited as long as it can maintain airtightness and can be stirred. Any of plastic containers made of other plastics, etc., and glass containers (however, if water is mixed, there is a risk of corrosion). The reaction vessel should be selected based on the reaction volume, reaction temperature, and reaction pressure.

The reaction between the (CF ₃ ) _n COF _2-n and tetrafluorooxetane is a reaction in which two or more tetrafluorooxetanes can be added to one (CF ₃ ) _n COF _2-n molecule, and the reaction product Is generally a mixture of compounds with different addition numbers of tetrafluorooxetane. Therefore, it is preferable to perform the separation operation for obtaining the fluorocarboxylic acid fluoride (1) from the above mixture prior to the fluorination.

The separation operation can be performed by rectification using a rectification column having an appropriate number of stages. The appropriate number of stages is determined by the boiling point of (CF ₃ ) _n COF _2-n as the remaining raw material, the boiling point of the aprotic polar solvent, the boiling point of the fluorocarboxylic acid fluoride (1), and the like.

When the fluorocarboxylic acid fluoride (1) is separated by the above separation operation, the fluorocarboxylic acid fluoride (1) is subjected to fluorination as necessary to obtain fluorocarboxylic acid fluorides (2a) and (2b). Can be obtained.

The _{fluorination, CoF 3, AgF 2, UF} 6, OF 2, N 2 F 2, OF 3 OF, IF 5, ClF fluorinating reagent such as _3; the _{F 2} conventionally known fluorine radical generating source such as a gas Can be used.
For the fluorination, a metal container, a fluororesin container or the like is used.
In the fluorination, a solvent may not be used, but can be used. For example, when a polar solvent such as acetonitrile is used, the fluorocarboxylic acid fluoride (2a) can be obtained in a high yield. If it is completely fluorinated, the fluorocarboxylic acid fluoride (2b) can be obtained.
When the fluorocarboxylic acid fluoride (2a) and the fluorocarboxylic acid fluoride (2b) are obtained as a mixture, they can be separated by a separation and purification method using a boiling point difference such as rectification or distillation. Since the difference in boiling point between the fluorocarboxylic acid fluoride (2a) and the fluorocarboxylic acid fluoride (2b) is small, a rectifying column having a high number of stages is required to obtain a high-purity product.

When it is difficult to separate the target fluorocarboxylic acid fluoride (1) by the separation operation, the terminal —COF is esterified with an alcohol such as methanol, and the following general formula (4)
CF ₃ (CF ₂ ) _n (OCH ₂ CF ₂ CF ₂ ) _m OCH ₂ CF ₂ COOR ⁴ (4)
(Wherein n represents 0 or 1, m represents 0 or an integer of 1 or more, and R ⁴ represents an alkyl group in which a hydrogen atom having 1 to 10 carbon atoms may be substituted with a fluorine atom). After converting to a mixture of terminal esterified products, the terminal esterified product of fluorocarboxylic acid fluoride (1) is separated.

The terminal esterified product of the fluorocarboxylic acid fluoride (1) has the same number of additions of the fluorocarboxylic acid fluoride (1) and tetrafluorooxetane, and the terminal is converted to —COOR ⁴ (R ⁴ is the same as above). Is.

Separation of the terminal esterified product of the fluorocarboxylic acid fluoride (1) can be usually performed by a separation and purification method using a boiling point difference such as rectification or distillation. Since the terminal esterified product of the fluorocarboxylic acid fluoride (1) has a higher boiling point than the fluorocarboxylic acid fluoride (1), it may be easily separated depending on the combination with the aprotic polar solvent. .

Further, since the terminal esterified product does not react with moisture as in the case where the terminal is —COF to generate hydrofluoric acid and corrode the glass, the glass-made apparatus can be used safely. .

The step (2) is a step of converting the terminal -COF of the fluorocarboxylic acid fluoride (3) into -COOM (M is the same as above).

As a method of converting terminal -COF to -COOM,
(A) The -COF at the end of the fluorocarboxylic acid fluoride (3) is hydrolyzed with acid to convert it to -COOH, and then neutralized with alkali to give -COOM ¹ (M ¹ is a monovalent Represents a salt)),
(B) A method of converting to —COOM ¹ by esterifying and separating the —COF at the terminal of the fluorocarboxylic acid fluoride (3), followed by saponification; or
(C) Esterify and separate -COF at the end of the fluorocarboxylic acid fluoride (3), saponify and convert to -COOM ¹ , then convert to -COOH using acid, and then neutralize with alkali Is preferably carried out by the method of converting to -COOM ¹ .

More specifically, in the step (A), the fluorocarboxylic acid fluoride (3) is hydrolyzed with an acid to remove by-product hydrofluoric acid, and distilled to obtain the following general formula. (5)
_{CF 3 (CF 2) n OCH} 2 CF 2 CF 2 ORfCOOH (5)
(Rf and n are the same as described above) is obtained, and then converted to -COOM ¹ by neutralization with an alkali if desired.

In the step (B), the terminal —COF is esterified and separated, and then the terminal —COOR ⁴ (R ⁴ is the same as above) is saponified to —COOM ¹ (M ¹ is the same as above). The method (C) is to saponify —COOR ⁴ (R ⁴ is the same as above) and then convert to —COOH using an acid, or optionally using an alkali. Summed-changes to COOM ¹ .

Examples of the acid include dilute sulfuric acid and hydrochloric acid, and examples of the alkali include alkali metals, alkaline earth metals, hydroxides thereof, aqueous ammonia, and the like.

By contacting the fluoroethercarboxylic acid of the present invention with fluorine, the following general formula (II)
CF ₃ (CF ₂ ) _n OCFXCF ₂ CF ₂ ORfCOOM (II)
(Wherein Rf is a partially or entirely fluorine-substituted C 2 alkylene group, n is 0 or 1, M is a monovalent alkali metal, NH ₄ or H, and X is H or F). A production method characterized by producing a fluoroethercarboxylic acid is also one aspect of the present invention.

The fluoroethercarboxylic acid represented by the general formula (II) can also be suitably used as a surfactant and has low bioaccumulation.

The fluoroethercarboxylic acid of the present invention can be suitably used as a surfactant. A surfactant comprising the above fluoroethercarboxylic acid is also one aspect of the present invention. The surfactant of the present invention can be used as a surfactant as long as it contains at least one fluoroethercarboxylic acid represented by the above general formula (I) or (II). It may contain two or more acids.

Since the surfactant of the present invention is composed of the above-mentioned fluoroethercarboxylic acid, it can exhibit an appropriate surface activity in various applications. The surfactant of the present invention can be used for applications such as production of fluorine-containing polymers.

The surfactant of the present invention is preferably used in the form of a monovalent alkali metal salt or ammonium salt from the viewpoint of water solubility, and can be easily removed by heat treatment and hardly remains in the resin. Of these, ammonium salts are more preferred.

The surfactant of the present invention is also preferably used in the form of carboxylic acid. In this case, the surface activity in water is improved compared to the salt, and for example, the surface tension at the same molar concentration is lower with carboxylic acid, and as a result, more stable and smaller polymer particles are obtained when used for polymerization. There are advantages that the obtained polymer colloid has high stability, the generation of aggregates during polymerization is small, and polymerization can be carried out to a high concentration.

The present invention is also a method for producing a fluorine-containing polymer, comprising a step of polymerizing a fluorine-containing monomer in an aqueous medium containing the above-described fluoroethercarboxylic acid.

In the method for producing a fluoropolymer of the present invention, the fluoropolymer can be efficiently produced if at least one of the above-mentioned fluoroethercarboxylic acids is used as a surfactant. Further, in the method for producing a fluoropolymer of the present invention, two or more of the above-mentioned fluoroethercarboxylic acids may be used simultaneously as a surfactant, or remain in a molded article made of a volatile polymer or a fluoropolymer. If possible, other compounds having surface activity other than the fluoroethercarboxylic acid may be used at the same time. As the other compounds having surface activity, those described above can be used.
Moreover, in the manufacturing method of the fluorine-containing polymer of this invention, in addition to the said fluoro ether carboxylic acid and the compound which has other surface active ability used as needed, an additive can be used in order to stabilize each compound. What was mentioned above can be used as said additive.

