JPH04312541A - Trimethylolalkane derivative and its production - Google Patents

Abstract

PURPOSE:To provide a new trimethylolalkane derivative producible in high purity without using formaldehyde undesirable to use from the safety point of view, exhibiting extremely excellent lubricity, easily and uniformly dispersible in water and useful as a base, emulsifier, lubricant, etc., for cosmetics, etc. CONSTITUTION:The trimethylolalkane derivative of formula I [n is integer of 0-4; A<1> to A<3> are H, -CH2CH(OH)CH2OR or group of formula II (R is 16-36C branched alkyl) provided that A<1> to A<3> are not H at the same time], e.g. monoether compound of trimethylol-propane glyceryl isostearyl ether. The compound of formula I can be produced by reacting a trimethylolalkane of formula III with a glycidyl ether of formula IV in an organic solvent in the presence of a basic catalyst.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel trimethylolalkane derivative useful as a base for cosmetics, an emulsifier, a lubricant, etc., and a method for producing the same.

0002

[Prior art and problems to be solved by the invention] Conventionally,
Polyol ethers such as polyoxyalkylene alkyl ether and polyoxyalkylene ether of sorbitan ester, and trimethylol compounds such as trimethylolpropane and trimethylolnonane are used as emulsifiers, solubilizers, and lubricants in cosmetics and cosmetics, and as alkyds. It is used as an industrial raw material for resins, polyurethane, polyester, etc.

Among these, polyol ethers such as polyoxyalkylene alkyl ethers and polyoxyalkylene ethers of sorbitan esters are produced by addition reactions of alkylene oxides such as ethylene oxide and propylene oxide, but the resulting products It is a mixture of polyoxyalkylenes with various chain lengths, and it is difficult to synthesize highly pure products, so when used in cosmetics, cosmetics, etc., sufficient performance may not be obtained. .

Furthermore, trimethylol compounds having long-chain alkyl groups, such as trimethylolpropane and trimethylolnonane, are solids with high melting points or have an inappropriate balance between hydrophilic and lipophilic groups, resulting in them not being uniformly absorbed into water. Since it has drawbacks such as difficulty in dispersion and poor compatibility with various solvents, it has not been satisfactory in terms of performance.

Furthermore, although the trimethylolmethyl branched alkane disclosed in JP-A-1-283235 has characteristics such as a low melting point and excellent dispersibility in water, it uses formaldehyde as a raw material. ,
A small amount of formaldehyde remained in the product, making it unsafe to use in cosmetics and cosmetics.

[0006] Therefore, trimethylol compounds useful as bases, emulsifiers, lubricants, etc. for cosmetics and the like have been desired.

[0007]

[Means for Solving the Problems] Under these circumstances, the present inventors have conducted extensive research and found that a novel trimethylolalkane derivative represented by the general formula (1) below is unfavorable in terms of safety. without using formaldehyde,
It can be produced with high purity, has excellent lubricity, and has characteristics such as being easily dispersed almost uniformly when mixed with water, and is also used as a cosmetic base, emulsifier, and lubricant. The present invention has been completed based on the discovery that the present invention exhibits extremely excellent performance that has never been seen before.

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

[
0009

[Chemical formula 8]

[In the formula, n represents an integer of 0 to 4, A1,
A2 and A3 are each a hydrogen atom or a group -CH2CH (
OH)CH2OR or

[0011]

[Chemical formula 9]

(R represents a branched alkyl group having 16 to 36 carbon atoms). However, A1, A2 and A3 are not all hydrogen atoms] and a method for producing the same.

Trimethylolalkane derivative of the present invention (
1) is produced by heating trimethylolalkane (4) and the corresponding glycidyl branched alkyl ether (5) in the presence of a basic catalyst, for example, as shown in the following reaction formula.

[0014]

[Chemical formula 10]

(wherein n and R have the same meanings as above)

Examples of the trimethylolalkane used in the present invention include trimethylolethane, trimethylolpropane, trimethylolbutane, and trimethylolpentane. These trimethylol alkanes can be used alone or in combination.

