JPH05131130A - Surfactant - Google Patents

Abstract

PURPOSE:To alternately develop the characteristics caused by a fluorine atom such as water repellency or oil repellency and hydrophilicity under various environments by using a specific fluoroalkyl group-containing compound having a definite range of a mean mol.wt. as the effective component of a surfactant. CONSTITUTION:A fluoroalkyl group-containing compound with a mean mol.wt. of 500-5000 represented by formula I [wherein R is H<+> or a methyl group, Y is H<+>, Na<+>, K<+> or NH4<+> and RF- is -(CF2)n1X or a group represented by formula II (wherein X is H<+>, F<-> or Cl<->, n1 is an integer of 1-10, n2 is an integer of 0-8 and m is an integer 1-250)] is used as the effective component of a surfactant. This surfactant can alternately develop the characteristics caused by a fluorine atom such as water repellency or oil repellency and hydrophilicity under various environments.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel surfactant, more specifically, a highly stable vesicle agent, medical material,
The present invention relates to a surfactant useful as an oxygen-enriched film, an additive for various lubricants, a paint, an ink leveling agent, a paint remover, a resist remover, a cleaning foaming agent, a fluororesin surface modifier, and the like.

[0002]

2. Description of the Related Art It has been widely known that fluoroalkyl group-containing carboxylic acids such as perfluorooctanoic acid exhibit high interfacial properties in an aqueous solution ["fluorine compound", pp. 187-190, Kodansha). (1979
)], And is used as a fluorine-based surfactant. However, since the known fluorine-based surfactant is a compound composed only of a hydrophilic group and a water-repellent group, it has various properties such as water-repellency and oil-repellency due to the fluorine atom and hydrophilicity. However, there is a problem that it is difficult to alternately express them under the environment.

Therefore, under the present circumstances, there is a strong demand for the development of a surfactant capable of more effectively exhibiting the above-mentioned characteristics attributable to the fluorine atom and hydrophilicity.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a surfactant capable of alternately exhibiting excellent properties such as water and oil repellency due to a fluorine atom and hydrophilicity under various environments. To provide.

[0005]

According to the present invention, a surfactant containing a fluoroalkyl group-containing compound (fluoroalkyl group-containing compound 1) having an average molecular weight of 500 to 50,000 represented by the following general formula 2 as an active ingredient. Will be provided.

[0006]

[Chemical 2]

The present invention will be described in more detail below.

The surfactant of the present invention is characterized by containing a specific fluoroalkyl group-containing compound as an active ingredient.

The specific fluoroalkyl group-containing compound used as an active ingredient in the surfactant of the present invention is
It is the fluoroalkyl group-containing compound 1 represented by the general formula 2. In the above-mentioned fluoroalkyl group-containing compound 1, if n ₁ exceeds 10, or n ₂ exceeds 8, the solubility in a solvent decreases, and therefore it cannot be used. Further, when m exceeds 250, the production is difficult. Furthermore, the average molecular weight of the fluoroalkyl group-containing compound 1 is in the range of 500 to 50,000. When the average molecular weight is out of the above range, the production is difficult.

Further, the fluoroalkyl group-containing compound 1
In particular, applicable RF, that is,-(CF ₂ ) n ₁ X or the following general formula 3 is specifically listed, F ₃ C-, F (C
_{F 2) 2 -, F (} CF 2) 3 -, F (CF 2) 4 -, F (CF
₂ ) ₅ −, F (CF ₂ ) ₆ −, F (CF ₂ ) ₇ −, F (C
_{F 2) 8 -, F (} CF 2) 9 -, F (CF 2) 10 -, HCF 2
_{-, H (CF 2) 2} -, H (CF 2) 3 -, H (CF 2)
_{4 -, H (CF 2)} 5 -, H (CF 2) 6 -, H (CF 2) 7
_{-, H (CF 2) 8} -, H (CF 2) 9 -, H (CF 2) 10
_{-, ClCF 2 -, Cl (} CF 2) 2 -, Cl (CF 2) 3
_{-, Cl (CF 2) 4} -, Cl (CF 2) 5 -, Cl (CF
_{2) 6 -, Cl (CF} 2) 7 -, Cl (CF 2) 8 -, Cl
(CF ₂ ) ₉ −, Cl (CF ₂ ) ₁₀ −, the following chemical formula 4,
Chemical formula 5, Chemical formula 6, Chemical formula 7, Chemical formula 8, Chemical formula 9, Chemical formula 10, Chemical formula 11, Chemical formula 1
It is 2.