In the method for producing a fluoropolymer of the present invention, the polymerization is carried out by charging the polymerization reactor with an aqueous medium, the above-mentioned fluoroethercarboxylic acid, a monomer, and other additives as required, and stirring the contents of the reactor. The reactor is maintained at a predetermined polymerization temperature, and then a predetermined amount of a polymerization initiator is added to start the polymerization reaction. After the polymerization reaction is started, a monomer, a polymerization initiator, a chain transfer agent, the above fluoroethercarboxylic acid, and the like may be additionally added according to the purpose.
In the above polymerization, the polymerization temperature is usually 5 to 120 ° C., and the polymerization pressure is 0.05 to 10 MPaG. The polymerization temperature and polymerization pressure are appropriately determined depending on the type of monomer used, the molecular weight of the target fluoropolymer, and the reaction rate.

In the method for producing a fluoropolymer of the present invention, it is preferable to adjust the pH at the start of polymerization, for example, to adjust the pH to 6 or less, preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. Thus, a more stable polymer colloid can be obtained.

The fluoroethercarboxylic acid is preferably added in a total addition amount of 0.0001 to 10% by mass with respect to 100% by mass of the aqueous medium. A more preferable lower limit is 0.001% by mass, and a more preferable upper limit is 1% by mass. If the amount is less than 0.0001% by mass, the dispersion force may be insufficient. If the amount exceeds 10% by mass, an effect commensurate with the amount added may not be obtained, and the polymerization rate may be decreased or the reaction may be stopped. There is. The amount of the compound added is appropriately determined depending on the type of monomer used, the molecular weight of the target fluoropolymer, and the like.

The polymerization initiator is not particularly limited as long as it can generate radicals in the polymerization temperature range, and known oil-soluble and / or water-soluble polymerization initiators can be used. Furthermore, the polymerization can be started as a redox in combination with a reducing agent or the like. The concentration of the polymerization initiator is appropriately determined depending on the type of monomer, the molecular weight of the target fluoropolymer, and the reaction rate.

The aqueous medium is a reaction medium for performing polymerization and means a liquid containing water. The aqueous medium is not particularly limited as long as it contains water, and water and, for example, a fluorine-free organic solvent such as alcohol, ether, and ketone, and / or a fluorine-containing organic solvent having a boiling point of 40 ° C. or lower. May be included. For example, when carrying out suspension polymerization, a fluorine-containing organic solvent such as C318 can be used.
In the above polymerization, a known chain transfer agent and radical scavenger may be further added depending on the purpose to adjust the polymerization rate and molecular weight.

The fluoropolymer production method also includes a step of emulsion polymerization of a monomer in an aqueous medium in the presence of the fluoroethercarboxylic acid to obtain an aqueous emulsion (seed dispersion), and the aqueous emulsion. It may include a step of emulsion polymerization (seed polymerization) of the monomer in the presence of (seed dispersion).

The fluorine-containing polymer is obtained by polymerizing a fluorine-containing monomer, and may be obtained by copolymerizing a fluorine-free monomer depending on the purpose.

Examples of the fluorine-containing monomer include a fluoroolefin, preferably a fluoroolefin having 2 to 10 carbon atoms; a cyclic fluorinated monomer; a formula CY ₂ = CYOR or CY ₂ = CYOR ² OR ³ (Y is , H or F, R and R ³ are alkyl groups having 1 to 8 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms, and R ² is part or all of the hydrogen atoms. And a fluorinated alkyl vinyl ether represented by a C 1-8 alkylene group substituted with a fluorine atom.

The fluoroolefin preferably has 2 to 6 carbon atoms. Examples of the fluoroolefin having 2 to 6 carbon atoms include tetrafluoroethylene [TFE], hexafluoropropylene [HFP], chlorotrifluoroethylene [CTFE], vinyl fluoride, vinylidene fluoride [VDF], Fluoroethylene, hexafluoroisobutylene, perfluorobutylethylene and the like can be mentioned. The cyclic fluorinated monomer is preferably perfluoro-2,2-dimethyl-1,3-dioxole [PDD], perfluoro-2-methylene-4-methyl-1,3-dioxolane [ PMD] and the like.
In the fluorinated alkyl vinyl ether, R and R ³ are preferably those having 1 to 4 carbon atoms, more preferably all hydrogen atoms are substituted with fluorine, and R ² Preferably has 2 to 4 carbon atoms, more preferably all of the hydrogen atoms are replaced by fluorine atoms.

Examples of the fluorine-free monomer include hydrocarbon monomers having reactivity with the fluorine-containing monomer. Examples of the hydrocarbon monomer include alkenes such as ethylene, propylene, butylene, and isobutylene; alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, and cyclohexyl vinyl ether; vinyl acetate, vinyl propionate, n -Vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl versatate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, benzoic acid Vinyl, vinyl para-t-butylbenzoate, vinyl cyclohexanecarboxylate, vinyl monochloroacetate, vinyl adipate, vinyl acrylate, vinyl methacrylate, croto Vinyl esters such as vinyl acid vinyl, vinyl sorbate, vinyl cinnamate, vinyl undecylenate, vinyl hydroxyacetate, vinyl hydroxypropioate, vinyl hydroxybutyrate, vinyl hydroxyvalerate, vinyl hydroxyisobutyrate and vinyl hydroxycyclohexanecarboxylate Alkyl allyl ethers such as ethyl allyl ether, propyl allyl ether, butyl allyl ether, isobutyl allyl ether, and cyclohexyl allyl ether; alkyl allyl ethers such as ethyl allyl ester, propyl allyl ester, butyl allyl ester, isobutyl allyl ester, and cyclohexyl allyl ester Examples include esters.

The fluorine-free monomer may also be a functional group-containing hydrocarbon monomer. Examples of the functional group-containing hydrocarbon monomers include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, hydroxycyclohexyl vinyl ether; itaconic acid, succinic acid, succinic anhydride, fumaric acid Non-fluorine-containing monomers having a carboxyl group such as acid, fumaric anhydride, crotonic acid, maleic acid, maleic anhydride, perfluorobutenoic acid; non-fluorine-containing monomers having a glycidyl group such as glycidyl vinyl ether and glycidyl allyl ether; aminoalkyl Non-fluorine-containing monomers having amino groups such as vinyl ether and aminoalkyl allyl ether; (meth) acrylamide, methylol acrylic Fluorine-containing monomers having an amide group of the amide.

As the fluorine-containing polymer suitably produced by the method for producing a fluorine-containing polymer of the present invention, a TFE polymer in which the monomer having the highest molar fraction of the monomer in the polymer (hereinafter, “most monomer”) is TFE, the most Examples thereof include a VDF polymer in which the monomer is VDF, a CTFE polymer in which the most monomer is CTFE, and the like.

The TFE polymer may preferably be a TFE homopolymer, or (1) TFE, (2) one or two or more fluorine-containing monomers other than TFE having 2 to 8 carbon atoms. In particular, it may be a copolymer comprising HFP or CTFE and (3) other monomers. (3) Other monomers include, for example, fluoro (alkyl vinyl ether) having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms; fluorodioxole; perfluoroalkylethylene; And hydroperfluoroolefin.
The TFE polymer may also be a copolymer of TFE and one or more fluorine-free monomers. Examples of the fluorine-free monomer include alkenes such as ethylene and propylene; vinyl esters; vinyl ethers. The TFE polymer is also a copolymer of TFE, one or more fluorine-containing monomers having 2 to 8 carbon atoms, and one or more fluorine-free monomers. Also good.

The VDF polymer may preferably be a VDF homopolymer [PVDF], or (1) VDF, (2) other than one or two or more VDFs having 2 to 8 carbon atoms. A copolymer comprising fluoroolefin, particularly TFE, HFP or CTFE, and (3) perfluoro (alkyl vinyl ether) having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms, etc. Also good.

