WO2007081008A1

WO2007081008A1 - Novel fluorine surface active agent and novel fluorine-containing compound

Info

Publication number: WO2007081008A1
Application number: PCT/JP2007/050423
Authority: WO
Inventors: Takashi Okazoe; Yuriko Akiyama
Original assignee: Asahi Glass Company, Limited
Priority date: 2006-01-16
Filing date: 2007-01-15
Publication date: 2007-07-19
Also published as: JPWO2007081008A1

Abstract

Disclosed are a novel fluorine surface active agent and a novel fluorine-containing compound. Specifically disclosed is a fluorine surface active agent composed of a fluorine-containing compound essentially having a structure wherein two hydrophilic groups and two chain fluorine-containing hydrophobic groups are respectively bonded to a ring directly or via a linking group. The ring is a four- or more-membered ring which is composed of carbon atoms only or carbon atoms and another different atom. The two hydrophilic groups are bonded to one carbon atom or two adjacent carbon atoms selected from the carbon atoms of the ring, while the two chain fluorine-containing hydrophobic groups are bonded to one carbon atom or two adjacent carbon atoms selected from the carbon atoms of the ring. Furthermore, the carbon atom to which the hydrophilic group is bonded and the carbon atom to which the chain fluorine-containing hydrophobic group is bonded are not adjacent to each other. Also specifically disclosed is a novel fluorine-containing compound represented by the following formula (A-1). (A-1)

Description

New cc-standard fluorosurfactants and new fluorine-containing compounds

Technical field

[0001] The present invention relates to a novel fluorine-based surfactant and a novel fluorine-containing compound.

Background art

[0002] A fluorine-containing compound having a hydrophilic group and a fluorine-containing hydrophobic group is excellent in chemical stability and surface activity, and is used as a surfactant. Examples of the hydrophilic group in the fluorine-containing compound include an ionic group, a cationic group, an amphoteric group, and a nonionic group. In addition, examples of the fluorine-containing hydrophobic group in the fluorine-containing compound include an etheric oxygen atom and may include a polyfluoroalkyl group.

[0003] As the fluorine-containing compound, an acyclic fluorine-containing compound having one hydrophilic group and two fluorine-containing hydrophobic groups (for example, a compound represented by the following formula (si)) (Patent Document) 1) and a compound represented by the following formula (s2) (see Patent Document 2) are known.

[0004] [Chemical 1]

CF ₃ (CF ₂ ) ₃ (CH2) 20 (0) C-CH ₂

CF ₃ (CF ₂ ) ₃ (CH2) 20 (0) C-CH-S0 ₃ Na

(S1) (S2) Patent Document 3 discloses a fluorine-containing surfactant having a ring structure represented by the following formula as a fluorine-based surfactant used in suspension polymerization or emulsion polymerization of fluorine-containing olefins in water. Compounds are described.

[0005] [Chemical 2]

Patent Document 1: Japanese Patent Application Laid-Open No. 64-536

Patent Document 2: JP-A-4-248543

Patent Document 3: Japanese Patent Laid-Open No. 7-292008

Disclosure of the invention

Problems to be solved by the invention

[0006] As a result of intensive studies on the molecular structure of a fluorine-containing compound having a hydrophilic group and a chain-like fluorine-containing hydrophobic group, the present inventors have found that two hydrophilic groups and two chain-containing fluorine-containing hydrophobic groups. It was found that a fluorine-containing compound having a group bonded to a specific ring is particularly excellent in surface activity.

Means for solving the problem

That is, the present invention has the following gist.

<1> A fluorine-containing compound having a structure in which two hydrophilic groups and two chain-like fluorine-containing hydrophobic groups are bonded to the ring either directly or through a linking group, respectively. It is a ring of four or more members composed of only a carbon atom or a carbon atom and a hetero atom, and the two hydrophilic groups are selected from one carbon atom or two adjacent atoms selected from the carbon atom of the ring. The two chain-like fluorine-containing hydrophobic groups are bonded to one carbon atom selected from the ring carbon atoms or two adjacent carbon atoms, and the hydrophilic group is bonded. A fluorine-containing surfactant comprising a fluorine-containing compound having a structure in which a ring carbon atom and a ring carbon atom to which a chain-like fluorine-containing hydrophobic group is bonded are not adjacent to each other.

<2> Ring force is a saturated ring composed of only 4 or more carbon atoms, or a saturated ring composed of 3 or more carbon atoms and 1 or 2 oxygen atoms. Fluorosurfactant listed.

<3> The above <1> or <1>, wherein the ring is a saturated ring composed of 3, 4 or 5 carbon atoms and 1 or 2 oxygen atoms and is a 5-membered or 6-membered ring Fluorine-based surfactant according to 2>.

