JPH0224814B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel polyfluoroalkyl group-containing compound and a method for producing the same. Conventionally, various surfactants such as anionic, cationic, and nonionic surfactants are known, and fluorinated interfaces having polyfluoroalkyl groups (hereinafter abbreviated as PFA groups) such as perfluoroalkyl groups have been known as surfactants. Activators are also known. Fluorinated surfactants exhibit unique surfactant properties and are therefore suitable for use as evaporation inhibitors (extinguishing agents) for volatile liquids, leveling agents for photographic gelatin layers, paint additives, and other various uses. Furthermore, anionic fluorinated surfactants are also widely used as emulsifiers in the production of fluorinated resins. Furthermore, Japanese Patent Application Laid-Open No. 53-45683 describes the general characteristics of an amphoteric surfactant such as being less affected by pH changes and less affected by salts, as well as the characteristics of a fluorinated surfactant. Fluorinated amphoteric surfactants have also been proposed. On the other hand, ordinary surfactants whose hydrophobic part is a monoalkyl group type form spherical micelles as molecular aggregates in aqueous solution, and surfactants whose hydrophobic part is a dialkyl group type, such as dialkyl ammonium salts and dialkyl phosphates, , are known to form endoplasmic reticulum (vesicles) with a bipartite membrane structure. Vesicles having such a bilayer membrane structure have an internal aqueous phase, and a phase transition between a gel phase and a liquid crystal phase exists. Attempts have been reported to use vesicles not only as a simple site for reproducing conventional biological reactions, but also as a site for various organic reactions to control reactions. The present inventors have discovered that a novel compound having two PFA groups in the molecule can be obtained by reacting glutamic acid or aspartic acid with a PFA group-containing alcohol. The inventors have also discovered that by appropriately converting the active hydrogen of the -NH ₂ group of such a new compound into a hydrophilic group, a new surfactant having two PFA groups can be obtained. The surfactant dissolves in water to form bilayer membrane-structured vesicles, and this bilayer membrane is extremely stable, and its ability to retain hydrophilic compounds and barrier ability against hydroxyl ions is higher than that of conventional hydrocarbon-type vesicles. They are characterized by being much larger than bilayer membrane vesicles. The present invention was completed based on the above findings, and firstly, the general formula Second, an alcohol represented by the general formula R _f -R-OH and glutamic acid or aspartic acid,
Upon reaction with the addition of p-toluenesulfonic acid, the general formula The present invention provides a novel method for producing a PFA group-containing compound, which is characterized by obtaining a compound () represented by: In the general formula, R _f ¹ and R _f ² are perfluoroalkyl groups represented by -C _o F _2o+1 , R ¹ and R ² are alkylene groups represented by -C _n H _2n -, and p is It is a number selected from 0 or 1, n is a positive integer of 4 to 14, m is a positive integer of 1 to 3, R _f is the above-mentioned R _f ¹ or R _f ² , and R is R ¹
Or ^R2 . Therefore, the above PFA group-containing compound () of the present invention
As raw material, general formula The PFA group-containing surfactant () represented by can be smoothly and advantageously synthesized. In the above general formula, R _f ¹ and R _f ² are perfluoroalkyl groups represented by -C _o F _2o+1 , and R ¹ and R ² are -C _n H _2n -
alkylene group represented by, p is a number selected from 0 or 1, Z is a hydrophilic group, Y is a hydrogen atom or Z, n is a positive integer of 4 to 14, m is a positive integer of 1 to 3 be. Therefore, the hydrophilic group Z is selected from the following. −COCH ₂ N(CH ₃ ) ₃・Cl, −COCH ₂ N
(CH ₃ ) ₂ CH ₂ COO, −COCH ₂ N(CH ₃ ) ₂ CH ₂ CH ₂ NH ₂・HBr,