The CTFE polymer may suitably be a CTFE homopolymer, (1) CTFE, (2) one or more fluoroolefins other than CTFE having 2 to 8 carbon atoms, In particular, it may be a copolymer comprising TFE or HFP and (3) perfluoro (alkyl vinyl ether) having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms.
The CTFE polymer may also be a copolymer of CTFE and one or more fluorine-free monomers. Examples of the fluorine-free monomers include alkenes such as ethylene and propylene; vinyl Esters; vinyl ethers and the like.

The fluoropolymer produced by the method for producing a fluoropolymer of the present invention can be glassy, plastic or elastomeric. These are amorphous or partially crystalline and can be subjected to compression firing, melt processing or non-melt processing.
In the method for producing a fluoropolymer of the present invention, for example, (I) a tetrafluoroethylene polymer [TFE polymer] is used as a non-melt processable resin, and (II) an ethylene / TFE copolymer is used as a melt processable resin. [ETFE], TFE / HFP copolymer [FEP], and TFE / perfluoro (alkyl vinyl ether) copolymer [PFA, MFA, etc.] are (III) TFE / propylene copolymer as elastomeric copolymer, TFE / propylene copolymer / third monomer copolymer (the third monomer is VDF, HFP, CTFE, perfluoro (alkyl vinyl ether), etc.), copolymer consisting of TFE and perfluoro (alkyl vinyl ether) HFP / ethylene copolymer, HFP / ethylene / TFE copolymer; PVDF; VDF / H Thermoplastic elastomers such as P copolymers, HFP / ethylene copolymers, VDF / TFE / HFP copolymers, and fluorine-containing segmented polymers described in JP-B 61-49327 can be preferably produced. .
The perfluoro (alkyl vinyl ether) has the formula:
Rf ³ (OCFQCF ₂ ) _k1 (OCR ⁴ Q ² CF ₂ CF ₂ ) _{k 2} (OCF ₂ ) _{k 3} OCF = CF ₂
(In the formula, Rf ³ represents a perfluoroalkyl group having 1 to 6 carbon atoms. K1, k2 and k3 are the same or different integers of 0 to 5. Q, Q ² and R ⁴ are Are the same or different and are F or CF _3. )

The fluoropolymer may have a core-shell structure. Examples of the fluorine-containing polymer having a core-shell structure include modified PTFE having a high molecular weight PTFE core and a lower molecular weight PTFE or modified PTFE shell in the particle. Examples of such modified PTFE include PTFE described in JP-T-2005-527652.

The above-mentioned (I) non-melt processable resin, (II) melt-processable resin and (III) elastomeric polymer which are preferably produced by the method for producing a fluoropolymer of the present invention are produced in the following manner. Is preferred.

(I) Non-melt processable resin In the method for producing a fluoropolymer of the present invention, the polymerization of TFE is usually carried out at a polymerization temperature of 10 to 100 ° C. and a polymerization pressure of 0.05 to 5 MPaG.
In the polymerization, pure water and the fluoroethercarboxylic acid are charged into a pressure-resistant reaction vessel equipped with a stirrer, and after deoxygenation, TFE is charged to a predetermined temperature, and a polymerization initiator is added to start the reaction. Since the pressure decreases as the reaction proceeds, additional TFE is added continuously or intermittently so as to maintain the initial pressure. When a predetermined amount of TFE is supplied, the supply is stopped, the TFE in the reaction vessel is purged, the temperature is returned to room temperature, and the reaction is terminated.

In the production of the TFE polymer, various known modifying monomers can be used in combination. In this specification, the tetrafluoroethylene polymer [TFE polymer] is not only a TFE homopolymer but also a copolymer of TFE and a modified monomer, which is non-melt processable (hereinafter referred to as “modified”). It is also a concept including “PTFE”).
Examples of the modifying monomer include perhaloolefins such as HFP and CTFE; fluoro (alkyl vinyl ether) having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms; and a ring such as fluorodioxole. Fluorinated monomers of the formula; perhaloalkylethylenes; ω-hydroperhaloolefins and the like. Depending on the purpose and the supply of TFE, the supply of the modified monomer can be performed by initial batch addition, or by continuous or intermittent addition.
The modified monomer content in the modified PTFE is usually in the range of 0.001 to 2 mol%.

In the production of the TFE polymer, the above-mentioned fluoroethercarboxylic acid can be used in the range of use in the production method of the above-mentioned fluoropolymer of the present invention, but usually 0.0001 to 2% by mass of the aqueous medium Add amount. The concentration of the fluoroethercarboxylic acid is not particularly limited as long as it is in the above range, but it is usually added at a critical micelle concentration (CMC) or less at the start of polymerization. When the addition amount is large, acicular particles having a large aspect ratio are formed, and the aqueous dispersion becomes a gel and the stability is impaired.

In the production of the TFE polymer, as a polymerization initiator, a persulfate (for example, ammonium persulfate) or an organic peroxide such as disuccinic acid peroxide or diglutaric acid peroxide is used alone or in the form of a mixture thereof. can do. Further, it may be used in combination with a reducing agent such as sodium sulfite to make a redox system. Furthermore, a radical scavenger such as hydroquinone or catechol can be added during polymerization, or a peroxide decomposing agent such as ammonium sulfite can be added to adjust the radical concentration in the system.

In the production of the TFE polymer, known chain transfer agents can be used. For example, saturated hydrocarbons such as methane, ethane, propane, and butane, and halogenated hydrocarbons such as chloromethane, dichloromethane, and difluoroethane. In addition, alcohols such as methanol and ethanol, hydrogen and the like can be mentioned, but those in a gaseous state at normal temperature and pressure are preferable.
The amount of the chain transfer agent used is usually 1 to 1000 ppm, preferably 1 to 500 ppm, based on the total amount of TFE supplied.

In the production of the TFE polymer, a saturated hydrocarbon having 12 or more carbon atoms that is substantially inert to the reaction and is liquid under the reaction conditions is used as a dispersion stabilizer in the reaction system. It can also be used at 2 to 10 parts by mass relative to parts by mass. Moreover, you may add ammonium carbonate, an ammonium phosphate, etc. as a buffering agent for adjusting pH during reaction.

When the polymerization of the TFE polymer is completed, an aqueous dispersion having a solid content concentration of 30 to 70% by mass and an average particle size of 50 to 500 nm can be obtained. Such an aqueous dispersion containing the fluoroethercarboxylic acid and the fluorine-containing polymer and having an average particle diameter of 50 to 500 nm is also one aspect of the present invention. Moreover, the aqueous dispersion which has the particle | grains which consist of a TFE polymer of a microparticle diameter of 0.3 micrometer or less can be obtained by using the said fluoro ether carboxylic acid. The TFE polymer at the end of the polymerization has a number average molecular weight of 1,000 to 10,000,000.

Fine powder can be produced by coagulating the aqueous dispersion.
The aqueous dispersion of the TFE polymer can be used for various applications as a fine powder after coagulation, washing and drying. Such a fine powder produced by coagulating the aqueous dispersion is also one aspect of the present invention. When coagulating the aqueous dispersion of the TFE polymer, the aqueous dispersion obtained by emulsion polymerization such as a polymer latex is usually diluted with water to a polymer concentration of 10 to 20% by mass. In some cases, the pH is adjusted to neutral or alkaline and then stirred more vigorously than stirring during the reaction in a vessel equipped with a stirrer. The coagulation may be performed while adding a water-soluble organic compound such as methanol or acetone, an inorganic salt such as potassium nitrate or ammonium carbonate, or an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid as a coagulant. The coagulation may be continuously performed using an in-line mixer or the like.

Before or during the coagulation, pigments for coloring and various fillers for improving the mechanical properties are added, so that the pigmented or filler-mixed TFE is uniformly mixed with the pigment and the filler. A polymer fine powder can be obtained.

