JP4497292B2 - Branched surfactant having fluoroalkyl group and hydrocarbon group - Google Patents

Description

  The present invention relates to a branched surfactant having a fluoroalkyl group and a hydrocarbon group.

  The surfactant of the present invention can be used together with liquid, subcritical or supercritical carbon dioxide to improve functions as a solvent for chemical reaction, washing, extraction, dyeing and the like.

  With the emergence of environmental problems, a technology that uses CO2 as a solvent instead of highly toxic organic solvents has attracted attention. In addition, if the compound can be handled in CO2, there is a possibility that the wastewater treatment cost can be greatly reduced, and its application to industrial fields where the wastewater treatment cost is high such as chemical reaction, washing, extraction, dyeing etc. is attracting special attention. .

  For such applications, a surfactant for mixing carbon dioxide and an aqueous solvent is required.

As a hybrid type fluorine compound having both a hydrocarbon group and a fluorinated alkyl group in the molecule, H (CF ₂ CF ₂ ) _n (CH ₂ CH ₂ O) _n OOCCH (OSO ₃ Na) CH ₂ COOR is available. Patent Document 1 describes an additive for improving the coating physical properties of the photosensitive material, and H (CF ₂ CF ₂ ) _n CH ₂ OCH ₂ CH (OSO ₃ Na) R is a patent for improving the coating physical properties of the photosensitive material. Patent Document 3 describes H (CF ₂ CF ₂ ) _n CH ₂ OCH ₂ CH (OSO ₃ Na) CH ₂ OR as an antistatic material for a photosensitive material.

On the other hand, surfactants that exhibit high functions in carbon dioxide are very limited, and sulfosuccinates having fluorine groups are reported in Non-Patent Documents 1 to 3, and are double-stranded or branched. There is a need for a hydrophobic group of structure. It was also known that the hybrid type has a higher function even in a branched structure. For example, Non-Patent Document 4 reported that C ₇ F ₁₅ CH (OSO ₃ Na) C ₇ H ₁₅ has a high function of taking water into carbon dioxide. However, this compound was not practical because of its low stability.

 For this reason, synthesis of stable and highly functional hybrid surfactants has recently been reported (Non-Patent Documents 5 to 8). However, these known hybrid surfactants do not exhibit a sufficient function in carbon dioxide (Non-patent Document 3).

The phosphate ester reported in Non-Patent Document 9 expresses a high function in carbon dioxide, but the phosphate ester may be hydrolyzed and has a problem in stability during long-term use.
Japanese Patent Laid-Open No. 51-32222 Japanese Examined Patent Publication No. 52-26687 Japanese Examined Patent Publication No. 52-26687 Progr, Colloid Polym, Sci. 2000, 115, 214 Langmu1r 2001, 17, 274 Langmuir 2003, 19 pp. 220 Langmuir l994, 10, 3536 Langmuirl 995, 11, 466 Abstract of Oil Chemistry Discussion 2000, 305, 306 Summary of Oil Chemistry Conference 2002, 101 J. Am. Chem. SOC. 2002, 124, 6516 J. Am. Chem. SOC. 2002, 124, 1834

  An object of the present invention is to provide an effective surfactant when handling polar compounds such as water in carbon dioxide.

The present invention provides the following surfactants.
Item 1. The following general formula (I)

(In the formula, Rf represents a fluoroalkyl group which may have an ether bond, Rh represents an alkyl group, X ¹ and X ² are the same or different and represent a divalent linking group, and p represents 0 or 1 and q is 0 or 1. n represents an integer of 1 to 10. M represents a hydrogen atom, an alkali metal, a 1/2 alkaline earth metal, or ammonium.)
A surfactant represented by
Item 2. The surfactant according to claim 1, wherein Rf has 5 to 12 carbon atoms.
Item 3. General formula: Rf (CH ₂ ) _n OOCCH (SO ₃ M) CH ₂ COORh
(Wherein Rf, Rh, n and M are as defined above.)
The surfactant of Claim 1 or 2 represented by these.
Item 4. General formula: Rf (CH ₂ ) _n OCCH (SO ₃ M) Rh
(Wherein Rf, Rh, n and M are as defined above.)
The surfactant of Claim 1 or 2 represented by these.
Item 5. Use of the surfactant according to any one of claims 1 to 4 for use in a solvent system containing carbon dioxide and a polar compound.
Item 6. Item 6. The use according to Item 5, wherein the polar compound is water.

