JP2008162980A - Glyceryl ether - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glyceryl ether excellent in hydrolysis resistance and stability in its wide liquid properties ranging from acidity to alkalinity, and highly useful in various kinds of perfumery including milky lotion, foundation, cleansing oil, sunscreen milky lotion, self-tanning lotion, shampoo, hair rinse, acid hair dye and body soap, and also in cleansers, lubricants, moisturizers, etc. <P>SOLUTION: The glyceryl ether is represented by formula (1) (wherein, R is a 7-hydroxy-9-methylpentadecane's alcohol residue represented by the formula shown). The glyceryl ether is obtained by a process wherein a condensation reaction of 7-hydroxy-9-methylpentadecane with 2-octanol is carried out under heating and refluxing in the presence of an alkaline substance catalyst and a metal catalyst, and the resulting reaction product is hydrogenated. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to glyceryl ether.

Glyceryl ether is naturally present together with squalene in unsaponified shark liver oil, has low toxicity, is not irritating to the skin, has a smooth feeling, and has excellent moisturizing properties. Widely used. However, since glyceryl ether obtained from shark liver oil or the like is an animal resource, there is a problem that its use is remarkably regulated from the viewpoint of animal welfare and animal resource protection. Furthermore, batyl alcohol, chimyl alcohol, and ceralkyl alcohol, which are monoglyceryl ethers obtained from shark liver oil and the like, are solid or semi-solid, and therefore have a problem of poor handling.
In order to solve the above problems, glyceryl ether was synthesized from various alcohols as an alternative to animal resources by the methods shown in (Patent Document 1), (Patent Document 2), and (Patent Document 3), Used in cleaning agents, lubricants, etc.
JP-A-5-43501 JP 58-134049 A JP 56-133281 A

However, the above conventional techniques have the following problems.
(1) When the raw material alcohol of glyceryl ether is an alcohol obtained by petrochemical synthesis, it contributes to the depletion of petroleum resources and has the problem that although there are individual differences, problems such as skin irritation are likely to occur. It was. Further, when used in a cosmetic, it has a problem of lacking moisture retention and moist feeling.
(2) When used in cosmetics, cleaning agents, lubricants, etc., it is affected by other ingredients and used under acidic or alkaline conditions. It is required to have high hydrolysis resistance. However, the present situation is that glyceryl ether excellent in stability in a wide liquidity from acidic to alkaline has not been obtained yet.

  The present invention solves the above-mentioned conventional problems, and an object of the present invention is to provide a glyceryl ether that is excellent in stability in a wide liquidity from acidic to alkaline.

In order to solve the above conventional problems, the glyceryl ether of the present invention has the following constitution.
The glyceryl ether of Claim 1 of this invention has the structure represented by Formula (1).

With this configuration, the following operation is obtained.
(1) It has high hydrolysis resistance and excellent stability in a wide range of liquidity from acidic to alkaline. This is presumably because it has an alcohol residue in which two long-chain alkyl groups are bonded to a secondary carbon bonded to oxygen, and thus acts as a steric hindrance to hydrolysis.

_{Here, CH 3 (CH 2) 5} CH (OH) CH 2 CH (CH 3) (CH 2) represented by 5 CH ₃ 7- hydroxy-9-methyl-pentadecane as a raw material of the glyceryl ether is 2- It is a dimerized 2-octanol obtained by Gerve reaction of octanol. As 2-octanol, when alcohol obtained by alkaline decomposition of ricinoleic acid in castor oil is used, its acquisition is easy, not a compound derived from petrochemical, but castor oil or ricinoleic acid obtained by squeezing castor bean seeds Because it is a plant-derived compound, it has no fear of depleting petroleum resources and is excellent in resource conservation and environmental conservation. Moreover, since it is a plant-derived compound, problems such as skin irritation hardly occur.