In addition, glycidyl branched alkyl ether (
5), the branched alkyl group (R) in the formula has 16 to 3 carbon atoms.
6, preferably 18 to 24, and mixtures thereof can also be used. Such a branched alkyl group R is represented by the following general formula (2)

[0018]

[Chemical formula 11]

(wherein p and q each represent an integer of 0 to 33, and the sum of p and q is 13 to 33), or the following general formula (3)

[0020]

[Chemical formula 12]

A group represented by the formula (wherein r and s each represent an integer of 0 to 33, and the sum of r and s is 11 to 31) is preferred.

Specific examples of glycidyl branched alkyl ethers include glycidyl methyl pentadecyl ether, glycidyl methyl hexadecyl ether, glycidyl methyl heptadecyl (isostearyl) ether, glycidyl methyl octadecyl ether, glycidyl methyl behenyl ether, and glycidyl ethyl hexadecyl. Ether, glycidyl ethyl octadecyl ether, glycidyl ethyl behenyl ether, glycidyl butyl dodecyl ether, glycidyl butyl hexadecyl ether, glycidyl butyl octadecyl ether, glycidyl hexyl decyl ether, glycidyl heptyl undecyl ether, glycidyl octyl dodecyl ether, glycidyl decyl dodecyl ether, glycidyl Examples include decyltetradecyl ether, glycidyldodecylhexadecyl ether, and glycidyltetradecyloctadecyl ether.

Trimethylolalkane (4) used
The reaction molar ratio between the glycidyl branched alkyl ether (5) and the glycidyl branched alkyl ether (5) can be appropriately selected depending on the degree of etherification of the desired trimethylolalkane derivative. for example,
To obtain the desired trimethylolalkane derivative with a high monoether content, the ratio is usually 1.2:1.0.
Trimethylolalkane may be used in excess at a ratio of ~10.0:1.0, and considering the amount of monoether produced and the recovery of raw material trimethylolalkane, the ratio is 2.0:1.0~6. A ratio of .0:1.0 is preferred. In addition, in order to obtain the desired trimethylolalkane derivative with a high diether content, it is usually necessary to
Glycidyl branched alkyl ether may be used in excess at a ratio of 0.3:1.0 to 1.1:1.0, and considering the amount of diether formed, the ratio is 0.4:1.0 to 1.1:1.0.
A ratio of 0.8:1.0 is preferred.

The reaction is usually carried out without a solvent, but it is preferable to use an organic solvent to aid in mixing the trimethylolalkane and glycidyl branched alkyl ether. Examples of such organic solvents include dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N-
Examples include methylpyrrolidone, and it is preferable to use 0.1 to 10.0 times the amount of trimethylolalkane.

Further, as a catalyst, an acid or basic catalyst which is generally known as a reaction catalyst for epoxy groups can be used, but when an acid catalyst is used, as a side reaction,
This is not preferable because a decomposition reaction of ether bonds and a dehydration reaction of hydroxyl groups in the generated trimethylolalkane derivative occur, so it is preferable to use a basic catalyst. The basic catalyst to be used is not particularly limited, but in terms of reactivity and economy, examples include sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, and sodium hydride. These basic catalysts are preferably used in an amount of 0.01 to 20.0% by weight, particularly 0.1 to 10.0% by weight, based on trimethylolalkane.

[0026] The reaction is carried out at a temperature of 50 to 200°C, preferably 8°C.
It is carried out at 0-150°C for 5-15 hours. If the reaction temperature is less than 50°C, the reaction rate will be slow, and if it exceeds 200°C, the product will be colored, which is not preferred.

[0027] In this reaction, if water is present in the reaction system, the epoxy group of the glycidyl branched alkyl ether will react with water and glyceryl ether will be produced as a by-product.
It is preferable to dissolve or disperse trimethylol alkane in an organic solvent, remove moisture by heating and blowing dry nitrogen gas, or heat and dehydrate under reduced pressure, and then add glycidyl branched alkyl ether and react. .

After the reaction is completed, the catalyst is neutralized by adding an acid such as acetic acid, citric acid, sulfuric acid, hydrochloric acid, or phosphoric acid, and then the organic solvent used in the reaction is removed. The organic solvent is preferably removed under reduced pressure, usually at a temperature below 120°C, to avoid thermal decomposition of the reaction product.

The reaction products thus obtained include:
In addition to the desired monoether form of trimethylolalkane derivatives, unreacted trimethylolalkane, and diethers of trimethylolalkane branched alkyl ethers in which two and/or three of the hydroxyl groups of trimethylolalkane are glyceryl etherified. It contains the triether form and the triether form. Among these methods, unreacted trimethylolalkane can be removed by precipitation by adding an organic solvent in which trimethylolalkane has low solubility such as acetone or dioxane to the reaction product, by distilling it off under reduced pressure, or by removing it by distillation between water and ethyl acetate. It can be removed by known purification methods such as extraction with an organic solvent such as methyl ethyl ketone or methyl ethyl ketone in a water/organic solvent system. The trimethylolalkane derivative of the present invention preferably has a high monoether content from the viewpoint of dispersibility in water, but diethers and triethers may be contained as long as there are no performance problems. can be used. In addition, if there is a problem in performance, it may be removed by extraction with a solvent such as hexane, isopropyl ether, ethyl ether, petroleum ether, etc., or by a known method such as various chromatography methods such as silica gel column chromatography. According to the purification method described above, the desired monoether form of trimethylolalkane can be isolated. however,
The monoether, diether, triether or a mixture thereof of the trimethylolalkane derivative of the present invention can be used as a mixture without such purification if there is no problem in use. Moreover, the trimethylol alkane derivative of the present invention can also be used in combination with a conventionally known cationic, anionic or nonionic surfactant.

[0030]

Effects of the Invention The trimethylolalkane derivatives of the present invention can be produced with high purity without using formaldehyde, which is undesirable from a safety standpoint, and have extremely excellent lubricity, making them suitable for almost all Because it is compatible with solvents and easily disperses almost uniformly when mixed with water, it is used as a cleaning agent, emulsifier, dispersant, wetting agent, solubilizer, etc. for toiletries and cosmetics. It is extremely useful.

[0031]

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. In the examples, 1H-NMR spectra were obtained using BRUKER AC-200P NMR SP.
Using ECTROMETER, CDCl3 (in the presence of D2O) was used as a solvent, concentration was 3%, internal standard was TMS, 25
The measurement was performed at ℃. In addition, the IR spectrum was measured at 25°C using a Hitachi 270-30 infrared spectrophotometer.
It was measured by the KBr liquid film method.

Example 1 80 g of trimethylolpropane, 100 g of dimethyl sulfoxide, and 1 g of sodium hydroxide were placed in a 300 ml flask, heated to 105° C. to dissolve, dry nitrogen gas was blown into the flask, and water and dimethyl sulfoxide were added to about 10 g of dimethyl sulfoxide.
The water in the reaction system was removed by distillation. After 39 g of glycidyl isostearyl ether was added dropwise to this over 1 hour, the mixture was reacted at 105° C. for 4 hours with stirring. After the reaction, 1.5 g of acetic acid was added to the reaction mixture to neutralize the catalyst, and dimethyl sulfoxide was completely distilled off at 80°C under reduced pressure. 500 ml of water was added to the residue and extracted with ethyl acetate (250 ml x 2) was carried out, and ethyl acetate was distilled off under reduced pressure to obtain 62 g of crude trimethylolpropane glyceryl isostearyl ether. When this crude product is separated and purified using silica gel column chromatography with an elution solvent of acetone:hexane = 5:1, the target monoether form of trimethylolpropane glyceryl isostearyl ether is eluted, and the eluate fraction is The fractions were collected and the solvent was distilled off to obtain 26 g (yield: 46%) of the target monoether form of trimethylolpropane glyceryl isostearyl ether as a colorless transparent liquid. The obtained NMR spectrum and IR spectrum are shown in FIG. 1 and FIG. 2, respectively. NMR (
CDCl3): δ (ppm) 3.94 (1H, m, -OCH2-CHOH-CH2O
-), 3.41 to 3.70 (12H, m, -CH2O
H, -OCH2-), 1.27-1.58 (31H,
b, -CH2-, -CH-), 0.83 (9H, m, -
CH3) IR (liquid film) cm-1: νO-H (-OH) 320
0 to 3400; νC-H (stretching) (-CH-, -C
H2-,-CH3)2850,2930; νC-H
(Bending angle) (-CH-, -CH2-, -CH3) 13
80,1440; νC-O (-C-O-) 11
10,1060