Drying of the wet powder obtained by coagulating the aqueous dispersion of the TFE polymer is usually in a state where the wet powder does not flow so much, preferably in a stationary state, such as vacuum, high frequency, hot air, etc. By means. Friction between powders, particularly at high temperatures, generally has an unfavorable effect on fine powder type TFE polymers. This is because particles of this type of TFE polymer easily fibrillate even with a small shearing force and lose the original stable particle structure.
The drying is performed at a drying temperature of 10 to 250 ° C, preferably 100 to 200 ° C.

The obtained TFE polymer fine powder is preferable for molding, and suitable applications include hydraulic systems such as aircrafts and automobiles, fuel-based tubes, flexible hoses such as chemicals and steam, and wire coating applications. Can be mentioned.

The aqueous dispersion of the TFE polymer obtained by the above polymerization is also stabilized by adding a nonionic surfactant, further concentrated, and as a composition to which an organic or inorganic filler is added depending on the purpose. It is also preferable to use it for various purposes. The above composition has a non-adhesiveness and a low coefficient of friction when coated on a base material made of metal or ceramics, and has excellent gloss, smoothness, abrasion resistance, weather resistance and heat resistance. It is suitable for coating rolls, cooking utensils, etc., impregnating glass cloth, and the like.

The aqueous dispersion of the TFE polymer or the TFE polymer fine powder is also preferably used as a processing aid. When used as a processing aid, mixing the aqueous dispersion or fine powder with a host polymer or the like improves the melt strength during the melting process of the host polymer and improves the mechanical strength, electrical properties, and difficulty of the resulting polymer. It is possible to improve the flammability, the dripping prevention property, and the slidability.
The aqueous TFE polymer dispersion or the TFE polymer fine powder is also preferably used as a binder for batteries.

The aqueous dispersion of the TFE polymer or the TFE polymer fine powder is also preferably used as a processing aid after being combined with a resin other than the TFE polymer. Examples of the aqueous dispersion or the fine powder include JP-A-11-49912, JP-A-2003-24693, US Pat. No. 5,804,654, JP-A-11-29679, and JP-A-2003-2980. It is suitable as a raw material for PTFE described in the publication. The processing aid using the aqueous dispersion or the fine powder is not inferior to the processing aid described in each of the above publications.

The aqueous dispersion of the TFE polymer is also preferably co-coagulated by mixing with an aqueous dispersion of a heat-melt processable fluororesin and coagulating. The co-coagulated powder is suitable as a processing aid.

Examples of the heat-melt processable fluororesin include FEP, PFA, ETFE, and EFEP, among which FEP is preferable.

The fluorine-free resin to which the co-coagulated powder is added may be a powder, a pellet, or an emulsion. The addition is preferably performed while applying a shearing force by a known method such as extrusion kneading or roll kneading in that each resin is sufficiently mixed.

The aqueous TFE polymer dispersion is also preferably used as a dust suppressing agent. A method for suppressing dust from a dust generating material by fibrillating a TFE polymer by mixing the dust suppressing treatment agent with a dust generating material and subjecting the mixture to a compression-shearing action at a temperature of 20 to 200 ° C. For example, it can be used in methods such as Japanese Patent No. 2827152 and Japanese Patent No. 2538783. The aqueous dispersion of the TFE polymer can be suitably used for, for example, the dust suppressing treatment composition described in International Publication No. 2007/004250, and the dust suppression described in International Publication No. 2007/000812. It can also be suitably used for a processing method.

The dust suppression treatment agent is suitably used for dust suppression treatment in the fields of building materials, soil stabilization materials, solidification materials, fertilizers, landfill disposal of incinerated ash and harmful substances, explosion-proof fields, cosmetics fields, and the like.

The aqueous dispersion of the TFE polymer is also preferably used as a raw material for obtaining TFE polymer fibers by a dispersion spinning method (Dispersion Spinning method). The dispersion spinning method refers to mixing an aqueous dispersion of the TFE polymer and an aqueous dispersion of a matrix polymer, and extruding the mixture to form an intermediate fiber structure. The intermediate fiber structure Is a method of decomposing the matrix polymer and sintering the TFE polymer particles to obtain TFE polymer fibers.

High molecular weight PTFE can also be produced using the above-mentioned fluoroethercarboxylic acid. The high molecular weight PTFE powder obtained by emulsion polymerization is also useful as a raw material for the PTFE porous body (membrane). For example, after extruding and rolling high molecular weight PTFE powder, it is unfired or semi-fired and stretched in at least one direction (preferably roll-stretched in the rolling direction and then stretched in the width direction by a tenter) to obtain a porous PTFE ( Film) can be obtained. By stretching, PTFE is easily fibrillated to form a porous PTFE body (membrane) composed of nodules and fibers.

This porous body (membrane) is useful as various filters, and can be preferably used as a chemical solution filter, particularly as an air filter medium.

Low molecular weight PTFE can also be produced using the above-mentioned fluoroethercarboxylic acid. The low molecular weight PTFE may be produced by polymerization, or the high molecular weight PTFE obtained by polymerization may be produced by reducing the molecular weight by a known method (thermal decomposition, radiation irradiation decomposition, etc.).

Low molecular weight PTFE (also called PTFE micropowder) with a molecular weight of 600,000 or less has excellent chemical stability, extremely low surface energy, and is less prone to fibrillation, improving slipperiness and coating surface quality As additives for the purpose of, for example, it is suitable for the production of plastics, inks, cosmetics, paints, greases, office automation equipment members, toners and the like (see, for example, JP-A-10-147617).

Further, in the presence of a chain transfer agent, the above-mentioned fluoroethercarboxylic acid is dispersed in an aqueous medium as a polymerization initiator and an emulsifier, and TFE or a monomer that can be copolymerized with TFE is polymerized with TFE. Molecular weight PTFE may be obtained.

When low molecular weight PTFE obtained by emulsion polymerization is used as a powder, it can be made into powder particles by coagulating the aqueous dispersion.

An unfired tape (raw tape) can also be obtained from the PTFE fine powder obtained using the above-mentioned fluoroethercarboxylic acid.

The method for producing a fluoroethercarboxylic acid of the present invention comprises the following general formula (I) from the coagulation or waste water generated by washing and / or off-gas generated in the drying step.
_{CF 3 (CF 2) n OCH} 2 CF 2 CF 2 ORfCOOM (I)
(Wherein Rf is a partially or entirely fluorine-substituted alkylene group having 2 carbon atoms, n is 0 or 1, M represents a monovalent alkali metal, NH ₄ or H) 1 or 2 More than one type of fluoroethercarboxylic acid and / or the following general formula (II)
CF ₃ (CF ₂ ) _n OCFXCF ₂ CF ₂ ORfCOOM (II)
(Wherein Rf is a partially or entirely fluorine-substituted C 2 alkylene group, n is 0 or 1, M is a monovalent alkali metal, NH ₄ or H, and X is H or F). One or two or more kinds of fluoroethercarboxylic acids may be recovered and purified. A method for producing such regenerated fluoroethercarboxylic acid is also one aspect of the present invention. Although it does not specifically limit as a method of performing the said collection | recovery and refinement | purification, It can carry out by a well-known method.

(II) Melt processable resin (1) In the method for producing a fluoropolymer of the present invention, FEP polymerization is preferably performed at a polymerization temperature of 60 to 100 ° C. and a polymerization pressure of 0.7 to 4.5 MpaG.
The preferable monomer composition (mass%) of FEP is TFE: HFP = (60-95) :( 5-40), More preferably, it is (85-90) :( 10-15). The FEP may further be modified with perfluoro (alkyl vinyl ether) s as a third component and modified within a range of 0.5 to 2% by mass of the total monomers.
In the polymerization of the FEP, the fluoroethercarboxylic acid can be used in the range of use in the method for producing a fluoropolymer of the present invention, but usually 0.0001 to 2% by mass with respect to 100% by mass of the aqueous medium. Add amount.
In the FEP polymerization, cyclohexane, methanol, ethanol, carbon tetrachloride, chloroform, methylene chloride, methyl chloride, etc. are preferably used as the chain transfer agent, and ammonium carbonate, disodium hydrogen phosphate as the pH buffering agent. Etc. are preferably used.