As a method for producing glyceryl ether from dimerized 2-octanol, various known methods can be used. For example, (a) a method in which dimerized 2-octanol is converted to a halide, reacted with a hydroxyl group-protected glycerol alkali metal alcoholate to lead to 4-alkoxymethyl-1,3-dioxolane, and then hydrolyzed. (B) A method of deriving glycidyl ether from dimerized 2-octanol and epihalohydrin and hydrolyzing it. (C) Deriving glycidyl ether from dimerized 2-octanol and epihalohydrin, and reacting this with carboxylic acid. And (d) a method in which a carbonyl compound is added to glycidyl ether derived from dimerized 2-octanol to lead to a 1,3-dioxysolane compound, which is then hydrolyzed.
Among them, a method represented by the formula (2) in which glycidyl ether is derived from dimerized 2-octanol and epihalohydrin, reacted with carboxylic acid such as acetic acid, and then hydrolyzed is preferably used. Thereby, even if it is a secondary alcohol and at the same time dimerized 2-octanol having low reactivity due to steric hindrance, it is possible to produce monoglyceryl ether with high yield and high purity.

  Here, examples of the epihalohydrin include epichlorohydrin, epibromohydrin, and epiiodohydrin, and epichlorohydrin is particularly preferable because of its availability.

  In the present invention, halohydrin etherification of dimerized 2-octanol and epihalohydrin is 0.5 to 1.5 moles, preferably 0.6 to 1.5 moles of epihalohydrin with respect to dimerized 2-octanol. The catalyst is used in an amount of 0.001 to 0.2 mol times, preferably 0.005 to 0.1 mol times the amount of dimerized 2-octanol, and the reaction temperature is 10 to 150 ° C., preferably 50 It may be performed at ˜110 ° C. for 0.5 to 10 hours.

  Catalysts include Bronsted acids such as hydrochloric acid and sulfuric acid, and metals containing at least one element such as boron, aluminum, silicon, titanium, iron, cobalt, zinc, zirconium, tin, and antimony, commonly called Lewis acids. An acid catalyst such as a compound can be used. Lewis acids include boron trifluoride ether complex, boron trifluoride acetic acid complex, boron trifluoride phenol complex, aluminum chloride, aluminum bromide, zinc chloride, tin tetrachloride, antimony chloride, titanium tetrachloride, silicon tetrachloride. , Ferric chloride, ferric bromide, cobaltous chloride, cobaltous bromide, zirconium chloride, boron oxide, acidic activated alumina and the like. Moreover, aluminum triisopropoxide, titanium tetraisopropoxide, zirconium tetraisopropoxide, etc., which are alkoxides such as aluminum, titanium, and zirconium, can also be used.

In order to obtain glycidyl ether from the halohydrin ether obtained by the above reaction, alkali may be added to the reaction mixture and the ring may be closed by dehalogenation reaction.
Examples of the alkali used for the ring closure reaction of halohydrin ether include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide. Sodium hydroxide and potassium hydroxide are preferred. Moreover, it is preferable to use 1.0 to 5.0 mol times, especially 1.5 to 3.0 mol times alkali of preparation of epihalohydrin ether. Further, the reaction temperature is preferably 40 to 110 ° C., and the reaction is preferably performed for 6 to 12 hours.

The glycidyl ether can be obtained by reacting the obtained glycidyl ether with a carboxylic acid such as formic acid, acetic acid or propionic acid and then hydrolyzing the glycidyl ether with an aqueous alkaline solution or the like.
The amount of carboxylic acid such as acetic acid used is preferably a uniform phase by adding carboxylic acid to glycidyl ether and water. That is, it is 0.5-5 weight part with respect to 1 weight part of glycidyl ether, Preferably it is 1.5-3 weight part. As the amount becomes less than 1.5 parts by weight, the reaction system becomes non-uniform and the reaction rate tends to decrease remarkably. As the amount exceeds 3 parts by weight, the amount of glyceryl ether carboxylic acid ester produced increases, and the amount of alkali used for the hydrolysis treatment tends to increase. In particular, if the amount is less than 0.5 parts by weight or more than 5 parts by weight, these tendencies become remarkable, so that neither is preferable.
The reaction temperature is preferably 60 to 110 ° C., and is preferably reacted for 5 to 10 hours.

  The usage-amount of the water used for the hydrolysis reaction of glycidyl ether is 2-10 mol with respect to 1 mol of glycidyl ether, Preferably it is 4-7 mol. As the amount becomes less than 4 mol, a high-boiling by-product tends to be generated, and the yield of the target glyceryl ether tends to decrease. As the amount exceeds 7 mol, the reaction system tends to become non-uniform, and the reaction rate tends to decrease. In particular, when the amount is less than 2 moles or more than 10 moles, these tendencies are remarkable.