<4> The fluorine according to any one of the above <1> to <3>, wherein one or more selected groups are bonded to a ring carbon atom by a hydrogen atom, a fluorine atom, an alkyl group, and an alkoxy group. Surfactants.

<5> The hydrophilic group is directly bonded to the ring according to any one of the above <1> to <4> Fluorosurfactant.

<6> The hydrophilic group is a group selected from the group consisting of a carboxyl group, a carboxyl group-derived group, a sulfonic acid group, and a sulfonic acid group-derived group, according to any one of the above <1> to <5> Fluorosurfactant.

<7> The fluorine-containing surfactant according to any one of the above <1> to <6>, wherein the chain-like fluorine-containing hydrophobic group is directly bonded to the ring.

<8> The chain fluorine-containing hydrophobic group has an etheric oxygen atom having 1 to 20 carbon atoms and may be V, or may be a polyfluoroalkyl group in the above 1> to <7> !, The fluorine-based surfactant according to any one of the above.

<9> The fluorine-containing surfactant according to any one of the above <1> to <8>, wherein the fluorine-containing compound is a compound represented by the following formula (S).

[0008] [Chemical 3]

However, the symbols in the formula have the following meanings (the same shall apply hereinafter): o

X ¹ and X ² : each independently —O— or —CF—.

2

Y: group represented by the formula — CY ¹ Y ² — or group represented by the formula — CFY FY ⁴ — (where Y ¹ , 、 ² , Υ ³ , and Υ ⁴ are each independently a carboxyl group, Derived group of carboxylic group, sulfonic acid group, and group strength of derivatized group of sulfonic acid group Selected group, or a polyfluoroalkyl group having a C 1-10 etheric oxygen atom having the group ) ₀

Ζ: a group represented by the formula — CZZ ² — or a group represented by the formula — CFZ ³ CFZ ⁴ — (wherein Z and Z ⁴ each independently have an etheric oxygen atom having 1 to 20 carbon atoms) And a polyfluoroalkyl group that may be present).

<10> A compound represented by the following formula (A).

[0009] [Chemical 4]

However, the symbol in a formula shows the following meaning.

Q ^A1 and Q ^A2 : each independently a single bond, carbon number 1 to: perfluoroalkylene group of L0, or carbon atom number 2 to 10 containing an etheric oxygen atom between one carbon atom Oalkylene group.

T ^A : — C (0) OH or C (0) ONH.

Four

R ^A1 and R ^A2 : each independently a C ^{1 to} C: perfluoroalkyl group having L 0 or a C 2 to C 10 perfluoroalkyl group containing an etheric oxygen atom between one carbon atom. The invention's effect

[0010] According to the present invention, a fluorosurfactant having excellent surface activity is provided. The present invention also provides a novel fluorine-containing compound that is useful as a surfactant. BEST MODE FOR CARRYING OUT THE INVENTION

In the present specification, the compound represented by the formula (1) is also referred to as a compound (1). The same applies to compounds represented by other formulas.

The fluorosurfactant of the present invention comprises two hydrophilic groups, two chain-like fluorine-containing hydrophobic groups, and a force, each of which contains a structure bonded to a ring directly or via a linking group. The ring is a carbon atom or a ring of four or more members composed of a carbon atom and a heteroatom, and the two hydrophilic groups are carbon atoms of the ring. Bonded to a carbon atom or two adjacent carbon atoms, and the two chain-containing fluorine-containing hydrophobic groups are bonded to one carbon atom or two adjacent carbon atoms selected from the carbon atom of the ring, And a fluorine-containing compound having a structure in which a ring carbon atom to which a hydrophilic group is bonded and a ring carbon atom to which a chain-like fluorine-containing hydrophobic group is bonded are not adjacent to each other.

[0012] The ring in the fluorine-containing compound is a saturated ring composed of only 4 or more carbon atoms. It is preferably a saturated ring composed of 3 or more carbon atoms and 1 or 2 oxygen atoms. It is composed of 3 or more carbon atoms and 1 or 2 oxygen atoms. Particularly preferred is a saturated ring. Further, the upper limit of carbon atoms in the saturated ring is not particularly limited, and preferably 10 or less, particularly preferably 5 or less.

A preferred embodiment of the ring in the fluorine-containing compound is a saturated ring composed of 3, 4 or 5 carbon atoms and 1 or 2 oxygen atoms, and is a 5-membered or 6-membered ring. A ring is mentioned.