  Hereinafter, the present invention will be described in more detail.

The surfactant of the present invention can mix CO ₂ (supercritical, subcritical or liquid) and polar compounds such as water, and can treat organic / inorganic chemical reactions or plating using CO ₂ as a solvent and polar compounds such as water. This makes it possible to improve the efficiency of electrochemical reactions such as dyeing and extraction.

Examples of polar compounds to be mixed with the CO ₂ solvent include water, alcohols (such as methanol, ethanol, propanol, and butanol), hydrous alcohols, glycols such as DMF, DMSO, formamide, ethylene glycol, and propylene glycol, and water such as acetonitrile and THF. Or the organic solvent miscible with water, or the mixed solvent of water and these organic solvents is mentioned, Preferably water is mentioned. Furthermore, metal fine particles, inorganic salts, organic salts, or biological compounds such as phospholipids, saccharides, proteins, and carbohydrates can be used.

  Such a surfactant is preferably a hybrid surfactant having a sulfonic acid group and having one fluoroalkyl group and one alkyl group.

In the surfactant of general formula (I):
Rf is a linear or branched alkyl group having one or more fluorine atoms, which may have an ether bond, and may be a perfluoroalkyl group which may have an ether bond. Rf has 4 to 50 carbon atoms, and when Rf is a fluoroalkyl group having no ether bond, the carbon number is 4 to 20, preferably 5 to 18, more preferably 5 to 12, and Rf is ether. In the case of a fluoroalkyl group having a bond, it is 4 to 50, preferably 5 to 40, more preferably 5 to 35.

As a preferred specific example of Rf, in the case of a fluoroalkyl group having no ether bond,
C _m F _{2m + 1} − (n represents an integer of 4 to 20, m represents an integer of 1 to 10);
HC _m F _2m − (n represents an integer of 4 to 20, m represents an integer of 1 to 10);
In the case of a fluoroalkyl group having an ether bond,
CF ₃ CF (CF ₃ ) (CF ₂ ) _m- (m represents an integer of 4 to 20);
CF ₃ CF (CF ₃ ) (CF ₂ ) _m CF (CF ₃ ) CF _2- (m represents an integer of 4 to 20);
C _m F _{2m + 1} O (CF ₂ CF ₂ O) _r CF ₂ − (m represents an integer of 1 to 10, r represents an integer of 1 to 15);
C _m F _{2m + 1} O (CF (CF ₃ ) CF ₂ O) _r CF (CF ₃ ) − (m represents an integer of 1 to 10, r represents an integer of 1 to 15)
HC _m F _2m O (CF ₂ CF ₂ O) _r CF ₂ − (m represents an integer of 1 to 10, r represents an integer of 1 to 15);
HC _m F _2m O (CF (CF ₃ ) CF ₂ O) _r CF (CF ₃ )-(m represents an integer of 1 to 10, r represents an integer of 1 to 15)
Is exemplified.

Rh is a linear or branched alkyl group having 3 to 18, preferably 4 to 12, and more preferably 4 to 10 carbon atoms. Preferable specific examples of Rh include (n-, sec-, iso-, tert-) butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl:
The divalent linking groups represented by X ¹ and X ² include O, S, NH, NR, C = O, C (O) O, OC (O), C (O) S, SC (O) , C (O) NH, C (O) NR, NH (O) C, NR (O) C (where R is a C1-C4 linear or branched alkyl group). and, X ¹ and / or X ² and CH (SO ₃ M) further between an alkylene group having a good straight or branched be fluorinated (e.g., (CH2) m, (CF2 ) n , CF (CF3), (CF2) n (CH2), etc., m and n are integers of 1 to 3).

Examples of preferable divalent linking groups represented by X ¹ and X ² include the following.

_{- (CH 2) n COO- (} n is an integer of 0 to 4, preferably 0 or 1.)
_{- (CH 2) n O- (} n is an integer of 0 to 4, preferably 0 or 1.)
M is a hydrogen atom, alkali metal (Na, K, Li, Cs), 1/2 alkaline earth metal (Ca, Mg, Ba), ammonium (NH ₄ ), quaternary ammonium (NR ₄ ; R is C 1- Represents a C4 linear or branched alkyl group).