The invention according to claim 2 of the present invention is the glyceryl ether according to claim 1, wherein the 7-hydroxy-9-methylpentadecane comprises 2-octanol as an alkali substance and a metal catalyst. The reaction mixture is heated and refluxed under condensation to obtain a reaction product, and then the reaction product is hydrogenated.
With this configuration, in addition to the operation obtained in the first aspect, the following operation can be obtained.
(1) When 2-octanol is heated and condensed in the presence of a catalyst composed of an alkaline substance and a metal catalyst, water is removed from two molecules of 2-octanol by a Guerbe reaction, and a reaction product containing one molecule of dimerized alcohol is obtained. Therefore, mass production is possible at low cost.
(2) Although 2-octanol of the raw material was a secondary alcohol, it was found that the dimerized alcohol obtained by the Gerbe reaction had only one chemical structural formula. For this reason, it is possible to mass-produce dimer alcohol having high purity without the need for separation and purification.
(3) Since 2-octanol, the starting material, has a high boiling point of 179 ° C, just put 2-octanol, an alkaline substance and a metal catalyst in a vessel equipped with a water separator with a reflux condenser and heat it at normal pressure. However, since the reaction can be promoted at the boiling point of 2-octanol (179 ° C) to promote desorption of water and the Gerve reaction can be activated, a large production facility such as a pressurized container is not required, and the production cost is significantly reduced. In addition, it is excellent in energy saving.
(4) Since a catalyst made of an alkaline substance is used in the Gelbe reaction, the reaction vessel (pressurized vessel) is severely corroded in the reaction under high temperature and pressure, and the durability of the reaction vessel becomes a problem. Therefore, corrosion of the reaction vessel is hardly a problem and the durability of the reaction vessel is excellent.

Here, examples of the catalyst made of an alkaline substance include metallic sodium, sodium alcoholate, sodium hydroxide, metallic potassium, potassium hydroxide, and lithium hydroxide.
Among these, alkali metal hydroxides are preferably used. It is because it is excellent in handleability.
The addition amount of the catalyst is 0.01 to 10 parts by mass, preferably 0.02 to 8 parts by mass, more preferably 0.03 to 5 parts by mass with respect to 100 parts by mass of 2-octanol. As the amount added is less than 0.03 parts by mass, the reaction rate tends to decrease and the yield also decreases. As the amount exceeds 5 parts by mass, the amount of high-boiling by-products such as trimers increases. Is seen. These tendencies become more prominent as the addition amount is less than 0.02 parts by mass and as the addition amount is more than 8 parts by mass. In particular, when the addition amount is less than 0.01 parts by mass or more than 10 parts by mass, these tendencies become remarkable, which is not preferable.
The catalyst made of an alkaline substance may be added either in the form of a solid or in the form of an aqueous solution, but it is preferable to add the catalyst in an aqueous solution because it can be homogenized more quickly. The aqueous solution preferably has a concentration as high as possible. This is because the reaction rate can be increased and the energy required for distilling off water can be reduced.

As the metal catalyst, Raney catalysts such as nickel, chromium and copper, Group 8 platinum group elements such as platinum, palladium, ruthenium and rhodium can be used. Moreover, what carried | supported the group 8 platinum group element etc. on the support | carrier can be used. As the carrier, alumina, carbon or the like can be used.
The metal catalyst is added in the form of powder, and the addition amount is 0.01 to 5 parts by mass, preferably 0.05 to 4 parts by mass with respect to 100 parts by mass of 2-octanol. As the amount added is less than 0.05 parts by mass, the reaction rate tends to decrease and the yield also decreases. As the amount exceeds 4 parts by mass, the reaction rate increases but the running cost tends to increase. In particular, when the addition amount is less than 0.01 parts by mass or more than 5 parts by mass, these tendencies become remarkable, which is not preferable.