[0013] Groups other than the two hydrophilic groups and the two chain-like fluorine-containing hydrophobic groups bonded to the ring carbon atom in the fluorine-containing compound are a hydrogen atom, a fluorine atom, an alkyl group, and an alkoxy group. Group Force One or more groups selected are preferably a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group force having 1 to 6 carbon atoms. A hydrogen atom or a fluorine atom with a particularly preferred hydrogen atom or a fluorine atom being particularly preferred is most preferred.

The two hydrophilic groups in the fluorine-containing compound are preferably directly bonded to the ring, which may be directly bonded to the ring via a linking group which may be directly bonded to the ring. The linking group is a difluoromethylene group, which is preferably a perfluoroalkylene group having 1 to 5 carbon atoms, which is preferably a polyfluoroalkylene group which may have an etheric oxygen atom having 1 to 10 carbon atoms. Is particularly preferred.

The two hydrophilic groups are preferably the same hydrophilic group, which may be the same hydrophilic group or different hydrophilic groups. The kind of the hydrophilic group is not particularly limited, and a carboxyl group, a derivative group thereof, a sulfonic acid group, or a derivative group thereof is particularly preferable.

The derivative group of the carboxyl group is a group represented by the formula —C (0) OW ^R1 or a formula —C (0) N (

-w ^R2 ) (-w ^R3 ) is preferred. The group represented by the group represented by c (o) ow ^R1 is particularly preferred.

However, the symbol in a formula shows the following meaning.

w ^R1 : Lithium, potassium, sodium, or ammonium.

W ^R2 : A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms. w: Quaternary ammonium halide salt, betaine, amine oxide, and carboxylate group power of force selected 1 compound with 1 or more hydrogen atoms bonded to carbon atoms, 1 hydrogen atom removed, 1 Valent group.

W ^R2 and W ^R3 may be bonded to each other to form a divalent group. The divalent group is a quaternary ammonium halide salt, betaine, amine oxide, and a group force that also has an amino acid salt power, and a compound power that requires two or more hydrogen atoms bonded to carbon atoms. Except that it is preferably a divalent group.

[0015] Specific examples of the group represented by the formula C (0) OW ^R1 include C (0) OLi, 1C (0) ONa, 1C (0) OK, -C (0) ONH .

Four

Specific examples of the group represented by the formula — C (0) N (—W ^R2 ) (— W ^R3 ) include C (0) NH (— (CH) COONH), —C (0) NH (-( CH) N + (CH) Γ), one C (0) NH (— (CH

2 5 4 2 3 3 3 2

) N + (CH) (CH COO_)), — C (0) NH (— (CH) N (CH) (→ 0)), — C (O)

3 3 2 2 2 3 3 2

N (-CH CH) (-CH COOK) and the like can be mentioned.

2 3 2

[0016] The derivative group of the sulfonic acid group is a group represented by the formula SO (OW ^sl ) or a formula SO N (—

A group represented by 2 2 w ^S2 ) (-w ^S3 ) is preferred.

w ^sl : Lithium, potassium, sodium, or ammonium.

W ^S2 and W ^S3 : each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms.

[0017] The two chain-like fluorine-containing hydrophobic groups in the fluorine-containing compound are directly bonded to the ring, which may be directly bonded to the ring via a linking group or may be bonded to the ring. I like it.

The two chain fluorine-containing hydrophobic groups may be the same chain fluorine-containing hydrophobic group or different chain fluorine-containing hydrophobic groups. The type of the chain fluorine-containing hydrophobic group is not particularly limited, and has an etheric oxygen atom having 1 to 20 carbon atoms! /, May! /, A carbon preferred for a polyfluoroalkyl group. A perfluoroalkyl group having 1 to 10 carbon atoms is more preferable, and a perfluoroalkyl group having 4 to 10 carbon atoms is particularly preferable!

The molecular weight of the fluorine-containing compound is 300-3000 force <, 600-1500 force The fluorine atom content of the fluorine-containing compound is preferably from 30 to 70 mass%, particularly preferably from 45 to 70 mass%.

[0018] The reason why the fluorosurfactant of the present invention has an excellent surface active action is not necessarily clear, but two hydrophilic groups and two chain fluorine-containing hydrophobic groups are each a carbon. This is thought to be due to the structure in which the hydrophilic and hydrophobic parts are relatively unevenly distributed in the molecule by binding to a specific position on the ring.

The fluorine-containing compound in the present invention is preferably the following compound (S).

[0019] [Chemical 5]

However, the symbol in a formula shows the following meaning.

X ¹ and X ² are each —O ^2, are each —CF—, or

2

It is preferable that one is O and the other is CF-

2

It is particularly preferred.

[0020] Y is a group represented by the formula —CY or a group represented by the formula —CFY ³ CFY ⁴ —.