(2) In the method for producing a fluoropolymer of the present invention, polymerization of TFE / perfluoro (alkyl vinyl ether) copolymer such as PFA and MFA is usually performed at a polymerization temperature of 60 to 100 ° C. and a polymerization pressure of 0.7 to 2. It is preferable to carry out at 5 MpaG.
A preferable monomer composition (mol%) of the TFE / perfluoro (alkyl vinyl ether) copolymer is TFE: perfluoro (alkyl vinyl ether) = (95 to 99.7) :( 0.3 to 5), more preferably. Is (97-99) :( 1-3). Examples of the perfluoro (alkyl vinyl ether), _formula: CF 2 = CFORf ⁴ (wherein, Rf ⁴ is a perfluoroalkyl group having 1 to 6 carbon atoms) preferably used those represented by.
In the polymerization of the TFE / perfluoro (alkyl vinyl ether) copolymer, the above-mentioned fluoroethercarboxylic acid can be used in the range of use in the method for producing a fluoropolymer of the present invention, but usually 100% by mass of an aqueous medium. It is preferable to add in an amount of 0.0001 to 10% by mass based on the amount.
In the polymerization of the TFE / perfluoro (alkyl vinyl ether) copolymer, it is preferable to use cyclohexane, methanol, ethanol, carbon tetrachloride, chloroform, methylene chloride, methyl chloride, methane, ethane or the like as a chain transfer agent. As a buffering agent, it is preferable to use ammonium carbonate, disodium hydrogen phosphate or the like.

(3) In the method for producing a fluorine-containing polymer of the present invention, the polymerization of ETFE is preferably performed at a polymerization temperature of 20 to 100 ° C. and a polymerization pressure of 0.5 to 0.8 MPaG.
A preferred monomer composition (mol%) of ETFE is TFE: ethylene = (50 to 99) :( 50 to 1). As the ETFE, a third monomer may be used and modified within a range of 0 to 20% by mass of the total monomers. Preferably, TFE: ethylene: third monomer = (63 to 94) :( 27 to 2) :( 4 to 10). As the third monomer, perfluorobutylethylene, perfluorobutylethylene, 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH ₂ ═CFCF ₂ CF ₂ CF ₂ H), 2-trifluoromethyl-3,3,3-trifluoropropene ((CF ₃ ) ₂ C═CH ₂ ) is preferred.
In the polymerization of ETFE, the above-mentioned fluoroethercarboxylic acid can be used in the range of use in the method for producing a fluoropolymer of the present invention, but is usually 0.0001 to 2% by mass relative to 100% by mass of the aqueous medium. Add in the amount of.
In the above ETFE polymerization, it is preferable to use cyclohexane, methanol, ethanol, carbon tetrachloride, chloroform, methylene chloride, methyl chloride or the like as the chain transfer agent.

(4) An electrolyte polymer precursor can also be produced using the method for producing a fluoropolymer of the present invention. In the method for producing a fluoropolymer of the present invention, the polymerization of the electrolyte polymer precursor is preferably performed at a polymerization temperature of 20 to 100 ° C. and a polymerization pressure of 0.3 to 2.0 MPaG. The electrolyte polymer precursor is composed of a vinyl ether monomer as shown below, and can be converted into an ion-exchangeable polymer through a hydrolysis treatment.

As the vinyl ether monomer used in the electrolyte polymer precursor ^{_{CF 2 = CF-O- (CF}} 2 CFY 1 -O) n - (CFY 2) m -A
(Wherein Y ¹ represents a fluorine atom, a chlorine atom or a perfluoroalkyl group. N represents an integer of 0 to 3. The n Y ^{1 s} may be the same or different. Y ² represents a fluorine atom or a chlorine atom, m represents an integer of 1 to 5. m Y ² may be the same or different, and A represents —SO. ₂ represents X ¹ and / or —COZ ^1. X ¹ represents a halogen atom, and Z ¹ represents an alkoxyl group having 1 to 4 carbon atoms. A preferable monomer composition (mol%) of the electrolyte polymer precursor is TFE: vinyl ether = (50 to 93) :( 50 to 7).

What modified | denatured with the 3rd monomer within the range which is 0-20 mass% of all the monomers may be used. Examples of the third monomer include polyfunctional monomers such as CTFE, vinylidene fluoride, perfluoroalkyl vinyl ether, and divinylbenzene.

The electrolyte polymer precursor thus obtained can be used in a fuel cell or the like as a polymer electrolyte membrane after being formed into a film, for example, and then subjected to hydrolysis with an alkaline solution and treatment with a mineral acid.

The melt-processable resin obtained by the above-described method is also preferably used as a raw material for obtaining melt-processable resin fibers by a spinning and drawing method. The above-mentioned spinning and drawing method is a method of melt-working by melt spinning a melt-processable resin, cooling and solidifying to obtain an undrawn yarn, and then drawing the undrawn yarn by running through a heated cylindrical body. This is a method for obtaining resin fibers.
The aqueous dispersion of the melt processable resin or the melt processable resin is also preferably used as a binder for a battery.

(III) Elastomeric Polymer In the method for producing a fluoropolymer of the present invention, the polymerization of the elastomeric polymer is carried out by charging pure water and the above fluoroethercarboxylic acid into a pressure-resistant reaction vessel equipped with a stirrer, A monomer is charged, the temperature is set to a predetermined level, a polymerization initiator is added, and the reaction is started. Since the pressure decreases as the reaction proceeds, additional monomer is added continuously or intermittently to maintain the initial pressure. When a predetermined amount of monomer is supplied, the supply is stopped, the monomer in the reaction vessel is purged, the temperature is returned to room temperature, and the reaction is terminated. When emulsion polymerization is performed, it is preferable to continuously remove the polymer latex from the reaction vessel.
In particular, when producing a thermoplastic elastomer, as disclosed in International Publication No. 00/01741 pamphlet, by once synthesizing the fluorine-containing polymer fine particles at a high concentration and then diluting and further polymerizing, It is also possible to use a method that can increase the final polymerization rate as compared with normal polymerization.

The polymerization of the elastomeric polymer is appropriately selected from the viewpoints of physical properties of the target polymer and control of the polymerization rate. The polymerization temperature is usually -20 to 200 ° C, preferably 5 to 150 ° C, and the polymerization pressure is usually normal. It is carried out at 0.5 to 10 MPaG, preferably 1 to 7 MPaG. Moreover, it is preferable to maintain pH in a polymerization medium normally at 2.5-9 using the pH adjuster etc. which are mentioned later by a well-known method etc.

Examples of the monomer used for the polymerization of the elastomeric polymer include, in addition to vinylidene fluoride, fluorine-containing ethylenically unsaturated monomers having at least the same number of fluorine atoms as carbon atoms and capable of copolymerizing with vinylidene fluoride. Examples of the fluorine-containing ethylenically unsaturated monomer include trifluoropropene, pentafluoropropene, hexafluorobutene, and octafluorobutene. Among these, hexafluoropropene is particularly suitable due to the elastomeric properties obtained when it blocks polymer crystal growth. Examples of the fluorine-containing ethylenically unsaturated monomer include trifluoroethylene, TFE, and CTFE. A fluorine-containing monomer having one or two or more chlorine and / or bromine substituents may be used. it can. Perfluoro (alkyl vinyl ether) such as perfluoro (methyl vinyl ether) can also be used. TFE and HFP are preferred for producing elastomeric polymers.
A preferable monomer composition (mass%) of the elastomeric polymer is vinylidene fluoride: HFP: TFE = (20 to 70) :( 30 to 48) :( 0 to 32). Elastomeric polymers of this composition exhibit good elastomeric properties, chemical resistance and thermal stability.