[0011]

[Chemical 3]

[0012]

[Chemical 4]

[0013]

[Chemical 5]

[0014]

[Chemical 6]

[0015]

[Chemical 7]

[0016]

[Chemical 8]

[0017]

[Chemical 9]

[0018]

[Chemical 10]

[0019]

[Chemical 11]

[0020]

[Chemical 12]

Specific examples of the fluoroalkyl group-containing compound 1 include those represented by the following general formulas 13 and 14,
Chemical formula 15, Chemical formula 16, Chemical formula 17, Chemical formula 18, Chemical formula 19, Chemical formula 20, Chemical formula 21, Chemical formula 22, Chemical formula 23, Chemical formula 24, Chemical formula 25, Chemical formula 26, Chemical formula 2
7, Chemical 28, Chemical 29, Chemical 30, Chemical 31, Chemical 32, Chemical 3
3, chemical 34, chemical 35, chemical 36, chemical 37, chemical 38, chemical 3
9, chemical formula 40, chemical formula 41, chemical formula 42, chemical formula 43, chemical formula 44, chemical formula 4
5, chemical 46, chemical 47, chemical 48, chemical 49, chemical 50, chemical 5
1, 52, 53, 54, 55, 56, 5
7, Chemical Formula 58, Chemical Formula 59, Chemical Formula 60, and the like can be preferably used, and when used, they can be used alone or as a mixture (wherein, m represents an integer of 1 to 250).

[0022]

[Chemical 13]

[0023]

[Chemical 14]

[0024]

[Chemical 15]

[0025]

[Chemical 16]

[0026]

[Chemical 17]

[0027]

[Chemical 18]

[0028]

[Chemical 19]

[0029]

[Chemical 20]

[0030]

[Chemical 21]

[0031]

[Chemical formula 22]

[0032]

[Chemical formula 23]

[0033]

[Chemical formula 24]

[0034]

[Chemical 25]

[0035]

[Chemical formula 26]

[0036]

[Chemical 27]

[0037]

[Chemical 28]

[0038]

[Chemical 29]

[0039]

[Chemical 30]

[0040]

[Chemical 31]

[0041]

[Chemical 32]

[0042]

[Chemical 33]

[0043]

[Chemical 34]

[0044]

[Chemical 35]

[0045]

[Chemical 36]

[0046]

[Chemical 37]

[0047]

[Chemical 38]

[0048]

[Chemical Formula 39]

[0049]

[Chemical 40]

[0050]

[Chemical 41]

[0051]

[Chemical 42]

[0052]

[Chemical 43]

[0053]

[Chemical 44]

[0054]

[Chemical 45]

[0055]

[Chemical 46]

[0056]

[Chemical 47]

[0057]

[Chemical 48]

[0058]

[Chemical 49]

[0059]

[Chemical 50]

[0060]

[Chemical 51]

[0061]

[Chemical 52]

[0062]

[Chemical 53]

[0063]

[Chemical 54]

[0064]

[Chemical 55]

[0065]

[Chemical 56]

[0066]

[Chemical 57]

[0067]

[Chemical 58]

[0068]

[Chemical 59]

[0069]

[Chemical 60]