^{^{However, Υ \ Υ 2, Υ 3}} , and Upsilon ⁴ are each independently a carboxyl group, derivative groups, sulfonic acid groups, and groups selected from the group consisting of induction of sulfonic groups a carboxyl group or a base, 1 to C: a polyfluoroalkyl group optionally having an etheric oxygen atom of L0. Among these, γ \ γ ² , γ ³ , and γ ⁴ are each independently preferably C (0) OLi, C (0) ONa, carboxy group-derived group or sulfonate group-derived group. C (0) OK or C (0) ONH is more preferred, C (0) ONH

4 4 is particularly preferred. Y ¹ and Y ² are preferably the same group. Y ³ and Y ⁴ are preferably the same group.

[0021] Z is a group represented by the group or the formula CFZ ³ CFZ ⁴ Formula CZ Z ^2. However,

Z ³ and Z ⁴ each independently represent a polyfluoroalkyl group optionally having an etheric oxygen atom having 1 to 20 carbon atoms. Among them, zzz and And z ⁴ are each independently a perfluoroalkyl group having 4 to 10 carbon atoms, preferably a perfluoroalkyl group having 1 to 10 carbon atoms. Z ¹ and Z ² may be the same group or different groups. Z ³ and Z ⁴ may be the same group or different groups.

[0022] Preferred embodiments of the compound (S) include the following compound (A) and the following compound (B).

[0023] [Chemical 6]

The symbols in compound (A) have the same meaning as described above.

Q ^A1 and Q ^A2 in the compound (A) are each particularly preferably a single bond or a single bond, preferably a perfluoroalkylene group having 1 to 10 carbon atoms. Q ^A1 and Q ^A2 may be the same or different.

In the compound (A), C (0) ONH is preferable.

Four

In the compound (A), R ^A1 and R ^A2 are each independently preferably a perfluoroalkyl group having 4 to 10 carbon atoms, which is preferably a C 1 to C perfluoroalkyl group! / ヽ. R ^A1 and R ^A2 may be the same group or different groups.

The symbols in the compound (B) have the following meanings.

Q ^B1 and Q ^B2 are each independently a single bond, carbon number 1 to: perfluoroalkylene group of LO, or carbon atom Perfluoro having 2 to 10 carbon atoms including an etheric oxygen atom between carbon atoms Loalkylene group.

T ^B : -C (O) OH or C (O) ONH.

Four

R ^B1 and R ^B2 : each independently, a C 1 to C: perfluoroalkyl group having L 0, or a C 2 to C 10 perfluorinated alkyl group containing an etheric oxygen atom between carbon atoms. [0025] Q ^m and in the compound) are particularly preferably a single bond or a single bond, preferably a perfluoroalkylene group having 1 to 10 carbon atoms. Q ^B1 and Q ^B2 may be the same group or different groups.

T ^B in the compound (B) is preferably —C (0) ONH.

R 1 and R 2 in the compound) are each independently preferably a perfluoroalkyl group having 1 to 10 carbon atoms, preferably a perfluoroalkyl group having 4 to 10 carbon atoms, preferably a LO perfluoroalkyl group! / ヽ. R ^m and R ^B2 may be the same or different.

[0026] Specific examples of the compound (A) include the following compounds.

[0027] [Chemical 7]

Specific examples of the compound (B) include the following compounds.

[0028] [Chemical 8]

CF ₃ (CF ₂ ) ₃ ,. (CF2) ₃ CF ₃

ゝ CF ₂ C (0) ONH _{4 The} compound (A) is a novel compound unknown in the literature.

The method for producing the compound (A) is not particularly limited, and it is preferably produced by chemical conversion of the —COF group of the following compound (A1).

[0029] [Chemical 9]

The chemical conversion is not particularly limited, and a known method can be applied. For example, it is preferable that the compound (Α) wherein -C (Ο) ΟΗ is produced by reacting the compound (A1) with methanol and then subjecting it to a hydrolysis reaction. Further, T ^Alpha is - C (0) compound which is ONH (A) is

Four

Preferably, T ^A is prepared by reacting one C (0) compound is OH (A) and ammonia

[0030] Specific examples of the compound (A1) include the following compounds.

[0031] [Chemical 10]

The compound (Al) is obtained by subjecting the following compound (A5) and the following compound (A4) to an acetal reaction to obtain the following compound (A3), and then fluorinating the compound (A3) to produce the following compound (A2 It is preferable that the compound (A2) is produced by an ester decomposition reaction.