[Formula] Br −(CH ₂ CH ₂ O) ₅ H In the present invention, it is important to have two PFA groups in the molecule, and this provides various excellent properties as a PFA group-containing surfactant (). Characteristics are demonstrated. That is, the surfactant () dissolves in water to form a vesicle with a bilayer membrane structure, and this bilayer membrane is extremely stable and has a high ability to retain hydrophilic compounds in the aqueous phase within the vesicle and hydroxyl ions. It is characterized by a high barrier ability against. In addition, the aqueous solution of the surfactant (2) is characterized by almost no foaming, and has the ability to lower surface tension. By mixing it with an ordinary fluorinated surfactant, it is possible to obtain a surfactant with low foaming properties and high surface activity. The PFA group-containing compound () of the present invention can be produced by various synthetic methods, but it is usually produced by a smooth and advantageous esterification reaction between a fluoroalcohol having the general formula R _f -R-OH and glutamic acid or aspartic acid as described above. can be synthesized into In such a synthesis method, the reaction is carried out using benzene, toluene, cyclohexane, 1,2-dimethoxyethane, 1,2
- Preferably carried out in an inert solvent such as dichloroethane. The present esterification reaction is usually suitably carried out in the presence of an acid catalyst consisting of p-toluenesulfonic acid, which is an esterification reaction catalyst. Reaction temperature is 50-150℃, preferably 70-100℃
degree is suitable. The amount of catalyst used is preferably about 1 to 1.5 mol per 1 mol of glutamic acid or aspartic acid. Also, 1.5 fluoroalcohols per mole of glutamic acid or aspartic acid
A reaction molar ratio of about 3 to 3 moles, preferably about 2 to 2.4 moles, can be employed. Thus, the PFA group-containing surfactant () in the present invention can be easily synthesized by converting the active hydrogen of the -NH ₂ group of the compound () into various hydrophilic groups Z. The conversion reaction in this case is not particularly limited, and a wide variety of means can be employed. Of course, Y in the specific surfactant () may be a hydrogen atom, or Y may be any of various hydrophilic groups Z. In the latter case, the two hydrophilic groups Z may be of the same type or different types. For example, the following synthesis route may be exemplified. Typical specific examples of the specific surfactant () of the present invention include the following. That is, For example, Such specific structure is
Confirmed by means such as NMR spectroscopy, elemental analysis, and IR spectroscopy. In the present invention, R _f is a perfluoroalkyl group represented by -C _o F _2o+1 , and n is a positive integer of 4 to 14, preferably 6 to 12. Of course,
R _f may be linear or branched, and R ¹ _f and R ² _f may be the same or different. Further, R _f may be a mixture of a plurality of compounds in which n is different. Similarly, R can also be linear or branched, but -CH ₂ CH ₂ -, where m = 2, is exemplified as a preferred example, and R ¹
and R ² may be different. As the hydrophilic group Z, a wide range of amphoteric groups such as cationic, anionic, nonionic, and betaine types can be employed. Examples include the quaternary ammonium type as mentioned above, the betaine type as mentioned above, the polyoxyethylene type as mentioned above, and the amine oxide type as mentioned above. The specific surfactant () of the present invention can be widely employed in various uses utilizing the above-mentioned properties. For example, wetting agents for photographic emulsions, leveling agents for floor waxes, wetting agents for paints, dispersants for synthetic latex,
It exhibits excellent effects as a dispersant for powdered pesticides, etc. Next, examples of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by such description. In addition, in the following examples, surface tension and foaming properties were measured as follows. That is, surface tension was measured using Wilhelmy's hanging plate method while keeping an aqueous surfactant solution diluted to a predetermined concentration at 25°C. In addition, the foaming property is also 25
It was measured by the method of Ross & Miles using a 0.1% by weight aqueous solution at °C. Example 1 L-glutamic acid was added to a 500 ml flask equipped with a stirrer, a reflux condenser with a Dean-Stark separator, and a thermometer.

[Formula] 5g (0.034 mol), CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OH40g (0.086 mol, P-
9 g (0.047 mol) of toluene sulfonic acid and 300 ml of toluene were charged, and heated under reflux for 4 hours while keeping the contents in a suspended state with stirring and separating the produced water. After the reaction, let it cool and collect the precipitated solid.
Recrystallized from ethanol as white powder with melting point of 110℃
Obtained 35g. The yield is 85% based on the raw material fluoroalcohol, and the white powder is L-glutamic acid bis-(1H, 1H, 2H,
It was confirmed that it was 2H-perfluorodedyl) ester-p-toluenesulfonate. Example 2 The p-obtained in Example 1 was placed in a 300 ml flask equipped with a stirrer, a dropping funnel, and a thermometer.
8 g (6.6 x 10 ^-3 mol) of toluene sulfonate, 1.5 g (0.015 mol) triethylamine and 100 ml chloroform were charged and dissolved, and stirred under ice cooling.