120-260 degreeC is used suitably for the temperature to heat-condense. If the temperature is lower than 120 ° C., it is difficult to remove water, and the Gerbe reaction may not proceed. Moreover, since it will produce | generate many by-products, such as high boiling point substances other than dimerization alcohol, when it becomes higher than 260 degreeC, it is unpreferable.
Heat condensation can be performed under normal pressure. Since 2-octanol, the starting material, has a high boiling point of 179 ° C., just put 2-octanol, an alkaline substance and a metal catalyst in a vessel equipped with a water separator equipped with a reflux condenser and heat it, even under normal pressure. This is because the reaction can be promoted at the boiling point of octanol (179 ° C.) to promote desorption of water and activate the Gerbe reaction. For this reason, a large-scale production facility such as a pressurized container is unnecessary, the production cost can be remarkably reduced, and energy saving is excellent. Furthermore, since this gel reaction uses a catalyst made of an alkaline substance, the reaction vessel (pressurized vessel) is severely corroded in the reaction under high temperature and pressure, and the durability of the reaction vessel becomes a problem. Therefore, it is also excellent in that there is almost no need to consider corrosion and durability of the reaction vessel.

  Furthermore, since there are compounds in the reaction that are dimerized but not converted to alcohol, hydrogenation of the reaction can increase the yield of 7-hydroxy-9-methylpentadecane. it can. Since the reaction product obtained by the 2-octanol Gerve reaction has a larger amount of a compound not converted to dimerized alcohol than the reaction product obtained by the Gerve reaction of the primary alcohol, the reaction product is hydrogenated. This is because the amount of dimerized alcohol produced can be increased.

Here, as a method of hydrogenating the reactant, hydrogenation of group 8 elements of periodic table such as iron, cobalt, nickel, platinum, palladium, ruthenium, rhodium, copper, rhenium, Raney catalyst, nickel boride catalyst, etc. A method of catalytic hydrogenation using a catalyst is used. As the hydrogenation catalyst, those supported on a carrier such as alumina, silica alumina, diatomaceous earth, silica, carbon, activated carbon, natural and synthetic zeolite can be used in order to stabilize the activity at high temperature.
In addition, an acidic reducing agent such as zinc / acetic acid and iron / acetic acid, an alkaline reducing agent such as zinc / caustic soda, sodium / alcohol and sodium amalgam, a neutral reducing agent such as aluminum amalgam, and the like can also be used.

  As hydrogenation conditions, the hydrogen pressure is preferably 2 to 5 MPa, the reaction temperature is 70 to 150 ° C., and the reaction time is 1 to 5 hours. If the hydrogen pressure is less than 2 MPa, the hydrogenation is not performed sufficiently. If the hydrogen pressure exceeds 5 MPa, a pressure device or safety device is required, and the scale of the production facility increases. This is because productivity is lacking. Further, if the reaction temperature is less than 70 ° C., the reaction takes a long time and the productivity is lowered, and if it exceeds 150 ° C., the tendency to cause a reverse reaction (dehydrogenation) increases. Further, when the reaction time is less than 1 hour, hydrogenation is not sufficiently performed, and when it exceeds 5 hours, productivity is lowered.

  In addition, after hydrogenating a reaction material, the purity of 7-hydroxy-9-methylpentadecane can be raised more by separating and refine | purifying with a column as needed.

As described above, according to the glyceryl ether of the present invention, the following advantageous effects can be obtained.
According to the invention of claim 1,
(1) It is possible to provide a glyceryl ether excellent in stability having high hydrolysis resistance in a wide liquidity from acidic to alkaline.

According to invention of Claim 2, in addition to the effect of Claim 1,
(1) Since raw material alcohol is obtained under normal pressure, a large-scale production facility such as a pressurized container is not required, production cost can be significantly reduced, and glyceryl ether excellent in energy saving can be provided.
(2) Since the raw material alcohol is obtained by a reaction under normal pressure, corrosion of the reaction vessel is hardly a problem, and glyceryl ether excellent in durability of the reaction vessel can be provided.

Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples.
(Preparation of 7-hydroxy-9-methylpentadecane)
7-Hydroxy-9-methylpentadecane, which is a raw material for the glycidyl ether of Examples, was prepared and identified by the following method.
A 1-liter three-necked flask is equipped with a thermometer, a stirrer, and a water separator with a reflux condenser, and 400 g of 2-octanol (manufactured by Ogura Gosei Kogyo Co., Ltd.), 0.65 g of a 48 wt% potassium hydroxide solution and carbon support 1.6 g of palladium (manufactured by N.E. Chemcat Co., Ltd., 5 wt% supported) was added and heated. The mixture was heated to the boiling point of 2-octanol (179 ° C.) and refluxed for 6 hours to complete the reaction. The temperature of the reaction product at this time was 220 ° C. After filtering palladium on carbon in the reaction product, the reaction product was washed with water. 2 g of Raney nickel (sponge nickel catalyst R-200 manufactured by Nikko Rica Co., Ltd.) was added to this reaction product, the hydrogen pressure was set to 4 MPa, the hydrogenation reaction was performed at 110 ° C. for 4 hours, and the reaction mixture after the hydrogenation was distilled. did.
A fraction having a boiling point of 140 ° C. (6.0 × 10 ⁻⁴ MPa) was collected. The yield was 241 g.

(Evaluation of fraction)
The obtained fraction was evaluated by the following means.
(1) Gas chromatography (manufactured by Shimadzu Corporation, GC-14B): Using column DB-1 (manufactured by J & W Scientific), the column temperature was raised from 80 ° C. at 10 ° C./min, and after reaching 300 ° C. for 10 minutes. The measurement was carried out at that temperature.
(2) NMR: A sample was dissolved in deuterated chloroform, and a proton NMR spectrum and a C ¹³ NMR spectrum were measured using a 500 MHz nuclear magnetic resonance apparatus (manufactured by JEOL, JNM-A500) with tetramethylsilane as an internal standard.
(3) High resolution mass spectrum: Measured by the FAB method using a double-focusing gas chromatograph mass spectrometer (JEOL Ltd., JMS-SX102A).
(4) Hydroxyl value: Determined according to JIS K0070-1992.
(5) Iodine value: Determined according to JIS K0070-1992.
(6) Viscosity: Measured using a TV-2 type viscometer (cone plate type) manufactured by Toki Sangyo Co., Ltd. according to JIS K7117-2: 1999. The measurement temperature was 25 ° C.

This fraction had two peaks from gas chromatography. The purity analyzed by gas chromatography was 98.5%. Further, a refractive index ⁿ 20 D = 1.4465, an iodine value was 0.6.
With respect to this fraction, hexane-ethyl acetate (9/1) was used as a developing solvent, and the two peak compounds on gas chromatography were separated as single products by column chromatography (column: silica gel).
Next, high-resolution mass spectra were measured for these two single compounds. The molecular weights obtained from the high resolution mass spectrum were 225.2552 and 225.2592, respectively. This was in good agreement with the calculated molecular weight of 225.2584 for the chemical formula C ₁₆ H ₃₃ . Therefore, the molecular weight indicated by the high-resolution mass spectrum could be identified as the molecular weight of C ₁₆ H ₃₃ . However, since the molecular weight is observed as M (molecular weight) +1 in the FAB method, it can be estimated that the actual molecular weight is 224. Furthermore, each fragmentation was the same.
Next, the hydroxyl value of this fraction was 225 (theoretical value 231). Moreover, the peak which was not converted to TMS did not exist in the gas chromatography after converting this fraction into trimethylsilyl (TMS). Therefore, it was confirmed that the compound of this fraction has a hydroxyl group.
From the above, it was possible to determine that the molecular weight 224 obtained from the high resolution mass spectrum was the molecular weight of the compound dehydrated during the measurement of the mass spectrum. That is, the two peaks of the gas chromatograph were a molecular weight 242 (a value obtained by adding a molecular weight 18 of H ₂ O to a molecular weight 224), and it was found to be a dimerized alcohol having the chemical formula C ₁₆ H ₃₄ O.
NMR spectra were measured for the isolated compounds of each of the two peaks (hereinafter referred to as the first peak and the second peak) of the gas chromatograph. The ^C 13 NMR spectra of the compound of the first peak in Figure 1, showing respectively the ^C 13 NMR spectrum of the compound of the second peak in Figure 2.