[Chemical 11]

However, the symbols in the formula have the following meanings (the same shall apply hereinafter): o E ^a : —C (0) 0—or CH 0 (0) C

2

E ^A : —C (0) 0—or —CF 0 (0) C

2

R ^al: fluorinated in the same group as radicals or R ^A1 to be R ^A1.

R ^a2: fluorinated in the same group as radicals or R ^A2 as the R ^A2.

Q ^al: single bond, fluorinated in the Q ^A1 group or the same group as Q ^A1,.

Q ^a2: a single bond, fluorinated in Q ^A2 become group or Q ^A2 same group as.

V ^al and V ^a2 _: each independently an alkyl group which may contain a tellurium oxygen atom between carbon atoms having 120 carbon atoms and carbon atoms, or ether between carbon atoms having 120 carbon atoms and carbon atoms A perfluoroalkyl group containing a reactive oxygen atom.

V ^A1 and V ^A2 _: each independently a perfluoroalkyl group containing a tellurium oxygen atom between a carbon atom having 120 carbon atoms and a carbon atom.

[0033] R ^A1 R ^A2 Q ^A1 and Q ^A2 have the same meaning as described above.

R ^al is preferably a group that is fluorinated and becomes R ^A1 R ^a2 is preferably a group that is fluorinated and becomes R ^A2 Each independently, an alkyl group having 1 to 10 carbon atoms, or a carbon atom Particularly preferred is an alkyl group having 2 10 carbon atoms containing an etheric oxygen atom.

[0034] Q ^{al prefers} a single bond or fluorinated group to form Q ^A1 Q ^{a2 prefers} a single bond or fluorinated group to form Q ^A2 independently of each other, a single bond, carbon An alkylene group having 1 10 carbon atoms, or an alkylene group having 2 10 carbon atoms containing an etheric oxygen atom between carbon atoms is more preferable, and a single bond is particularly preferable! /.

The acetal reaction, the fluorination reaction, and the ester decomposition reaction are preferably carried out according to known methods.

The fluorination reaction is particularly preferably carried out by a liquid phase fluorination method, preferably a liquid phase fluorination method, an electrolytic fluorination method or a cobalt fluorination method. As the liquid phase fluorination method, the liquid phase fluorination method described in International Publication No. 00Z56694 pamphlet is preferable.

[0035] Specific examples of the compound (A5) include the following compounds.

[0036] [Chemical 12]

Specific examples of the compound (A4) include the following compounds.

[0037] [Chemical 13]

Specific examples of the compound (A3) include the following compounds.

[0038] [Chem. 14]

CH ₃ OiO) CCH ,,, CH ₂ C (0> OCH ₃

o, o

CH3 (CH2) 4 ', (CH2) 4CHa

Specific examples of the compound (A2) include the following compounds.

[0039] [Chemical 15]

The compound (B) is also a novel compound whose literature is unknown.

[0040] The production method of the compound (B) is not particularly limited, and it is preferably produced by chemical conversion of the COF group of the following compound (B1).

[0041] [Chemical 16]

(B1)

The chemical conversion is not particularly limited, and a known method can be applied. For ^example, τ Β gar C The compound (B) which is (O) OH is preferably produced by reacting the compound (Bl) with methanol and then performing a hydrolysis reaction. In addition, a compound in which T ^B is —C (0) ONH (

Four

B) is preferably produced by reacting ammonia with a compound (B) in which T ^B is —C (0) OH.

[0042] Specific examples of the compound (B1) include the following compounds.

[0043] [Chemical 17]

Compound (Bl) is obtained by subjecting the following compound (B5) and the following compound (B4) to an acetalization reaction to obtain the following compound (B3), and then fluorinating the compound (B3) to obtain the following compound (B2). It is preferable that the compound (B2) is produced by an ester decomposition reaction.

[0044] [Chemical 18]

v

E ^b : —C (0) 0—or CH 0 (0) C- ₀

2

E ^B : — C (0) 0— or CF 0 (0) C

2

R ^bl: fluorinated in the same group as radicals or R ^B1 as the R ^B1.

R ^_b2: fluorinated in the same group as radicals or R ^B2 serving as R ^B2.

Q ^bl : a single bond, a group that is fluorinated to form Q ^B1 , or the same group as Q ^B1 . Q ^b2: single bond, fluorinated in the Q ^B2 group or Q ^B2 same group as.

V ^bl and V ^_b2: each independently, a carbon atom number of 1 20 carbon atoms - an alkyl group which may contain a te Le oxygen atom between carbon atoms or carbon atoms of a carbon number of 1 20, - ether between carbon atoms A perfluoroalkyl group containing a reactive oxygen atom.