A solution of 2 g (6.9×10 ⁻³ mol) of chloroform was gradually introduced dropwise. Thereafter, the reaction was stirred at room temperature for 24 hours. After the reaction, the solvent chloroform was distilled off under reduced pressure,
Water was added to the residue to collect insoluble materials, which were recrystallized from methanol. 8.1 g of white powder with a melting point of 92.5-94°C was obtained. The yield based on the raw material p-toluenesulfonate was 94%, and elemental analysis, IR spectrum and
From the NMR spectrum, the white powder was L-glutamic acid-N-[p-(ω-bromobutyloxy)-benzoyl]-bis-(1H, 1H,
It was confirmed that it was 2H, 2H-perfluorodecyl) ester. Example 3 A flask with an internal volume of 100 ml was charged with 2 g (1.5 x 10 ^-3 mol) of the ester obtained in Example 2 and 50 ml of tetrahydrofuran/benzene (volume ratio 1/1), and a large excess of trimethylamine gas was blown into the flask. Thereafter, the container was tightly stoppered and reacted with stirring at room temperature for 50 hours. After the reaction, the precipitated white solid was collected and recrystallized from ethanol/n-hexane. Melting point 140℃,
1.3 g of white powder with a thermal decomposition temperature of 255° C. was obtained, and therefore the yield was 65% based on the raw material ester. The elemental analysis value of this compound is actually measured: C: 34.41, H:
2.79, N: 2.09, and the calculated values as C ₃₉ H ₃₉ N ₂ O ₆ BrF ₃₄ were C: 34.61, H: 2.61, N: 2.07. From the NMR spectrum, the compound is It was confirmed that it was brominated-L-glutamic acid-N-[p-(ω-trimethylammoniumbutyloxy)-benzoyl]-bis-(1H,1H,2H,2H-perfluorodecyl) ester (2). . Example 4 In Example 2,

Using the same procedure except using ClCH ₂ COCl in place of [Formula], the yield was 90% based on the raw material p-toluenesulfonate.
%in A compound was obtained. Example 5 By the same procedure as in Example 3, except that the compound obtained in Example 4 was used instead of the ester obtained in Example 2, Compound (a) was obtained. Example 6 In place of trimethylamine in Example 5 Otherwise, by similar steps using A compound was obtained. Next, this compound is reacted with hydrogen bromide. Compound (c) was obtained. Example 7 In a 500 ml flask equipped with a stirrer, a reflux condenser with a Dean-Stark separator, and a thermometer, 5.5 g (0.041 mol) of L-aspartic acid,
43 g (0.083 mol) of R ⁹ _f CH ₂ CH ₂ OH (R ⁹ _f is a mixture of C ₆ F ₁₃ to C ₁₂ F ₂₅ with an average of C ₉ F ₁₉ ), 9 g (0.047 mol) of p-toluenesulfonic acid and toluene 300
ml, keep the contents in suspension under stirring,
The mixture was heated under reflux for 5 hours while separating the water produced.
After the reaction was allowed to cool, the precipitated solid was collected and recrystallized from ethanol to obtain 40 g of a white powder with a softening point of 130-135°C. The yield is 90% based on the raw material fluoroalcohol, and the white powder is L-aspartic acid-bis-(1H, 1H,
p of 2H,2H-perfluoroalkyl) ester
- It was confirmed that this is a toluene sulfonate. Example 8 Using the p-toluenesulfonate obtained in Example 7, the raw material p was prepared in the same manner as in Example 4.
-With a yield of 95% based on toluene sulfonate A compound was obtained. This compound was reacted with triethylamine in the same manner as in Example 3, Compound (d) was obtained. Example 9 10 g of p-toluenesulfonate obtained in Example 7, 0.5 g of sodium hydroxide, and 100 ml of tetrahydrofuran were placed in a flask with an internal volume of 50 ml.
Warmed to ℃. The reaction was carried out for 5 hours while stirring vigorously and blowing ethylene oxide at a rate of 10 ml/min. Compound (e) was obtained. Table 1 below shows the results of measuring the surface tension and foaming properties of an aqueous solution of a typical example of the surfactant (2) of the present invention synthesized by the above method.

[Table] In Table 1, (a), (b), (c), (d), and (e) are as follows, respectively.

Claims (1)

[Claims] 1. General formula (However, R _f ¹ and _f ² in the formula are perfluoroalkyl groups represented by -C _o F _2o+1 , R ¹ and R ² are -C _n
Alkylene group represented by H _2n -, p is 0 or 1
n is a positive integer from 4 to 14,
m is a positive integer of 1 to 3). 2 General formula R _f -R-OH (wherein R _f is R _f ¹ or R _f ² and is a perfluoroalkyl group represented by -C _o F _{2o + 1} , R is R ¹ or R ² an alkylene group represented by -C _n H _2n -, n is a positive integer of 4 to 14, m is a positive integer of 1 to 3), and glutamic acid or aspartic acid, p- Upon reaction with the addition of toluenesulfonic acid, the general formula (However, R _f ¹ , R _f ² , R ¹ , and R ² in the formula are as described above, and p is a number selected from 0 or 1.)
1. A method for producing a polyfluoroalkyl group-containing compound, which comprises obtaining a compound represented by: