JP3208204B2 - Fluorinated etherified polyhydric alcohol and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine-containing etherified polyhydric alcohol useful as a surface modifier for cosmetics and the like, an emulsifier, a cleaning component, and a lubricant, and a method for producing the same.

[0002]

2. Description of the Related Art Surfactants containing a fluoroalkyl group in which a hydrogen atom on a carbon atom has been replaced with a fluoro group,
Due to its strong water and oil repellency and high surface energy lowering ability, it is used for special applications such as functional materials and information materials. For example, JP-A-64-14263 and JP-A-3-215562 disclose the use of a polyfluoroalkyl alcohol and a fluorine-containing alkyl surfactant containing a polyoxyalkylene chain as an agricultural synthetic resin coating material. Have been.

In recent years, oils containing a perfluoroalkyl group have been used for cosmetics, and a surfactant capable of stably emulsifying these fluorine-containing oils and water has been desired.

Examples of such a surfactant include compounds in which a polyoxyalkylene chain or a polyglycerin (here, polyglycerin is a glycerin polymer higher than diglycerin) is introduced into a hydrophilic group. There is a disadvantage that the emulsifying power is reduced due to distribution in the hydrophilic portion.

On the other hand, as a compound having excellent emulsifying power, for example, JP-A-4-275248 discloses a fluorine-containing glycerin derivative.
69, page 1-8 (1992) describes perfluoroalkyl fatty acid esters of trehalose and sucrose. However, fluorine-containing glycerin derivatives are
O / W emulsifiers have the drawback of reduced emulsification stability because they are W / O emulsifiers, and perfluoroalkyl fatty acid esters of trehalose and sucrose have excellent O / W emulsifying ability, but have an ester bond. There is a problem that it is easily hydrolyzed because of having.

[0006]

Accordingly, it has been desired to develop a surfactant which has excellent hydrolysis resistance and forms a stable O / W emulsion system with a fluorine-containing oil agent.

[0007]

Under these circumstances, the present inventors have conducted intensive studies, and as a result, have found that a novel fluorinated etherified polyhydric alcohol represented by the following general formula (1) comprises a fluorinated oil and water. Has a stable O / W emulsifying system forming ability, exhibits excellent lubricating properties, is compatible with almost all solvents, and easily and almost uniformly when mixed with water. It has properties such as being dispersible and has excellent hydrolysis resistance, and it has been found that this compound is also useful as a surface modifier, an emulsifier, a cleaning component or a lubricant for hair and skin cosmetics. Thus, the present invention has been completed.

That is, the present invention provides the following general formula (1)

[0009]

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Wherein G is a residue obtained by removing all the hydrogen atoms of hydroxyl groups from sugar alcohols selected from pentaerythritol, sorbitol, mannitol, maltitol, erythritol, inositol, xylitol, dipentaerythritol and tripentaerythritol. Is shown. A: represents an alkylene group having 2 to 4 carbon atoms. Where p × q
Each A may be a different group. B: a hydrogen atom, a group represented by the following general formula (2) or a group represented by the following general formula (3)

[0011]

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(Where R _f represents a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, and m represents a number of 0 to 3). However, q Bs may be different groups, and not all q Bs are hydrogen atoms. p: Indicates the number of 0 to 10. q: Indicates a number of 4 or more. And a process for producing the same.

In the general formula (1) representing the novel fluorinated etherified polyhydric alcohol of the present invention, pentaerythritol and sorbitol are particularly preferred as the sugar alcohols of G.

In the general formula (1), examples of the alkylene group of A include an ethylene group, a trimethylene group, a propylene group, a butylene group and the like. There are p × q groups represented by A in the fluorinated etherified polyhydric alcohol (1) of the present invention, but these may be the same or different.

In the definition of B, general formula (2) or general formula
In the group represented by (3), R _fHas 1 to 20 carbon atoms
Represents a linear or branched fluoroalkyl group, wherein m is 0
The numbers of ~ 3 are shown. R in these groups_f(CH_Two)_m-Tool
As a body example, for example, C_TwoF_Five-, C_TwoF_FiveCH_Two-, C_Four
F₉-, C_FourF₉CH_Two-, C_FourF₉(CH_Two)_Two-, C_FourF
₉(CH_Two)_Four-, C₆F₁₃-, C₆F₁₃CH_Two-, C₆F₁₃
(CH_Two)_Two-, C₆F₁₃(CH_Two)_Three-, C₈F₁₇-, C₈
F₁₇CH_Two-, C₈F₁₇(CH_Two)_Two-, C₈F₁₇(CH_Two)
_Three-, C_TenF_{twenty one}-, C_TenF_{twenty one}CH_Two-, C_TenF_{twenty one}(C
H_Two)_Three-, C_{1 Two}F_{twenty five}(CH_Two)_Two-, C₁₄F₂₉(CH_Two)_Two
-, C₁₆F₃₃(CH_Two)_Two-, C₁₈F₃₇(CH_Two)_Two-, C
₂₀F₄₁(CH_Two)_Two-And the like. Of these specific examples
In the group, the fluoroalkyl group is linear or branched
It may be.

P represents a number of 0 to 10, and q represents a number of 4 or more.

Preferred specific examples of the fluorinated etherified polyhydric alcohol (1) of the present invention are shown below.

[0018]

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[0019]

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Wherein R _f and m have the same meaning as described above. The fluorinated etherified polyhydric alcohol of the present invention is obtained by adding a fluorinated glycidyl ether represented by the general formula (5) to a polyhydric alcohol represented by the general formula (4) in accordance with the following reaction formula. Can be produced by reacting in the presence of

[0021]

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Wherein G, A, R _f , p, q and m have the same meaning as described above. In the polyhydric alcohol (4) (excluding polyglycerin) used in the production method of the present invention,
In some cases, impurities other than the polyhydric alcohol corresponding to the target reaction product may be contained.However, if there is no problem in the reaction and application of the reaction product, conduct the reaction with the impurities contained. If there is a problem, purification can be performed by a known purification method before use in the reaction.

The fluorinated glycidyl ether (5) used in the production method of the present invention can be obtained by a known production method. For example, a fluorinated alcohol (7) is added to epihalohydrin (6) according to the following reaction formula. It can be produced by reacting in the presence of an alkali.

[0024]

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[In the formula, X represents a halogen atom, and R _f and m have the same meaning as described above. The fluorine-containing glycidyl ether (5) used in the production method of the present invention may be a single compound or a mixture of two or more compounds.

The reaction molar ratio between the polyhydric alcohol represented by the general formula (4) and the fluorinated glycidyl ether represented by the general formula (5) used in the reaction in the production method of the present invention is determined by the desired fluorinated etherification. It can be appropriately selected depending on the degree of etherification of the polyhydric alcohol (1). For example,
In order to obtain the desired monoether compound of the fluorinated etherified polyhydric alcohol having a high monoether content, usually, (4):
(5) The polyhydric alcohol may be used in excess at a molar ratio of 1.2: 1.0 to 4.0: 1.0, and the production amount of the monoether compound and the recovery of the raw material polyhydric alcohol may be reduced. Considering this, it is more preferable that (4) :( 5) = 1.5: 1.0-3.
It is desirable to use an excess of polyhydric alcohol in a molar ratio of 0: 1.0. Further, for example, in order to obtain a target fluorinated etherified polyhydric alcohol having a high diether content, usually (4) :( 5) = 0.3: 1.0-1.
An excess of the fluorinated glycidyl ether may be used at a ratio of 1: 1.0, and in consideration of the amount of the generated diether, (4) :( 5) = 0.4 to 1.0 to 0.8: 1.0
More preferably, the reaction is carried out at a molar ratio of

The reaction for adding the fluorinated glycidyl ether (5) to the polyhydric alcohol (4) is usually carried out without solvent, but the mixing of the polyhydric alcohol (4) and the fluorinated glycidyl ether (5) is carried out. Organic solvents can also be used to assist. Specific examples of such an organic solvent include, for example, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and the like. The amount of the organic solvent used is usually 0.1 to 1 based on the polyhydric alcohol (4) used.
A range of 0.0 times is preferable.

As the catalyst used in the reaction, an alkali or acidic catalyst generally known as a reaction catalyst for an epoxy group can be used. Examples of the alkali catalyst include, but are not particularly limited to, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, sodium hydride and the like from the viewpoint of reactivity and economy. Examples of the acidic catalyst include inorganic acids such as sulfuric acid and phosphoric acid, Lewis acids such as boron trifluoride, and paratoluenesulfonic acid.
The amount of the catalyst to be used may be generally in the range of 0.01 to 0.5 mol times based on the fluorinated glycidyl ether (5) to be used. It is desirable to use in a range of up to 0.2 mole times.

The reaction temperature is usually preferably from 0 to 200 ° C, more preferably from 20 to 150 ° C. Reaction temperature is 0
When the temperature is lower than 200C, the reaction rate is low. When the temperature exceeds 200C, the product is undesirably colored.

In the production method of the present invention, the obtained fluorinated etherified polyhydric alcohol (1) has the general formula (2)
And / or a group having a group represented by the general formula (3). In order to obtain a group having a large number of groups represented by the general formula (2), the reaction is carried out using a basic catalyst. In order to obtain a compound having many groups represented by the general formula (3), the reaction may be performed using an acidic catalyst.

In addition, in the reaction of the production method of the present invention, if water is present in the reaction system, the epoxy group of the fluorinated glycidyl ether (5) reacts with water to produce glyceryl ether as a by-product. It is preferable to dissolve or disperse the alcohol (4) and heat it to blow dry nitrogen gas, or to heat and dehydrate under reduced pressure to remove water and then add fluorine-containing glycidyl ether (5) to react. .

After completion of the reaction, the acid or alkali used as a catalyst was neutralized by adding acetic acid, citric acid, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate and the like. Thereafter, the solvent used for the reaction is removed. Here, the removal of the solvent is usually preferably performed under reduced pressure at a temperature of 120 ° C. or lower in order to avoid thermal decomposition of the reaction product.

The thus obtained fluorinated etherified polyhydric alcohol (1) of the present invention has a molecular weight of 1 per target molecule.
Unreacted polyvalent as well as a monoether compound in which two ether groups are bonded, a diether compound in which two ether groups are bonded in one molecule, and a multimol adduct in which three or more ether groups are bonded in one molecule. Contains alcohol. The unreacted polyhydric alcohol does not need to be purified and removed unless there is a problem in use.However, a solvent which does not substantially dissolve a polyol such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butanol, or acetone is added to the reaction product. To remove unreacted polyhydric alcohol by precipitation, or by a known purification method such as a method using a two-layer extraction solvent system using water and an organic solvent such as ethyl acetate, methyl ethyl ketone, and chloroform. it can.

The fluorinated etherified polyhydric alcohol (1) of the present invention can be used as a mixture of a monoether compound, a diether compound and a polymolar adduct if there is no problem in performance. If separation is necessary, for example, if purification is performed by a known purification method such as a method of extracting with a solvent such as hexane, isopropyl ether, ethyl ether, petroleum ether, or various chromatography represented by silica gel column chromatography, The desired fluorinated etherified polyhydric alcohol can be isolated and obtained.

The fluorinated etherified polyhydric alcohol (1) of the present invention thus obtained is used as a surface modifier,
Although it can be blended as an emulsifier, a washing component, a lubricant, etc., a conventionally known cationic, anionic or nonionic surfactant can also be used in combination.

[0036]

Industrial Applicability The fluorinated etherified polyhydric alcohol (1) of the present invention has good O / W emulsifiability with a fluorinated oil agent and excellent hydrolysis resistance, and is useful for skin cosmetics and cosmetics. It is extremely useful as a surface modifier, emulsifier, cleaning component or lubricant for hair cosmetics.

[0037]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto.

In this example, the ¹ H-NMR spectrum was measured using an AC-200P NMR manufactured by BRUKER.
Using SPECTOROMETER, CDCl ₃ (D ₂
O) as a solvent, concentration 3%, internal standard TMS, 2
The measurement was performed at 5 ° C. The IR spectrum was measured at 25 ° C. using a 270-30 infrared spectrophotometer manufactured by Hitachi, Ltd.
Was measured by the KBr method. Further, the composition of the fluorinated etherified polyhydric alcohol is described by Tosoh Corporation's CCPD GP.
C system (column: G2000HLX + G1000H
XL, eluent: tetrahydrofuran, temperature 40 ° C., detector: differential refractometer).

Example 1 103 g of pentaerythritol, 258 g of dimethyl sulfoxide and 2.0 g of sodium hydroxide were placed in a 500 ml flask, dissolved by heating at 105 ° C., and water and dimethyl sulfoxide were blown into the flask by blowing dry nitrogen gas to about 20 g.
g, and water in the reaction system was removed. To this 2-
After 91 g of heptadecafluorooctylethyl glycidyl ether was dropped into the flask over 2 hours, the reaction was carried out with stirring at 110 ° C. for 24 hours. After the reaction was completed, 3.0 g of acetic acid was added to the reaction mixture to neutralize the catalyst.
Dimethyl sulfoxide was completely distilled off at 80 ° C. under reduced pressure, and 99% ethanol was added to the residue, and unreacted pentaerythritol precipitated was filtered off. After evaporating ethanol from the obtained filtrate under reduced pressure, the residue was extracted with ethyl acetate by adding 500 ml of water and 500 ml of ethyl acetate.
The solvent was distilled off from the ethyl acetate soluble fraction to obtain 102 g of a dark yellow pentaerythritol / 2-heptadecafluorooctylethyl glycidyl ether adduct. As a result of GPC analysis of the product, the composition was found to be 75% monoether, 20% diether and 5% tri / tetraether.

[0040]¹H-NMR (CDCl_Three) δ (ppm): 2.53 (m, -CF_Two-CH
_Two -,-C-CH (OH) -C-), 3.35 (m, -CH ₂ OH, CH_Two-CH ₂ -O, -O-CH ₂ -
C, -CH_TwoOH), 3.70 (m, -CH ₂ -CH (OH) -CH_Two-), 4.20 (m, -CH_Two-C
H (OH) -CH ₂ -), 4.80 (m, -CH_Two-CH(OH) -CH_Two-). IR (cm^-1): 3200-3400 (OH), 1250 (C-F), 1210 (C-F), 11
40 (C-O-C), 1000 (C-OH).

Example 2 73 g of sorbitol and 200 g of N-methylpyrrolidone
Was placed in a 500 ml flask, heated to 80 ° C., and about 20 g of N-methylpyrrolidone was distilled off under reduced pressure to remove water in the reaction system. After cooling the mixture to 30 ° C., 1.0 g of boron trifluoride etherate (47%) was added. Further, 42 g of 2-tridecafluorohexylethyl glycidyl ether was added dropwise to the reaction solution in 2 hours, and the mixture was reacted at 50 ° C. with stirring for 12 hours. After completion of the reaction, 1.5 g of a 48% aqueous sodium hydroxide solution was added to the reaction mixture to neutralize the catalyst, and N-methylpyrrolidone was removed under reduced pressure at 80
At 100 ° C., and the residue is mixed with acetone 500
g was added and unreacted sorbitol precipitated was filtered off. Acetone was distilled off from the obtained filtrate under reduced pressure to obtain 52 g of a light yellow sorbitol / 2-tridecafluorohexylethyl glycidyl ether adduct. GPC of this product
As a result of analysis, the composition was found to be 72% monoether, 18% diether, 6% triether, and 4% tetra / penta / hexaether.

[0042]¹H-NMR (CDCl_Three) δ (ppm): 2.54 (m, CF_Two-CH
_Two -), 3.40 to 4.35 (m), 4.80 (m, -CH_Two-CH(OH) -CH_Two-). IR (cm^-1): 3200-3400 (OH), 1240 (C-F), 1210 (C-F), 11
40 (C-O-C), 1020 (C-OH).

Test Example 1 The emulsifying power of a fluorinated oil (perfluorodecalin) was tested using the fluorinated etherified polyhydric alcohol of the present invention obtained in Examples 1 and 2 and a conventionally known surfactant. Was done.

(Method) 5 g of perfluorodecalin and 5 ml of ion-exchanged water are added to a 20 ml test tube with a lid. After further adding 0.3 g of the test compound, the test tube was vigorously shaken for 1 minute, and then allowed to stand at 25 ° C. to measure the daily change of the average particle size of the emulsified particles with a particle size distribution analyzer (CAPA500, manufactured by Horiba, Ltd.). ). Table 1 shows the results.

[0045]

[Table 1]

As is evident from the results in Table 1, the fluorinated etherified polyhydric alcohol of the present invention is superior to the conventional surfactant in the emulsifying power of perfluorodecalin.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 43/13 C07C 41/03 C07B 61/00 300

Claims (2)

(57) [Claims] 1. The following general formula (1): [Wherein, G represents a residue obtained by removing all hydrogen atoms of hydroxyl groups from sugar alcohols selected from pentaerythritol, sorbitol, mannitol, maltitol, erythritol, inositol, xylitol, dipentaerythritol and tripentaerythritol. A: represents an alkylene group having 2 to 4 carbon atoms. Where p × q
Each A may be a different group. B: a hydrogen atom, a group represented by the following general formula (2) or a group represented by the following general formula (3) (Here, R _f represents a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, and m represents a number of 0 to 3). However, q Bs may be different groups, and not all q Bs are hydrogen atoms. p: Indicates the number of 0 to 10. q: Indicates a number of 4 or more. ] A fluorinated etherified polyhydric alcohol represented by the formula: 2. The following general formula (4): [Wherein, G represents a residue obtained by removing all hydrogen atoms of hydroxyl groups from sugar alcohols selected from pentaerythritol, sorbitol, mannitol, maltitol, erythritol, inositol, xylitol, dipentaerythritol and tripentaerythritol. A: represents an alkylene group having 2 to 4 carbon atoms. Where p × q
Each A may be a different group. p: Indicates the number of 0 to 10. q: Indicates a number of 4 or more. And a polyhydric alcohol represented by the following general formula (5): [Wherein, R _f represents a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. m: Indicates the number of 0 to 3. 2. The process for producing a fluorinated etherified polyhydric alcohol according to claim 1, wherein the reaction is carried out in the presence of an alkali catalyst or an acid catalyst.