V ^B1 and V ^_B2: each independently, a carbon atom number of 1 20 carbon atoms - contain ether oxygen atom between carbon atoms, even I, pel full O b alkyl group.

[0045] R ^m R ^B2 Q ^B1 and Q ^B2 have the same meaning as described above.

R ^bl is preferably a group fluorinated to become R ^B1 R ^b2 is preferably a group fluorinated to become R ^B2 Each independently, an alkyl group having 1 to 10 carbon atoms, or a carbon atom Particularly preferred is an alkyl group having 2 10 carbon atoms containing an etheric oxygen atom.

Q ^bl is preferably a single bond or fluorinated group to form Q ^B1 Q ^b2 is preferably a single bond or fluorinated group to form Q ^B2 independently of each other, a single bond, carbon number 1 10 And an alkylene group having 2 to 10 carbon atoms containing an etheric oxygen atom between carbon atoms, more preferably a single bond!

[0046] The fluorination reaction is particularly preferably carried out by a liquid phase fluorination method, preferably a liquid phase fluorination method, an electrolytic fluorination method, or a cobalt fluorination method. As the liquid phase fluorination method, the liquid phase fluorination method described in International Publication No. 00Z56694 pamphlet is preferable.

[0047] Specific examples of the compound (B5) include the following compounds.

[0048] [Chemical 19]

Specific examples of the compound (B4) include the following compounds.

[0049] [Chemical 20]

CH3 (SH 2) 3 (CH2) 3 CH3 (CH) 4 H ₂ ) 4CH3 CH ₃ (v ^ H ₂ ) 5 (CH2 sCH3

H CH— CH Specific examples of the compound (B3) include the following compounds _c

[0050] [Chemical 21]

CH ₃ (H2) 5. (CH2) ₅ CH ₃ CH ₃ (CH ₂ ) ₄ '(CH2) 4CH3

0 Ό o, O

CH ₃ 0 (0) C "C (0) OCH ₃ CH ₃ 0 (0) CCH ₂ CH ₂ C (0) OCH ₃

Specific examples of the compound (B2) include the following compounds _c

[0051] [Chemical 22]

The compound (A) and the compound (B) of the present invention are useful as a monomer raw material, a fluorosurfactant and the like, and particularly useful as a fluorosurfactant.

Example

[0052] Hereinafter, the present invention will be described in detail by way of examples. The present invention should not be construed as being limited to these examples.

Hereafter, CF-CICF CHC1F and CHCl CF CF are mixed with R-225 and CC1, respectively.

2 2 2 2 3

FCC1F is R-113, gas chromatography is GC, nuclear magnetic resonance method is NMR,

twenty two

Tetramethylsilane is referred to as TMS.

[0053] [Example 1] Production example of compound (A-1)

Using the following compound (A5-1) and the following compound (A4-1) as starting materials, the following compound (A-1) was produced according to the following synthesis scheme.

[0054] [Chemical 23] CH) CC) OCH3

CH ₃ (CH ₂ヽ_CH2 ) _5C H ₃ + \ _QH

(A5-1) (A4-1)

(A-C1) (A-1)

[0055] [Example 1 1] Production example of compound (A3-1)

A three-necked flask equipped with a Dean Stark (internal volume: 1 L) was charged with compound (A5-1) (125. 87 g), compound (A4-1) (123.21 g), p-toluenesulfonic acid (0.998 g), After adding toluene (700 mL), the temperature inside the flask was raised to about 70 ° C. to obtain a uniform yellow solution. The flask was heated until toluene was refluxed. After reacting for 10 hours under reflux of toluene, p-toluenesulfonic acid (2.0 g) was further added and reacted for 10 hours to obtain a crude reaction solution (179.98 g). The reaction crude liquid was purified by column chromatography to obtain compound (A3-1) (76. 57 g).

[0056] [Example 1 2] Production example of compound (A2-1)

An autoclave (made of nickel, internal volume 3000 mL) was prepared, and a NaF pellet packed bed was installed at the gas outlet of the autoclave. R-113 (1600 g) was placed in an autoclave and stirred while maintaining at 25 ° C. As it was, nitrogen gas was blown into the autoclave for 1 hour, and then fluorine gas diluted to 20% by volume with nitrogen gas (hereinafter referred to as 20% fluorine gas) was blown. Next, a solution obtained by dissolving the compound (A3-1) (25.0 g) obtained in Example 1-1 in R-113 was introduced into an autoclave, and 20% fluorine gas was blown in as it was.