Example 2 72 g of trimethylolethane, 5 g of N-methylpyrrolidone
0g and 1g of sodium hydroxide were placed in a 300ml flask, heated to 120°C to dissolve, dry nitrogen gas was blown into the flask, water and about 10g of N-methylpyrrolidone were distilled out, and water in the reaction system was removed. After 39 g of glycidyl isostearyl ether was added dropwise to this over 2 hours, the mixture was reacted at 120° C. with stirring for 4 hours. After the reaction, 1.5 g of acetic acid was added to the reaction mixture to neutralize the catalyst, N-methylpyrrolidone was completely distilled off at 80°C under reduced pressure, and unreacted trimethylolethane was removed using a Smith distiller. The residue was removed by distillation to obtain 55 g of crudely purified trimethylolethane glyceryl isostearyl ether. When this crude product is separated and purified using silica gel column chromatography with an elution solvent of hexane:acetone = 4:1, the target monoether form of trimethylolethane glyceryl isostearyl ether is eluted, and the eluate fraction is The fractions were collected and the solvent was distilled off to obtain 20 g (yield: 39%) of the desired monoether form of trimethylolethane glyceryl isostearyl ether. NMR (CDCl3): δ (ppm) 3.95 (1H, m, -OCH2-CHOH-CH2O
-), 3.40 to 3.69 (12H, m, -CH2O
H, -OCH2-), 1.28-1.57 (29H,
b, -CH2-, -CH-), 0.89 (9H, m, -
CH3) IR (liquid film) cm-1: νO-H (-OH) 320
0 to 3400; νC-H (stretching) (-CH-, -C
H2-,-CH3)2840,2910; νC-H
(Bending angle) (-CH-, -CH2-, -CH3) 13
70,1450; νC-O (-C-O-) 11
10,1070

Example 3 300 ml of 80 g of trimethylolpropane, 50 g of dimethyl sulfoxide and 0.8 g of sodium hydroxide
Place in a flask, heat to 120°C to dissolve, blow dry nitrogen gas, and add water and dimethyl sulfoxide to about 1
Water in the reaction system was removed by distilling 0 g. 40 g of glycidyl octyl dodecyl ether was added dropwise to this over 2 hours, and the mixture was reacted with stirring at 120° C. for 6 hours. After the reaction, 1.2 g of acetic acid was added to the reaction mixture to neutralize the catalyst, and dimethyl sulfoxide was heated at 80°C under reduced pressure.
The residue was completely distilled off, 500 ml of water was added to the residue, and extracted with 1000 ml of methyl ethyl ketone (500 ml x 2). The obtained methyl ethyl ketone layer was dried with glass salt, filtered and the solvent was distilled off to obtain 53 g of a crude product of trimethylolpropane glyceryl octyl dodecyl ether. When this crude product is separated and purified using silica gel column chromatography with an elution solvent of hexane:acetone=5:1, the target monoether form of trimethylolpropane glyceryl octyl dodecyl ether is eluted, and the eluate fraction is The fraction was collected and the solvent was distilled off, and 29 g of the desired monoether form of trimethylolpropane glyceryl octyl dodecyl ether (yield 4.
6%). NMR (CDCl3): δ (ppm) 3.97 (1H, m, -OCH2-CHOH-CH2O
-), 3.41 to 3.70 (12H, m, -CH2O
H, -OCH2-), 1.24-1.58 (35H,
b, -CH2-, -CH-), 0.85 (9H, m, -
CH3) IR (liquid film) cm-1: νO-H (-OH) 320
0 to 3400; νC-H (stretching) (-CH-, -C
H2-,-CH3)2860,2930; νC-H
(Bending angle) (-CH-, -CH2-, -CH3) 13
80,1440; νC-O (-C-O-) 11
20,1060