In the polymerization of the elastomeric polymer, the above-mentioned fluoroethercarboxylic acid can be used in the range of use in the method for producing a fluoropolymer of the present invention, but usually 0.0001 to 100% by mass of the aqueous medium. Add in an amount of 2% by weight.

In the polymerization of the elastomeric polymer, a known inorganic radical polymerization initiator can be used as the polymerization initiator. Examples of the inorganic radical polymerization initiator include conventionally known water-soluble inorganic peroxides such as sodium, potassium and ammonium persulfates, perphosphates, perborates, percarbonates and permanganates. Useful. The radical polymerization initiator further includes a reducing agent such as sodium, potassium or ammonium sulfite, bisulfite, metabisulfite, hyposulfite, thiosulfate, phosphite or hypophosphite. Or by a metal compound that is easily oxidized, such as a ferrous salt, a cuprous salt, or a silver salt. A suitable inorganic radical polymerization initiator is ammonium persulfate, and it is more preferred to use it in a redox system with ammonium persulfate and sodium bisulfite.
The concentration of the polymerization initiator added is appropriately determined depending on the molecular weight of the target fluorine-containing polymer and the polymerization reaction rate, but is 0.0001 to 10% by mass, preferably 0.01% with respect to 100% by mass of the total amount of monomers. Set to an amount of ~ 5% by weight.

In the polymerization of the elastomeric polymer, a known chain transfer agent can be used, but in the polymerization of PVDF, a hydrocarbon, ester, ether, alcohol, ketone, chlorine compound, carbonate, or the like is used. In the thermoplastic elastomer, hydrocarbons, esters, ethers, alcohols, chlorine compounds, iodine compounds, and the like can be used. Among them, acetone and isopropyl alcohol are preferable for the polymerization of PVDF, and isopentane, diethyl malonate and ethyl acetate are preferable for the polymerization of the thermoplastic elastomer from the viewpoint that the reaction rate is difficult to decrease, and I (CF ₂ ) ₄ I , I (CF ₂ ) ₆ I, ICH ₂ I and the like are preferred from the viewpoint that they can be iodinated at the polymer terminal and can be used as a reactive polymer.
The amount of the chain transfer agent used is usually 0.5 × 10 ^{−3 to} 5 × 10 ⁻³ mol%, preferably 1.0 × 10 ^{−3 to} 3.5 × 10, based on the total amount of monomers supplied. ^-3 mol% is preferred.

In the polymerization of the elastomeric polymer, paraffin wax or the like can be preferably used as an emulsion stabilizer in the polymerization of PVDF, and in the polymerization of a thermoplastic elastomer, phosphate, sodium hydroxide, hydroxylation can be used as a pH adjuster. Potassium etc. can be used preferably.

The elastomeric polymer obtained by the method for producing a fluoropolymer of the present invention has a solid content concentration of 10 to 40% by mass and an average particle size of 0.03 to 1 μm, preferably 0.05 when polymerization is completed. ˜0.5 μm and a number average molecular weight of 1,000 to 2,000,000.

The elastomeric polymer obtained by the method for producing a fluoropolymer of the present invention is suitable for rubber molding processing by adding, concentrating, etc., a dispersion stabilizer such as a hydrocarbon surfactant, if necessary. It can be a dispersion. The dispersion is processed by adjusting pH, coagulation, heating, and the like. Each process is performed as follows.

The pH adjustment is performed by adding a mineral acid such as nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid and / or a carboxylic acid having 5 or less carbon atoms and having a pK = 4.2 or less to make the pH 2 or less.
The coagulation is performed by adding an alkaline earth metal salt. Examples of the alkaline earth metal salts include nitrates, chlorates and acetates of calcium or magnesium.
Either the pH adjustment or the coagulation may be performed first, but the pH adjustment is preferably performed first.
After each operation, washing is performed with the same volume of water as the elastomer to remove a small amount of impurities such as buffer solution and salt existing in the elastomer, and drying is performed. Drying is usually performed at about 70 to 200 ° C. while circulating air at a high temperature in a drying furnace.

The fluorine-containing polymer is usually in a concentration of 10 to 50% by mass of the aqueous dispersion obtained by performing the polymerization. In the aqueous dispersion, the preferred lower limit of the concentration of the fluoropolymer is 10% by mass, the more preferred lower limit is 15% by mass, the preferred upper limit is 40% by mass, the more preferred upper limit is 35% by mass, and the still more preferred upper limit is 30% by mass. It is.

The aqueous dispersion obtained by performing the above polymerization may be concentrated or dispersion-stabilized to form a dispersion, or as a powder or other solid material obtained by collecting and drying by coagulation or aggregation. Also good.

The fluoroethercarboxylic acid can also be suitably used as a dispersant for dispersing a fluorine-containing polymer obtained by polymerization in an aqueous medium.

The aqueous dispersion of the present invention contains particles made of a fluorine-containing polymer, the fluoroethercarboxylic acid, and an aqueous medium. The aqueous dispersion is one in which particles made of a fluorine-containing polymer are dispersed in an aqueous medium in the presence of the fluoroethercarboxylic acid.

The fluoroethercarboxylic acid is preferably 0.0001 to 15% by mass of the aqueous dispersion of the present invention. If it is less than 0.0001% by mass, the dispersion stability may be inferior. If it exceeds 15% by mass, there is no dispersion effect commensurate with the abundance and it is not practical. The more preferable lower limit of the fluoroethercarboxylic acid is 0.001% by mass, the more preferable upper limit is 10% by mass, and the still more preferable upper limit is 2% by mass.

The aqueous dispersion of the present invention comprises an aqueous dispersion obtained by performing the above-described polymerization, a dispersion obtained by concentrating or dispersing the aqueous dispersion, and a powder comprising a fluoropolymer. Any of those dispersed in an aqueous medium in the presence of the fluoroethercarboxylic acid may be used.

As a method for producing the aqueous dispersion of the present invention, the aqueous dispersion obtained by the polymerization is contacted with an anion exchange resin in the presence of a nonionic surfactant, and the step (A) ) Can be produced by the step (B) of concentrating so that the solid content concentration is 30 to 70% by mass with respect to 100% by mass of the aqueous dispersion. A method for producing such a purified aqueous dispersion is also one aspect of the present invention. The nonionic surfactant is not particularly limited, and examples thereof include those described above. Although the said anion is not specifically limited, A well-known thing can be used. Moreover, a well-known method can be used for the method made to contact with the said anion exchange resin.

A known method is employed as the concentration method, and examples thereof include phase separation, electric concentration, and ultrafiltration. In the concentration, the fluorine-containing polymer concentration can be concentrated to 30 to 70% by mass depending on the application. Concentration may impair dispersion stability. In that case, a dispersion stabilizer may be further added. As the dispersion stabilizer, the above-mentioned fluoroethercarboxylic acid or other various surfactants may be added. Examples of the various dispersion stabilizers include nonionic surfactants such as polyoxyalkyl ether, particularly polyoxyethylene alkylphenyl ether (for example, Triton X-100 (trade name) manufactured by Rohm & Haas), Polyoxyethylene isotridecyl ether (for example, Neugen TDS80C (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Leocor TD90D (trade name) manufactured by Lion, Genapol X080 (trade name) manufactured by Clariant), polyoxyethylene ether However, it is not limited to these.

The total amount of the dispersion stabilizer is 0.5 to 20% by mass with respect to the solid content of the dispersion. If it is less than 0.5% by mass, the dispersion stability may be inferior. If it exceeds 20% by mass, there is no dispersion effect commensurate with the abundance and this is not practical. A more preferable lower limit of the dispersion stabilizer is 2% by mass, and a more preferable upper limit is 12% by mass.

The fluoroethercarboxylic acid may be removed by the concentration operation. Since the fluoroethercarboxylic acid has high water solubility, the removal efficiency is higher than that of conventional fluorine-containing surfactants.