Next, nitrogen gas was blown into the autoclave, and then the contents of the autoclave were collected and analyzed by NMR. As a result, it was confirmed that the compound (A2-1) was produced. The content was confirmed to be a mixture of the compound (A2-1) and a compound in which one of the fluorine atoms of the compound (A2-1) was replaced with a hydrogen atom. F-NMR of compound (A2-1) (282.6 MHz, solvent: CDC1, standard: CF) δ (pp

3 6 6 m): -58.6 (6F), —82.3 (6F), —109.71 (2F), —117.47 to 117.83 (4F), — 120.77 to 121. 12 (4F), —122.27 (4F), — 123.13 (4F), —126.60 (4 F).

[0058] [Example 1 3] Production example of compound (Al-1)

The flask was charged with the compound (A2-1) (33. lg) obtained in Example 1-2 and KF powder (1. lg). The inside of the flask was heated to 40 ° C. and stirred for reaction for 8 hours. Thereafter, the obtained reaction crude liquid was distilled under reduced pressure to obtain a fraction (3.99 g) at 83 ° C./0.23 kPa (absolute pressure). As a result of analyzing the fraction by NMR, it was confirmed that the compound (A1-1) was produced.

¹⁹ F-NMR of compound (Al-1) (376. OMHz ゝ solvent: CDC1, standard: CFC1) δ (ρ

3 3 pm): 25.5 (2F), --81.6 (6F), --109.8 ~-111.1 (2F), --118.4 ~-118.6 (4F), -121.1 (4F), --122.4 (4F), —123.3 (4F), —127.3 (4F).

[0059] [Example 1 4] Production Example of Compound (Aim-1)

The solution obtained by adding the compound (A1-1) (2.14 g) dropwise to methanol (10 mL) was stirred and reacted for 2 hours. Next, the solution was washed successively with a saturated aqueous sodium hydrogen carbonate solution and ion-exchanged water to obtain a crude product. The crude product was purified by silica gel column chromatography, and further recrystallized and purified in a mixed solvent of cyclohexane and R-225 to obtain compound (Aim-1) (0.49 g).

¹⁹ F-NMR of compound (Aim-1) (376. OMHz ゝ solvent: CDC1, standard: CFC1) δ (

3 3 ppm): -81.2 (6F), -110.97 (2F), -118.5 (4F), -120.7 (4F) ゝ -122.3 (4F), -123.1 (4F), -126.6 (4F).

¹ H-NMR of compound (Aim-1) (300.4MHz, solvent: CDC1, standard: TMS) δ (p

Three

pm): 3.92 (6H)

[0060] [Example 1 5] Production example of compound (A-cl)

15 mass. A solution obtained by adding the compound (Aim-1) (0.49 g) to an aqueous solution (4. Og) containing / c ^ NaOH was stirred at 60 ° C for 5 hours. Next, an appropriate amount of 3 mol ZL hydrochloric acid aqueous solution was added to make the solution acidic, followed by solvent extraction (extraction solvent: R-225). Thereafter, the solvent was distilled off to obtain a white solid compound (A-cl) (0.4 g). F-NMR of compound (A-cl) (376. 0MHz, solvent: acetone, standard: CFC1) δ (p

3 pm): -80. 6 (6F), —110. 3 (2F), —116. 5 (4F), —119.4 (4F), —121.2 (4F),-122. 0 (4F ), —125. 5 (4F).

[0061] [Example 1 6] Production example of compound (A-1)

Compound (A—cl) (0.4 g) was charged into a round bottom flask (internal volume 30 mL). Next, in flasks internal temperature 25 ° C, while stirring the flask was added dropwise an aqueous solution containing 30 mass ^_0/0 of ammonia (2. 23 g). Further, 10 mL of water was added to the flask, and the flask was stirred at a temperature of 50 ° C. for 2 hours. Subsequently, nitrogen gas was blown into the flask to purge excess ammonia, and then the flask contents were frozen at a flask internal temperature of 78 ° C. Furthermore, the inside of the flask was dried under reduced pressure to obtain a white solid compound (A-1) (0.242 g).

¹⁹ F-NMR of compound (A-1) (376. OMHz, solvent: acetone, standard: CFC1) δ (ρρ

3 m): -80. 5 (6F), —108. 5 (2F), —115. 5 (4F), —119. 0 (4F), —121. 2 (4 F),-121. 9 ( 4F),-125. 6 (4F).

[0062] [Example 2] Evaluation example of surface active ability of compound (A-1)

An appropriate amount of compound (A-1) is added to water, an aqueous solution (A 1) containing 0.1% by mass of compound (A-1), and an aqueous solution containing 0.01% by mass of compound (A-1) (A2 ) The static surface tension of the aqueous solution (A1) was 18.3 mNZm, and the static surface tension of the aqueous solution (A2) was 35.3 mN / m.