Comparative Example 1 70 g of trimethylolpropane, 200 g of dimethyl sulfoxide and 1 g of sodium hydroxide were placed in a 500 ml flask, heated to 100° C. to dissolve, dry nitrogen gas was blown into the flask, and water and dimethyl sulfoxide were added to about 20 g of dimethyl sulfoxide.
The water in the reaction system was removed by distillation. After 33 g of glycidyl stearyl ether was added dropwise to this over 2 hours, the mixture was reacted with stirring at 110° C. for 5 hours. After the reaction, 1.5 g of acetic acid was added to the reaction mixture to neutralize the catalyst, and dimethyl sulfoxide was completely distilled off at 80°C under reduced pressure. 500 g of acetone was added to the residue to precipitate unreacted trimethylol. Propane was filtered off. Acetone was distilled off from the obtained filtrate under reduced pressure to obtain 45 g of crudely purified trimethylolpropane glyceryl stearyl ether. When this crude product is separated and purified using silica gel column chromatography with an elution solvent of hexane:acetone = 2:1, the target monoether form of trimethylolpropane glyceryl stearyl ether is eluted, and the eluate fraction is Collect the fraction, distill off the solvent,
22 g (yield: 47%) of the desired monoether form of trimethylolpropane glyceryl stearyl ether was obtained. It was confirmed by NMR and IR spectrum analysis that the obtained compound was a monoether of trimethylolpropane glyceryl stearyl ether.

Test Example 1 The properties at room temperature and the dispersibility in water (concentration 5% by weight) were investigated for the trimethylolalkane derivative of the present invention obtained in the example and the conventionally known compounds. The results are shown in Table 1. (Evaluation method) Properties at room temperature were examined by visual observation. To measure the dispersibility in water, 1 g of the sample was collected in a 30 ml sample bottle, ion-exchanged water was added thereto to give a sample concentration of 5% by weight, the sample bottle was shaken for 1 minute, and left to stand for 5 minutes. After that, the dispersion state was observed with the naked eye.

[0037]

[Table 1]

Test Example 2 Using the compounds of the present invention obtained in Examples, hair rinses having the compositions shown in Table 2 were produced, and their rinsing performance was investigated. The results are shown in Table 2. (Manufacturing method) To water heated to 70°C, the components heated and dissolved at the same temperature were added, stirred to mix, and then cooled to room temperature while stirring to obtain a hair rinse. (Evaluation method) 20g (length 15cm) of hair from a Japanese woman who has never undergone beauty treatments such as cold perm or bleaching is tied into bundles, and the hair bundles are treated with a commercially available shampoo containing an anion activator as the main ingredient. After washing, 2 g of the hair rinse shown in Table 2 was evenly applied, followed by rinsing with running water for 30 seconds, followed by towel drying. This wet hair bundle was subjected to sensory evaluation for softness, smoothness, and oiliness. The evaluation criteria were as follows: ◎ for particularly excellent results, ◯ for good results, △ for average results, and × for poor results.

[0039]

[Table 2]

[0040]

[Brief explanation of the drawing]

FIG. 1: N of the monoether form of trimethylolpropane glyceryl isostearyl ether obtained in Example 1.
It is a drawing showing an MR spectrum.

FIG. 2: Monoether I of trimethylolpropane glyceryl isostearyl ether obtained in Example 1.
It is a drawing showing an R spectrum.

Claims (6)

[Claims] Claim 1: The following general formula (1) [In the formula, n represents an integer of 0 to 4, A1, A2 and A3
are each a hydrogen atom or a group -CH2CH(OH)CH2
OR or [Formula 2] (R represents a branched alkyl group having 16 to 36 carbon atoms). However, A1, A2 and A3 are not all hydrogen atoms]. Claim 2: In general formula (1), n is 0 or 1
The trimethylolalkane derivative according to claim 1. Claim 3: In the general formula (1), R is represented by the following general formula (2): (wherein p and q each represent an integer of 0 to 33,
The trimethylolalkane derivative according to claim 1 or 2, wherein the sum of q and q is 13 to 33. [Claim 4] In the general formula (1), R is represented by the following general formula (3) [Image Omitted]
The trimethylolalkane derivative according to claim 1 or 2, wherein the sum of s and s is 11 to 31. 5. In general formula (1), one of A1, A2 and A3 is a group -CH2CH(OH)CH2O
The trimethylolalkane derivative according to any one of claims 1 to 4, which is R or [Image Omitted] (R represents a branched alkyl group having 16 to 36 carbon atoms). 6. Trimethylolalkane represented by the following general formula (4) [Chemical 6] (wherein n represents an integer of 0 to 4) and the following general formula (5) [Chemical 7] (In the formula, R represents a branched alkyl group having 16 to 36 carbon atoms) is reacted with a glycidyl ether in an organic solvent in the presence of a basic catalyst.
5. The method for producing a trimethylolalkane derivative according to any one of items 5 to 5.