As a balance between the CO2 affinity part (Rf) and the hydrophilic group (Rh),
(Rf carbon number) / (Rh carbon number) = 1/2 to 2/1 is preferable, and 2/3 to 3/2 is more preferable.

  The surfactant of the present invention is a commercially available product, or can be easily produced by those skilled in the art by a known method (for example, JP-A No. 51-32322).

  The amount of the surfactant used in the present invention is desirably about 0.001 to 2000 wt%, preferably about 0.01 to 500 wt%, more preferably about 0.1 to 100 wt% with respect to the polar compound handled in carbon dioxide. The amount of the surfactant used is different from the surfactant in a normal two-phase system, and the weight of the surfactant may be increased depending on the polar compound to be used. For example, when a chemical reaction is performed using a metal salt or the like as a catalyst in CO2, the amount of the surfactant used may exceed 100 wt%.

  The surfactant of the present invention is suitably used in a two-phase system between CO2 (liquid, subcritical, supercritical state) and water or a polar compound.

  According to the present invention, the interface that can realize a good mixed state when used in a carbon dioxide-polar compound system because it has high uptake into water carbon dioxide, which is a substance that is not compatible with carbon dioxide. An active agent is provided.

EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example and a comparative example, this invention is not limited only to this.
Examples 1-5
Compounds 1 to 5 were synthesized according to the description in JP-A-51-32222.

The physical property values of the obtained compound are shown below.
C ₆ F ₁₃ CH ₂ CH ₂ OOCCH (SO ₃ Na) CH ₂ COOC ₆ H ₁₃ 1
Colorless amorphous: ^l H-NMR (CD ₃ OD): δ 0.90 (t, J = 6.9Hz, 3H), 1.19-1.50 (m, 6H), 1.50-1.75 (m, 2H), 2.45-2.79 (m, 2H), 2.93-3.27 (m, 2H), 4.00-4.22 (m, 3H), 4.34-4.50 (m, 2H) .IR (KBr, cm ^-1 ): 2968, 1740, 1241, 1209, 1146, 1033 .

C ₆ F ₁₃ CH ₂ CH ₂ OOCCH (SO ₃ Na) CH ₂ COOC ₈ H ₁₇ 2
Colorless amorphous: ^l H-NMR (CD ₃ OD): δ 0.94 (t, J = 7.3Hz, 3H), 1.27-1.50 (m, 10H), 1.50-1.73 (m, 2H), 2.45-2.80 (m, 2H), 2.94-3.38 (m, 2H), 4.00-4.20 (m, 3H), 4.33-4.50 (m, 2H) .IR (KBr, cm ^-1 ): 2969, 1737, 1241, 1146, 1054.

C ₈ F ₁₇ CH ₂ CH ₂ OOCCH (SO ₃ Na) CH ₂ COOC ₁₀ H ₂₁ 3
Colorless amorphous: ^l H-NMR (CD ₃ OD): δ 0.89 (t, J = 6.8Hz, 3H), 1.15-1.45 (m, 14H), 1.50-1.75 (m, 2H), 2.45-2.79 (m, 2H), 2.94-3.27 (m, 2H), 4.02-4.22 (m, 3H), 4.36-4.51 (m, 2H). IR (KBr, cm ^-1 ): 2930, 1741, 1245, 1220, 1153, 1055 .

C ₈ F ₁₇ CH ₂ CH ₂ OOCCH (SO ₃ Na) CH ₂ COOC ₆ H ₁₃ 4
Colorless amorphous: ^l H-NMR (CD ₃ OD): δ 0.91 (t, J = 6.9Hz, 3H), 1.20-1.50 (m, 6H), 1.50-1.76 (m, 2H), 2.44-2.80 (m, 2H), 2.94-3.47 (m, 2H), 4.02-4.20 (m, 3H), 4.33-4.52 (m, 2H).). IR (KBr, cm ^-1 ): 2967, 1740, 1244, 1210, 1152 , 1054.