From the results of two-dimensional NMR with C ¹³ NMR and proton NMR, the measurement position can be attributed to the C ¹³ NMR absorption position of each carbon as shown in (Table 1). The carbon at each position is represented by the formula (3).
_{^{C 1 H 3 C 2 H 2}} C 3 H 2 C 4 H 2 C 5 H 2 C 6 H 2 C 7 H (OH) C 8 H 2 C 9 H (C 16 H 3) -C 10 H 2 C 11 H ₂ C ¹² H ₂ C ¹³ H ₂ C ¹⁴ H ₂ C ¹⁵ H ₃ (3)

From the above results, it was confirmed that the compound showing the two peaks of the fraction was 7-hydroxy-9-methylpentadecane. The two peaks are in a diastereomeric relationship.
In addition, the viscosity of this fraction (compound having two peaks) was 31 mPa · s.
As described above, 7-hydroxy-9-methylpentadecane could be identified and prepared.

(Example 1)
800 g of 7-hydroxy-9-methylpentadecane, 8.2 g of aluminum triisopropoxide as a catalyst and 5.6 g of sulfuric acid were placed in a four-necked flask and heated to 90 ° C. with stirring. Epichlorohydrin (337 g) was added dropwise over 2 hours and then aged for 2 hours.
After cooling the reaction mixture to 50 ° C., 882 g of 40% aqueous sodium hydroxide solution was added, the temperature was raised to 80 ° C., and the mixture was stirred for 8 hours. After separating the aqueous layer, the organic layer was cooled to 40 ° C. and washed twice with 400 mL of water to obtain 1152 g of crude 7-hydroxy-9-methylpentadecane monoglycidyl ether. Purification by vacuum distillation (0.4 kPa, 176 ° C.) gave 698 g of 7-hydroxy-9-methylpentadecane monoglycidyl ether.
698 g of 7-hydroxy-9-methylpentadecane monoglycidyl ether, 1400 g of acetic acid and 250 g of water were placed in a four-necked flask and stirred at 80 ° C. for 4 hours. After completion of the reaction, acetic acid and water were distilled off under reduced pressure. Next, 980 g of a 10% aqueous sodium hydroxide solution was added and treated at 50 ° C. for 4 hours. After separation of the aqueous layer, 600 g of hexane was added to the organic layer and washed twice with 300 mL of water, and the solvent hexane was distilled off under reduced pressure. Purification by vacuum distillation (0.5 kPa, 214 ° C.) gave 488 g of 7-hydroxy-9-methylpentadecane monoglyceryl ether (purity 99.8%).
The fraction was evaluated by gas chromatography (GC-8A, manufactured by Shimadzu Corporation) under the following conditions.
Filler: DB-17 (manufactured by J & W SCIENTIFIC), film thickness: 0.25 μm, column: capillary 0.32 mmφ × 30 m, column temperature: 120 ° C. to 290 ° C. (15 minutes), heating rate 10 ° C./min, inlet Temperature: 250 ° C., detector temperature 250 ° C.

(Comparative Example 1)
The corresponding glyceryl ether was prepared using hexyldecanol having the same carbon number 16 as 7-hydroxy-9-methylpentadecane as a starting material.
1900 g of hexyldecanol, 19.5 g of aluminum triisopropoxide as a catalyst and 13.3 g of sulfuric acid were placed in a four-necked flask, and the temperature was raised to 90 ° C. with stirring. Epichlorohydrin 800 g was added dropwise over 2 hours, and then aged for 2 hours. The reaction mixture was cooled to 50 ° C., 1180 g of 40% aqueous sodium hydroxide solution was added, the temperature was raised to 80 ° C., and the mixture was stirred for 8 hours. After separating the aqueous layer, the organic layer was cooled to 40 ° C. and washed twice with 400 mL of water to obtain 2325 g of crude hexyldecyl monoglycidyl ether. Purification by vacuum distillation (0.4 kPa, 190 ° C.) gave 1631 g of hexyldecylglycidyl ether.
1631 g of hexyl decyl glycidyl ether, 1800 g of acetic acid and 400 mL of water were placed in a four-necked flask and stirred at 90 ° C. for 7 hours. After completion of the reaction, acetic acid and water were distilled off under reduced pressure. Next, 650 g of a 10% aqueous sodium hydroxide solution was added, and the mixture was treated at 70 ° C. for 5 hours. After the aqueous layer was separated, 1600 g of hexane was added to the organic layer, washed twice with 600 mL of water, and the solvent hexane was distilled off under reduced pressure. Purification by vacuum distillation (0.4 kPa, 211 ° C.) gave 883 g of hexyldecylglyceryl ether (purity 98.3%).