Industrial applicability

[0063] According to the present invention, a fluorosurfactant having excellent surface activity is provided. Moreover, according to the present invention, a novel fluorine-containing compound useful as a fluorine-based surfactant or the like is provided.

The fluorosurfactant of the present invention includes an emulsifier, an ink, a paint, a resist, etc. used for emulsion polymerization of a fluorine-containing monomer (tetrafluoroethylene, hexafluoropropylene, etc.) in an aqueous medium. Water and oil repellents used to improve the wettability or permeability of foams, foam stabilizers, foaming aids and leveling agents (wax etc.) used to improve foam generation or fire extinguishing performance. Cleaning agent, mold release agent, antifungal agent, latex stabilizer, agricultural use It is useful as a film antifogging agent, pigment dispersant, antifouling agent and the like. The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2006-007495 filed on January 16, 2006 are hereby incorporated by reference. It is something that is incorporated.

Claims

The scope of the claims

[1] A fluorine-containing compound having a structure in which two hydrophilic groups and two chain-like fluorine-containing hydrophobic groups are each bonded to a ring directly or via a linking group. A four or more-membered ring composed of only a carbon atom or a carbon atom and a heteroatom, wherein the two hydrophilic groups are one carbon atom of the ring or two adjacent ones. Bonded to a carbon atom, the two chain-like fluorine-containing hydrophobic groups are bonded to one carbon atom selected from the ring carbon atoms or two adjacent carbon atoms, and a hydrophilic group is bonded. A fluorine-containing surfactant comprising: a fluorine-containing compound having a structure in which a ring carbon atom and a ring-like fluorine-containing hydrophobic group bonded to a ring carbon atom are not adjacent to each other.

[2] The ring according to claim 1, wherein the ring is a saturated ring composed of only 4 or more carbon atoms, or a saturated ring composed of 3 or more carbon atoms and 1 or 2 oxygen atoms. The fluorine-type surfactant of description.

[3] The ring according to claim 1 or 2, wherein the ring is a saturated ring composed of 3, 4 or 5 carbon atoms and 1 or 2 oxygen atoms, and is a 5-membered or 6-membered ring. The fluorine-type surfactant of description.

[4] The fluorine-based interface according to any one of [1] to [3], wherein one or more groups selected from a group force selected from a hydrogen atom, a fluorine atom, an alkyl group, and an alkoxy group are bonded to a carbon atom of the ring. Activator.

[5] The fluorosurfactant according to any one of claims 1 to 4, wherein the hydrophilic group is directly bonded to the ring.

[6] The hydrophilic group is a group selected from the group consisting of a carboxyl group, a carboxyl group-derived group, a sulfonic acid group, and a sulfonic acid group-derived group. Fluorosurfactant.

[7] The fluorine-containing surfactant according to any one of [1] to [6], wherein the chain-like fluorine-containing hydrophobic group is directly bonded to the ring.

[8] The fluorinated group according to any one of [1] to [7], wherein the chain fluorine-containing hydrophobic group is a polyfluoroalkyl group optionally having an etheric oxygen atom having 1 to 20 carbon atoms. Surfactant. The fluorine-containing surfactant according to any one of claims 1 to 8, wherein the fluorine-containing compound is a compound represented by the following formula (S).

[Chemical 1]

However, the symbol in a formula shows the following meaning.

X ¹ and X ² : each independently O or —CF—.

2

Y: Formula — a group represented by CY ¹ Y ² or a group represented by formula CFY FY ⁴ (Y

, Γ ² , Υ ³ , and γ ⁴ are each independently a carboxyl group, a carboxyl group-derived group, a sulfonic acid group, and a group force that is a derived group of a sulfonic acid group. A polyfluoroalkyl group optionally having an etheric oxygen atom of 1 to 10 is shown. ) ₀

Ζ: a group represented by the formula —CZ Z ² — or a group represented by the formula —CFZ ³ CFZ ⁴ — (however,

And Z ⁴ each independently represent a polyfluoroalkyl group optionally having an etheric oxygen atom having 1 to 20 carbon atoms. ).

A compound represented by the following formula (A).

[Chemical 2]

However, the symbol in a formula shows the following meaning.

Q ^A1 and Q ^A2 : each independently a single bond, carbon number 1 to: L0 perfluoroalkylene group, or carbon atom Perfluoro having 2 to 10 carbon atoms including an etheric oxygen atom between carbon atoms Loalkylene group.

T ^A : — C (O) OH or C (O) ONH

R ^A1 and each independently, a C 1-: perfluoroalkyl group of L 0, or Is a C 2-10 perfluoroalkyl group containing an etheric oxygen atom between carbon atoms.