C ₄ F ₉ CH ₂ CH ₂ OOCCH (SO ₃ Na) CH ₂ COOC ₄ H ₉ 5
Colorless amorphous: ^l H-NMR (CD ₃ OD): δ 0.94 (t, J = 7.3Hz, 3H), 1.25-1.50 (m, 2H), 1.50-1.73 (m, 2H), 2.45-2.80 (m, 2H), 2.94-3.37 (m, 2H), 4.02-4.22 (m, 3H), 4.33-4.50 (m, 2H). IR (KBr, cm- ¹ ): 2967, 1739, 1229, 1135, 1054.
Comparative Examples 1-5
Compounds having two fluoroalkyl groups (6-8) were synthesized according to Bull. Chem. SOC. Jpn. 1991, 64, 3262. Compound 9 was synthesized by the same method using an alcohol form C4F9CH2CH2CH2CH2OH obtained by further reducing a product obtained by radical addition reaction of C4F9I and CH2 = CHCH2CH2OH with lithium aluminum hydride. Further, Compound 10 was synthesized according to Langmuir 1994, 10, 3536.
The structure and compound number are shown below.
H (CF ₂ ) ₄ CH ₂ OOCCH (SO ₃ Na) CH ₂ COOCH ₂ (CF ₂ ) ₄ H 6
H (CF ₂ ) ₆ CH ₂ OOCCH (SO ₃ Na) CH ₂ COOCH ₂ (CF ₂ ) ₆ H 7
F (CF ₂ ) ₈ CH ₂ CH ₂ OOCCH (SO ₃ Na) CH ₂ COOCH ₂ CH ₂ (CF ₂ ) ₈ F 8
F (CF ₂ ) ₄ (CH ₂ ) ₄ OOCCH (SO ₃ Na) CH ₂ COO (CH ₂ ) ₄ (CF ₂ ) ₄ F 9
C ₇ F ₁₅ CH (OSO ₃ Na) C ₇ H ₁₅ 10
Properties of compound 9 colorless amorphous: ^l H-NMR (CD ₃ OD): δ 1.56-1.90 (m, 8H), 2.05-2.38 (m, 4H), 2.95-3.28 (m, 2H), 4.02-4.30 ( m, 5H). IR (KBr, cm ^-1 ): 2968, 1738, 1224, 1134, 1051.

Test example 1
Functional tests of the compounds of Examples and Comparative Examples were performed.
(1) Measurement method of W value and water uptake amount The evaluation value measuring apparatus shown in FIG. 1 was used, and the W value and the water uptake amount were measured according to the following steps 1) to 4).
1) Introduce 2 wt% of a surfactant with respect to carbon dioxide into a part in a pressure-resistant device (view cell) with a visible window.
2) Introduce carbon dioxide to the predetermined measurement pressure and temperature shown in the table, and then introduce water into part a from the six-way valve.
3) The contents were visually observed through a visible window (sapphire window), and it was determined that water was dissolved in carbon dioxide in a transparent and uniform state.
4) The W value and the water uptake amount were calculated from the maximum water introduction amount capable of maintaining a transparent state and the surfactant weight used in the measurement.

The predetermined measurement pressure and temperature of 2) are shown in Table 1 below.
Surfactant effect evaluation (determined by water uptake ability into carbon dioxide)
W value = in micelles (number of water molecules / number of surfactant molecules)
Water uptake = weight of water dissolved in carbon dioxide per gram of surfactant

  So far, compound 10 has been reported to be unstable but highly functional (Langmuir 1994, 10, 3536). Although the present inventor made additional trials, the function could not be expressed at all because the test was conducted at 50 ° C. in the same manner as other compounds. A sample was collected after the test and the cause was sought by instrumental analysis (NMR). A small but very complex peak was observed together with the hydrolyzed sulfate ester moiety (it is considered that the decomposition proceeded even at 50 ° C.). This is considered to be a major obstacle to practical use.

  As a more stable compound, the compounds 7 to 8 have been reported to have the highest functions so far (Langmuir 2001, -17, 274; 1997, 13, 6980). In particular, the compounds 1 to 4 have more functions than these.

  Furthermore, when the result of the compound 9 is seen, even if the total number of the two carbon chains is 8 for each of the fluorine chain and the hydrocarbon chain, it does not function sufficiently.