The aqueous dispersion obtained by carrying out the polymerization can also be prepared as an aqueous dispersion having a long pot life by subjecting it to a dispersion stabilization treatment without concentrating depending on the application. Examples of the dispersion stabilizer used include the same as those described above.

The use of the aqueous dispersion of the present invention is not particularly limited, and it is applied as it is as an aqueous dispersion, applied on a substrate, dried, and then fired as necessary; non-woven fabric, resin molded product After impregnating and drying a porous support such as glass, preferably by calcination; after coating and drying on a substrate such as glass, the substrate is immersed in water as necessary to peel off the substrate Examples thereof include cast film formation comprising obtaining a thin film, and examples of these applications include aqueous dispersion paints, electrode binders, electrode water repellents, and the like.

The aqueous dispersion of the present invention can be blended with known pigments, thickeners, dispersants, antifoaming agents, antifreeze agents, film forming aids, or other polymer compounds. It can be combined and used as a water-based paint for coating.

The present invention also includes at least one component selected from the wastewater generated by the coagulation described above, the wastewater generated by washing, and / or the offgas generated in the drying step, from the following general formula (I):
_{CF 3 (CF 2) n OCH} 2 CF 2 CF 2 ORfCOOM (I)
(Wherein Rf is a partially or entirely fluorine-substituted alkylene group having 2 carbon atoms, n is 0 or 1, M represents a monovalent alkali metal, NH ₄ or H) 1 or 2 More than one type of fluoroethercarboxylic acid and / or the following general formula (II)
CF ₃ (CF ₂ ) _n OCFXCF ₂ CF ₂ ORfCOOM (II)
(Wherein Rf is a partially or entirely fluorine-substituted C 2 alkylene group, n is 0 or 1, M is a monovalent alkali metal, NH ₄ or H, and X is H or F). It is also a method for producing a regenerated fluoroethercarboxylic acid characterized by including a step of recovering and purifying one or more fluoroethercarboxylic acids. Although it does not specifically limit as a method of performing the said collection | recovery and refinement | purification, It can carry out by a well-known method.

A method for recovering and purifying the fluoroethercarboxylic acid from the wastewater generated by the coagulation, the wastewater generated by washing, and the off-gas generated in the drying process is not particularly limited. For example, the methods described in US Patent Application Publication No. 2007/15937, US Patent Application Publication No. 2007/25902, and US Patent Application Publication No. 2007/27251 may be used. Specifically, the following methods are mentioned.

As a method for recovering the fluoroethercarboxylic acid from the wastewater, after adsorbing the fluoroethercarboxylic acid by contacting the wastewater with adsorbent particles such as ion exchange resin, activated carbon, silica gel, clay, zeolite, etc., the wastewater and the adsorbed particles The method of isolate | separating is mentioned. If the adsorbed particles adsorbing the fluoroethercarboxylic acid are incinerated, release of the fluoroethercarboxylic acid into the environment can be prevented.

Further, the fluoroethercarboxylic acid can be recovered by desorbing and eluting from the ion exchange resin particles adsorbed with the fluoroethercarboxylic acid by a known method. For example, when the ion exchange resin particles are anion exchange resin particles, the fluoroethercarboxylic acid or a salt thereof can be eluted by bringing the mineral acid into contact with the anion exchange resin. Subsequently, when a water-soluble organic solvent is added to the obtained eluate, it usually separates into two phases, so that the fluoroethercarboxylic acid can be recovered by recovering and neutralizing the lower phase containing the fluoroethercarboxylic acid. Examples of the water-soluble organic solvent include polar solvents such as alcohol, ketone and ether.

Other methods for recovering the fluoroethercarboxylic acid from the ion exchange resin particles include a method using an ammonium salt and a water-soluble organic solvent, and a method using an alcohol and optionally an acid. In the latter method, an ester derivative of fluoroethercarboxylic acid is formed, and can be easily separated from the alcohol by distillation.

When the waste water contains fluorine-containing polymer particles or other solid content, it is preferable to remove these before bringing the waste water into contact with the adsorbed particles. Examples of the method for removing the fluorine-containing polymer particles and other solids include a method in which an aluminum salt or the like is added to precipitate these and then the waste water and the precipitate are separated, and an electrocoagulation method. Moreover, you may remove by a mechanical method, for example, the crossflow filtration method, the depth filtration method, and the precoat filtration method are mentioned.

As a method for recovering the fluoroethercarboxylic acid from the off-gas, a scrubber is used to make contact with an organic solvent such as deionized water, an alkaline aqueous solution, or a glycol ether solvent, and a scrubber solution containing the fluoroethercarboxylic acid is obtained. The method of obtaining is mentioned. When a high-concentration alkaline aqueous solution is used as the alkaline aqueous solution, the scrubber solution can be recovered in a state where the fluoroethercarboxylic acid is phase-separated, so that the fluoroethercarboxylic acid can be easily recovered and reused. Examples of the alkali compound include alkali metal hydroxides and quaternary ammonium salts.

The scrubber solution containing the fluoroethercarboxylic acid may be concentrated using a reverse osmosis membrane or the like. The concentrated scrubber solution usually contains fluorine ions, but it is also possible to facilitate reuse of the fluoroethercarboxylic acid by adding alumina after the concentration to remove the fluorine ions. Alternatively, the fluoroethercarboxylic acid may be recovered by the method described above by contacting the adsorbent particles with a scrubber solution to adsorb the fluoroethercarboxylic acid.

The fluoroethercarboxylic acid recovered by any of the above methods can be reused in the production of the fluoropolymer.

Since the fluoroethercarboxylic acid of the present invention has the above-described configuration, it has low bioaccumulation properties and excellent surface activity. Therefore, the fluoroethercarboxylic acid can be used as a surfactant in the production of a fluoropolymer, As a dispersant for the combined aqueous dispersion composition, it can be suitably used in various other applications. Since the fluoropolymer production method of the present invention uses the fluoroethercarboxylic acid as a surfactant, the fluoropolymer can be produced efficiently.
Further, since the aqueous dispersion of the present invention is a dispersion of particles comprising a fluoropolymer in the presence of the fluoroethercarboxylic acid of the present invention or the surfactant of the present invention, stability, processability Etc.

Next, although this invention is demonstrated based on a synthesis example, an Example, and a comparative example, this invention is not limited only to this synthesis example and Example.
The method of measurement performed in each example is shown below.

Solid content concentration: It was determined from the decrease in mass when the obtained aqueous dispersion was dried at 150 ° C. for 1 hour.

Standard specific gravity (SSG): Measured according to ASTM D1457-69.

Average primary particle diameter (PTFE): Based on a calibration curve of the transmittance of 550 nm projection light per unit length and the average particle diameter determined by electron micrograph, diluted to a solid content concentration of about 0.02% by mass. Thus, it was indirectly determined from the transmittance.
The transmittance was measured using a dynamic light scattering measuring device Microtrack 9340UPA (Honeywell).

¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR were measured with a nuclear magnetic resonance apparatus NMR system 400 manufactured by VARIAN. Tetramethylsilane and CCl ₃ F are added to the sample as internal standard substances. In ¹ H-NMR (400 Hz), tetramethylsilane is 0 ppm, and in ¹⁹ F-NMR (376 Hz), CCl ₃ F is 0 ppm, ¹³ C— NMR (100 Hz) was measured with tetramethylsilane at 0 ppm.