In the present invention, the fluoroalkyl group-containing compound 1 can be prepared, for example, by the following general formula 61
The difluoroalkanoyl peroxide represented by and acrylic acid or methacrylic acid are preferably in a molar ratio of 1:
0.1 to 5000, particularly preferably 1: 0.5 to
Charge in the range of 1000, preferably reaction temperature -20
To + 150 ° C., particularly preferably 0 to 100 ° C., preferably 0.5 to 20 hours, particularly preferably 1
By reacting for 10 hours or the like, the above general formula 2
In, a fluoroalkyl group-containing compound 1 in which Y is a hydrogen atom can be obtained, and the compound obtained at this time is reacted with an alkali such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, etc. In 2, a compound in which Y is sodium, potassium or ammonium can be obtained. In addition, the reaction is
It can also be carried out in the presence of a halogenated aliphatic organic solvent such as trichlorotrifluoroethane.

[0071]

[Chemical formula 61]

The RF in the difluoroalkanoyl peroxide is the same as the RF specifically listed in the fluoroalkyl group-containing compound 1, and the difluoroalkanoyl peroxide is, for example, diperfluoroperoxide. 2-Methyl-3-oxahexanoyl, diperfluoro-2,5-dimethyl-3,6 peroxide
-Dioxanonanoyl, diperfluoro-2 peroxide,
Preferable examples include 5,8-trimethyl-3,6,9-trioxadodecanoyl, diperfluorobutyryl peroxide, diperfluoroheptanoyl peroxide and the like.

In order to prepare the surfactant of the present invention, it can be obtained by treating the fluoroalkyl group-containing compound 1 by a conventional method. Specifically, for example, it can be easily obtained by adding it to a water-soluble organic solvent such as water or alcohol, or a mixed solvent of water and a water-soluble organic solvent, and stirring or sonicating. At this time, the preparation temperature is preferably in the range of 5 to 50 ° C., and the concentration of the fluoroalkyl group-containing compound 1 is in the range of 10 ² g / L to 10 to ¹⁵ g / L with respect to the solvent. Preferably.

The surfactant of the present invention can be used by an ordinary method, and at this time, other known surfactants can be used in combination.

[0075]

EFFECT OF THE INVENTION In the surfactant of the present invention, the fluoroalkyl group-containing compound 1 which is the active ingredient is such that the fluoroalkyl group is bifunctional and the carboxylic acid group is monofunctional or polyfunctional. Since the hydrocarbon group is introduced as a spacer, excellent properties such as water and oil repellency due to the fluorine atom and hydrophilicity can be alternately expressed in various environments, and the stability is high. It is useful as a vesicle agent, a medical material, an oxygen-enriched film, an additive for various lubricants, a paint, an ink leveling agent, a paint remover, a resist stripping agent, a cleaning foaming agent, a fluorine resin surface modifier, and the like.

[0076]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0077]

[Synthesis Example 1] 21.6 g (300 mmol) of acrylic acid,
1,1, containing 99 g (100 mmol) of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide
150 g of 2-trichlorotrifluoroethane solution was added, and the reaction was carried out at 30 ° C. for 5 hours under a nitrogen atmosphere.
After completion of the reaction, the reaction solvent was removed, and the residue was purified by reprecipitation with a methanol-ethyl acetate system and then dried under vacuum to obtain a fluoroalkyl group-containing compound represented by the following structural formula 62 in a yield of 96. 1 g was obtained.

[0078]

[Chemical formula 62]

[0079]

[Synthesis Example 2] Diperfluoro-2-methyl-3-oxahexanoyl peroxide (3.22 g) was added to diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide.
0 mmol) and the charged amount of acrylic acid is 4.3 g (60 m
mol), and the reaction was carried out in the same manner as in Synthesis Example 1 to obtain 3.4 g of a fluoroalkyl group-containing compound represented by the following structural formula 63.

[0080]

[Chemical 63]

[0081]

Synthesis Example 3 Diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was replaced with diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl 13. 22 g (10 mmol) and the amount of acrylic acid charged was 21.6 g (300 mmol),
The reaction was carried out in the same manner as in Synthesis Example 1, and the following structural formula 64
The yield of the compound containing a fluoroalkyl group represented by
Obtained 0.9 g.