Is then sulfosuccinate having only hydrocarbon group compound 6 and the molecule AOT: Consider a mixture of 1: 1 (molar ratio) of _{C 8 H 17 OOCCH (SO 3} Na) CH 2 COOC 8 H 17 did.
As shown below, the same results were obtained as when compound 6 was functioning at half mole. From this result, it is not possible to obtain a function by mixing a compound having two hydrocarbon groups and a compound having two fluoroalkyl groups, and it must have both a fluoroalkyl group and a hydrocarbon group in one molecule. It can be seen that the high function of the present invention cannot be expressed.

  From the above results, the hybrid type sulfonic acid ester having both a fluorine group having a carbon number longer than 4 and a hydrocarbon chain having the same length in the molecule, and having a branched structure in carbon dioxide It can be seen that it exhibits high functionality when handling polar compounds such as water.

(A) It is the schematic which shows the measuring apparatus of W value. (B) It is a view cell detail drawing.

Claims (7)

A surfactant for use by adding to a solvent system containing liquid, subcritical or supercritical carbon dioxide and a polar compound, the surfactant having the following general formula (I)

(In the formula, Rf represents a fluoroalkyl group having 4 to 50 carbon atoms and optionally having an ether bond,
Rh represents an alkyl group having 3 to 18 carbon atoms ,
And (carbon number of Rf) / (carbon number of Rh) = 1/2 to 2/1 .
X ¹ has a structure linked by O (C) O;
X ² has a structure connected with C (O) O;
In addition, (CH ₂ ) _m (m is an integer of 1 to 3 ) may be further interposed between X ¹ and / or X ² and CH (SO ₃ M) .
p is 1 ,
q is 1 .
n shows the integer of 1-10.
M represents a hydrogen atom, an alkali metal, 1/2 alkaline earth metal or ammonium. )
In it represented by a surfactant. The surfactant according to claim 1, wherein Rf has 5 to 12 carbon atoms. Rf is
C _a F _{2a + 1} − (a represents an integer of 1 to 10),
HC _b F _2b- (b represents an integer of 1 to 10),
_{CF 3 CF (CF 3) (} CF 2) d - (d is an integer of 4-20),
_{CF 3 CF (CF 3) (} CF 2) e CF (CF 3) CF 2 - (e is an integer of 4-20),
_{C g F 2g + 1 O (} CF 2 CF 2 O) i CF 2 - (g is an integer of 1 to 10, i is an integer of 1 to 15),
_{C j F 2j + 1 O (} CF (CF 3) CF 2 O) k CF (CF 3) - (j is an integer of 1 to 10, k is an integer of 1 to 15),
_{HC s F 2s O (CF 2} CF 2 O) t CF 2 - (s is an integer of 1 to 10, t is an integer of 1 to 15), or
_{HC u F 2u O (CF (} CF 3) CF 2 O) v CF (CF 3) - (u is an integer of 1 to 10, v is an integer of 1 to 15)
The surfactant according to claim 1, wherein General formula: Rf (CH ₂ ) _n OOCCH (SO ₃ M) CH ₂ COORh
(Wherein Rf, Rh, n and M are as defined above.)
The surfactant in any one of Claims 1-3 represented by these . 請 Motomeko 1 liquid detergent according to any one of 4, a method used by adding to a solvent system comprising a subcritical or supercritical carbon dioxide and a polar compound. The method according to claim 5 , wherein the polar compound is water. A composition comprising the following (1) to (3):
(1) liquid, subcritical or supercritical carbon dioxide,
(2) polar compounds, and
(3) the following general formula (I),

(In the formula, Rf represents a fluoroalkyl group having 4 to 50 carbon atoms and optionally having an ether bond,
Rh represents an alkyl group having 3 to 18 carbon atoms,
And (carbon number of Rf) / (carbon number of Rh) = 1/2 to 2/1.
X ¹ has a structure linked by O (C) O;
X ² has a structure connected with C (O) O;
In addition, (CH ₂ ) _m (m is an integer of 1 to 3 ) may be further interposed between X ¹ and / or X ² and CH (SO ₃ M) .
p is 1,
q is 1.
n shows the integer of 1-10.
M represents a hydrogen atom, an alkali metal, 1/2 alkaline earth metal or ammonium. )
A surfactant represented by

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