(Evaluation of stability under alkaline conditions)
In a 30 mL sample tube, 1.2 g of glyceryl ether of Example 1 and Comparative Example 1 was added, diluted with 5 mL of toluene, and a 48% aqueous potassium hydroxide solution was added. After heating to 90 ° C. and stirring for 4 hours, the decomposition rate of glyceryl ether (alcohol production rate) was calculated from the peak area of the chart by gas chromatography.
3 is a gas chromatography chart before the test of glyceryl ether of Example 1, FIG. 4 is a gas chromatography chart after the test of glyceryl ether of Example 1, and FIG. 5 is a graph of the glyceryl ether of Comparative Example 1. FIG. 6 is a gas chromatography chart before the test, and FIG. 6 is a gas chromatography chart after the test of glyceryl ether of Comparative Example 1.
As a result, the alcohol production rate by decomposition of glyceryl ether in Example 1 was 2.8%, whereas the alcohol production rate by decomposition of glyceryl ether in Comparative Example 1 was 12.4%.
From this result, it was confirmed that the glyceryl ether of Comparative Example 1 was easily decomposed under alkaline conditions to produce an alcohol, whereas the glyceryl ether of Example 1 was more stable.

(Evaluation of stability under acidic conditions)
In a 30 mL sample tube, 1 g of glyceryl ether of Example 1 and Comparative Example 1 was placed, diluted with 5 mL of toluene, and 12N hydrochloric acid was added. After raising the temperature to 80 ° C. and stirring for 4 hours, the purity was measured by gas chromatography.
FIG. 7 is a gas chromatography chart after the test of glyceryl ether of Example 1, and FIG. 8 is a gas chromatography chart after the test of glyceryl ether of Comparative Example 1.
As a result, the purity of the glyceryl ether of Example 1 after the test was 97.2%, whereas the purity of the glyceryl ether of Comparative Example 1 after the test was 93.1%.
From these results, it was confirmed that the glyceryl ether of Comparative Example 1 was likely to be less pure under acidic conditions, whereas the glyceryl ether of Example 1 was more stable.
As a result of the evaluation of the stability under alkaline conditions and acidic conditions described above, the glyceryl ether of this example has high hydrolysis resistance in a wide range of liquidity from acidic to alkaline, and is excellent in stability. It was confirmed.

(Evaluation of moisture retention)
Each of the glyceryl ethers of Example 1 and Comparative Example 1 was applied to the backs of the hands of five subjects, and the feeling at that time was (a) warmth to the skin, (b) smooth, (c) hinyari A sensory test was conducted to choose from. Note that glycerin (manufactured by Ogura Gosei Kogyo Co., Ltd.), which is generally used as a humectant, was also evaluated as Comparative Example 2. Table 2 shows the sensory test results.

As shown in Table 2, it was confirmed that the glyceryl ether of Example 1 was equivalent to or higher than the glyceryl ether of Comparative Example 1 and had much better moisture retention than glycerin.
From the above, it was confirmed that the glyceryl ether of Example 1 has both high moisture retention and high hydrolysis resistance.

  The present invention relates to glyceryl ether and is excellent in stability in a wide range of liquidity from acidic to alkaline. Glyceryl ether that is extremely useful for cosmetics, cleaning agents, lubricants, moisturizers, and the like can be provided.

C ¹³ NMR spectrum of the first peak compound C ¹³ NMR spectrum of the second peak compound Gas chromatography chart before test of glyceryl ether of Example 1 Gas chromatography chart after test of glyceryl ether of Example 1 Gas chromatography chart of glyceryl ether of Comparative Example 1 before test Gas chromatography chart after test of glyceryl ether of Comparative Example 1 Gas chromatography chart after test of glyceryl ether of Example 1 Gas chromatography chart after test of glyceryl ether of Comparative Example 1

Claims (2)

Formula (1)
Glyceryl ether represented by   The 7-hydroxy-9-methylpentadecane was obtained by heating and refluxing 2-octanol in the presence of an alkaline substance catalyst and a metal catalyst to obtain a reaction product, and then hydrogenating the reaction product. The glyceryl ether according to claim 1.