[0082]

[Chemical 64]

[0083]

[Synthesis Example 4] The reaction was carried out in the same manner as in Synthesis Example 1 except that diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was replaced with diperfluorobutyryl peroxide. The yield of the compound having a fluoroalkyl group represented by Chemical formula 65 was 51.1 g.

[0084]

[Chemical 65]

[0085]

[Synthesis Example 5] The reaction was carried out in the same manner as in Synthesis Example 1 except that diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was replaced with diperfluoroheptanoyl peroxide. The yield of the fluoroalkyl group-containing compound represented by Chemical formula 66 was 80.9 g.

[0086]

[Chemical 66]

[0087]

Synthesis Example 6 A fluoroalkyl group-containing compound represented by the following structural formula 67 was obtained by adding 50 ml of 25 wt% ammonia water to 1 g of the fluoroalkyl group-containing compound synthesized in Synthesis Example 1 and reacting at room temperature for 2 days. Yield 0.9 g.

[0088]

[Chemical 67]

[0089]

Example 1 The fluoroalkyl group-containing compound obtained in Synthesis Example 1 was added to water (water for injection, manufactured by Otsuka Pharmaceutical Co., Ltd.) at a predetermined amount so that the concentration shown in Table 1 was reached, and the temperature was 25 ° C. In the above, ultrasonic treatment was performed to prepare the surfactant of the present invention. Then, the obtained surfactant was left to stand overnight at 25 ° C., and a Kyowa CBVP type surface tensiometer (trade name “A-3 type”,
Using Kyowa Chemical Co., Ltd., the surface tension was measured at a constant temperature of 25 ° C. Also, from the surface tension in Table 1,
The critical micelle concentration was calculated. The results are shown in Table 1.

[0090]

Examples 2 to 6 The same as Example 1 except that the fluoroalkyl group-containing compounds obtained in Synthesis Examples 2 to 6 were used in place of the fluoroalkyl group-containing compound obtained in Synthesis Example 1. Then, the surface tension and the critical micelle concentration were measured. The results are shown in Table 1.

[0091]

Comparative Example 1 The surface tension and the critical value were the same as in Example 1 except that polyacrylic acid (manufactured by Aldrich, average molecular weight 2000) was used instead of the fluoroalkyl group-containing compound obtained in Synthesis Example 1. The micelle concentration was measured.
The results are shown in Table 1.

[0092]

Comparative Example 2 The surface tension was measured in the same manner as in Example 1 except that perfluorododecanoic acid was used instead of the fluoroalkyl group-containing compound obtained in Synthesis Example 1, and the concentration was 10 ⁰ g / L. Was 32.0 (dyne / cm).

As is clear from the above results, the surfactant of the present invention exhibits excellent interfacial properties, especially at high concentrations.

[0094]

[Table 1]

[Procedure amendment]

[Submission date] January 28, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction content]

[0075]

EFFECT OF THE INVENTION In the surfactant of the present invention, the fluoroalkyl group-containing compound 1 which is the active ingredient is such that the fluoroalkyl group is bifunctional and the carboxylic acid group is monofunctional or polyfunctional. Since the hydrocarbon group is introduced as a spacer, excellent properties such as water and oil repellency due to the fluorine atom and hydrophilicity can be alternately expressed in various environments, and the stability is high. Vesicles, auxiliaries for pharmaceuticals and agricultural chemicals, medical materials, oxygen-enriched films, additives for various lubricants, paints, ink leveling agents, paint removers, resist strippers, cleaning air bubbles and fluorine resin surface modifiers. It is useful as

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C07C 59/135 8827-4H

Claims (1)

[Claims] 1. A surfactant containing a fluoroalkyl group-containing compound represented by the following general formula 1 and having an average molecular weight of 500 to 50,000 as an active ingredient. [Chemical 1]