Synthesis example 1
Synthesis of CF ₃ OCH ₂ CF ₂ CF ₂ OCH ₂ CF ₂ COONH ₄ Add 100 g of dehydrated tetraglyme and 5.4 g of cesium fluoride into a 3 L stainless steel autoclave and repeat nitrogen substitution and evacuation. After removing the water inside, 200 g of COF ₂ was introduced. While maintaining the internal temperature at 20 ° C., 400 g of tetrafluorooxetane was pressed into the autoclave over 3 hours. As the reaction proceeded, the pressure decreased. When the pressure reached 0.1 MPa, the internal pressure was released and 586 g of the lower layer was recovered from the liquid separated into two layers. This was distilled under reduced pressure to recover 126 g of fraction I having a boiling point of 45 ° C. and 389 g of fraction II having a boiling point of 63 ° C. (7000 Pa). As a result of measuring ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR, the fraction I was identified as CF ₃ OCH ₂ CF ₂ COF and the fraction II was identified as CF ₃ OCH ₂ CF ₂ CF ₂ OCH ₂ CF ₂ COF. It was done. This fraction II was hydrolyzed with a 20% aqueous potassium hydroxide solution, the pH was set to 1 with dilute sulfuric acid, and the lower layer separated into two layers was collected. Distillation under reduced pressure was performed to obtain 376 g of a fraction having a boiling point of 106 ° C. (1760 Pa). Furthermore, neutralization with ammonia water and freeze-drying were performed to obtain CF ₃ OCH ₂ CF ₂ CF ₂ OCH ₂ CF ₂ COONH ₄ .

Example 1
A stainless steel autoclave with a stirring blade with an internal volume of 3 L is charged with 1.5 L of deionized water, 60 g of paraffin wax (melting point 60 ° C.), and 1.5 g of CF ₃ OCH ₂ CF ₂ CF ₂ OCH ₂ CF ₂ COONH _4. The inside of the system was replaced with TFE. TFE was injected so that the internal temperature was 70 ° C. and the internal pressure was 0.78 MPa, and 3.75 g of a 1% by mass ammonium persulfate [APS] aqueous solution was charged to initiate the reaction. As the polymerization proceeded, the pressure in the polymerization system decreased, so TFE was continuously added to keep the internal pressure at 0.78 MPa and the reaction was continued. After 6.5 hours from the start of polymerization, TFE was purged to terminate the polymerization. The solid content concentration of this aqueous dispersion was 32.0% by mass, the standard specific gravity was 2.192, and the average primary particle size of the fluoropolymer was 245 nm.

Synthesis example 2
Synthesis method of CF ₃ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) COONH ₄ A 300 ml stainless steel autoclave equipped with stirring was charged with 150 ml of tetraglyme and 3 g (0.02 mol) of cesium fluoride and pressurized with nitrogen. After repeating the above to remove moisture in the container, 98 g (0.5 mol) of CF ₃ OCH ₂ CF ₂ COF was introduced while maintaining the internal temperature at −10 ° C. and stirred for 1 hour, and then hexafluoroepoxypropane [HFEP] 5 g was introduced. Since an increase in internal temperature was observed, while maintaining the internal temperature at −5 ° C. or lower, 5 g was intermittently introduced, and 40 g of HFEP was introduced in 2 hours. After 6 hours, the internal temperature was returned to room temperature and the pressure was released to complete the reaction. The contents were put into 300 ml of ice water, 150 g of 20% KOH aqueous solution was gradually added, and 1N sulfuric acid was further added and stirred to precipitate an oil layer. This oil layer was distilled under reduced pressure to obtain CF ₃ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) COOH.

Further, this was neutralized with aqueous ammonia and freeze-dried to obtain 75 g of CF ₃ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) COONH ₄ .

The spectrum data of the obtained CF ₃ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) COONH ₄ are shown below.
¹ H-NMR (δ, ppm): 4.37 (t) 7.61 (s)
¹⁹ F-NMR (δ, ppm): −62.79 (s, 3F) −81.22 (dd, 1F) −82.49 (s, 3F) −88.56 (d, 1F) −124.06 (T, 2F) -131.91 (d, 1F)

Example 2
Preparation of PTFE Latex A stainless steel autoclave with a stirring blade with an internal volume of 3 L, deionized water 1.5 L, paraffin wax 60 g (melting point 60 ° C.), and CF ₃ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) COONH ₄ 1.5 g was charged and the system was replaced with TFE. TFE was injected so that the internal temperature was 70 ° C. and the internal pressure was 0.78 MPa, and 3.75 g of a 1% by mass ammonium persulfate [APS] aqueous solution was charged to initiate the reaction. As the polymerization proceeded, the pressure in the polymerization system decreased, so TFE was continuously added to keep the internal pressure at 0.78 MPa and the reaction was continued. After 6.5 hours from the start of polymerization, TFE was purged to terminate the polymerization.

The solid content concentration of this aqueous dispersion was 32.5% by mass, the standard specific gravity was 2.182, and the average primary particle size of the fluoropolymer was 263 nm.

The fluoroethercarboxylic acid of the present invention can be used as a surfactant in the production of a fluoropolymer and as a dispersant for a fluoropolymer aqueous dispersion composition.

Claims (11)

The following general formula (I)
_{CF 3 (CF 2) n OCH} 2 CF 2 CF 2 ORfCOOM (I)
Wherein Rf is a partially or entirely fluorine-substituted alkylene group having 2 carbon atoms, n is 0 or 1, and M is a monovalent alkali metal, NH ₄ or H. Fluoroether carboxylic acid. Rf _{is, -CH 2 CF 2 -, -} CHFCF 2 -, - CF 2 CF 2 -, - CF (CF 3) - fluoroethercarboxylic acid according to claim 1, wherein a. By contacting the fluoroethercarboxylic acid according to claim 1 or 2 with fluorine, the following general formula (II)
CF ₃ (CF ₂ ) _n OCFXCF ₂ CF ₂ ORfCOOM (II)
(Wherein Rf is a partially or entirely fluorine-substituted C 2 alkylene group, n is 0 or 1, M is a monovalent alkali metal, NH ₄ or H, and X is H or F). The manufacturing method characterized by manufacturing the fluoro ether carboxylic acid manufactured. A surfactant comprising the fluoroethercarboxylic acid according to claim 1 or 2 and / or the fluoroethercarboxylic acid obtained by the production method according to claim 3. A surfactant for polymerization comprising the fluoroethercarboxylic acid according to claim 1 or 2 and / or the fluoroethercarboxylic acid obtained by the production method according to claim 3. It comprises a step of polymerizing a fluorine-containing monomer in an aqueous medium containing the fluoroethercarboxylic acid according to claim 1 or 2 and / or the fluoroethercarboxylic acid obtained by the production method according to claim 3. A method for producing a fluorine-containing polymer. The method for producing a fluoropolymer according to claim 6, wherein the content of the fluoroethercarboxylic acid is 0.0001 to 10 mass% with respect to 100 mass% of the aqueous medium. An aqueous dispersion containing a fluorine-containing polymer,
The fluoroethercarboxylic acid according to claim 1 or 2 and / or the fluoroethercarboxylic acid obtained by the production method according to claim 3,
The aqueous dispersion, wherein the fluoropolymer has an average particle size of 50 to 500 nm. The step (A) of contacting the aqueous dispersion according to claim 8 with an anion exchange resin in the presence of a nonionic surfactant, and the aqueous dispersion obtained in step (A) in the aqueous dispersion The manufacturing method of the refinement | purification aqueous dispersion characterized by including the process (B) concentrated so that solid content concentration may be 30-70 mass% with respect to 100 mass% of aqueous dispersion. A fine powder produced by coagulating the aqueous dispersion according to claim 8. The following general formula (I) is selected from at least one component selected from waste water generated by coagulation of the aqueous dispersion according to claim 8, waste water generated by washing, and off-gas generated in the drying step.
_{CF 3 (CF 2) n OCH} 2 CF 2 CF 2 ORfCOOM (I)
(Wherein Rf is a partially or entirely fluorine-substituted C 2 alkylene group, n is 0 or 1, M represents a monovalent alkali metal, NH ₄ or H). Or the following general formula (II)
CF ₃ (CF ₂ ) _n OCFXCF ₂ CF ₂ ORfCOOM (II)
(Wherein Rf is a partially or entirely fluorine-substituted C 2 alkylene group, n is 0 or 1, M is a monovalent alkali metal, NH ₄ or H, and X is H or F). A method for producing a regenerated fluoroethercarboxylic acid, comprising a step of recovering and purifying the fluoroethercarboxylic acid to be purified.