JP2008156289A - Method for producing monoalkyl glyceryl ether - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an industrially advantageous method for manufacturing a monoalkylglycerylether at high selectivity. <P>SOLUTION: The method for preparing monoalkylglycerylether comprises the process (I) of subjecting glycerin and a specific carbonyl compound to acetalization reaction in the presence of an acidic catalyst and the process (II) of hydrocracking the resulting reaction mixture obtained by the process (I) namely the raw material therefor containing glycerin and acetalized glycerin with a molar ratio of glycerin relative to the acetalized glycerin not lower than 1.5. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a monoalkyl glyceryl ether.

  As a conventional method for producing monoalkyl glyceryl ether, hydrolysis is performed via 1,3-dioxolane using alkyl glycidyl ether synthesized from alcohol and epichlorohydrin (Patent Documents 1 and 2) as an intermediate (patent) Document 3) and a method of directly hydrolyzing the alkyl glycidyl ether (Patent Document 4) are known.

As another production method, a method of hydrocracking an acetal or ketal obtained by reacting a carbonyl compound and glycerol (Patent Document 5) is known.
U.S. Pat. No. 3,024,273 Japanese Patent Publication No.57-36260 JP 56-133281 A JP 49-86307 A Japanese Patent No. 3573785

  However, in the methods of Patent Documents 1 to 4, there are problems that a large amount of waste such as salt is generated, and the productivity is poor and the process is complicated, so that the product becomes expensive. Moreover, the product obtained also in the method of patent document 5 turns into a mixture. That is, when the acetal or ketal of glycerin is hydrocracked without a solvent, a diether body [the following formula (A) and / or (B)] is produced. Therefore, a method for producing monoalkyl glyceryl ether with higher selectivity has been desired.

  Accordingly, an object of the present invention is to provide an industrially advantageous production method capable of producing monoalkyl glyceryl ether applicable to a wide range of applications with high selectivity.

  The present inventor selectively uses monoalkyl glyceryl by hydrolyzing a reaction product obtained from glycerol and an aldehyde or ketone as a raw material and using glycerol as a solvent in a predetermined ratio. The inventors have found that ether can be obtained, and have completed the present invention.

That is, this invention relates to the manufacturing method of monoalkyl glyceryl ether including following process (I) and (II).
Step (I): A step of reacting glycerin with a carbonyl compound represented by the following general formula (1) in the presence of an acidic catalyst to obtain a reaction mixture containing glycerin and an acetalized product of glycerin.

(In formula, R < ¹ > and R < ² > may be same or different, and are respectively a hydrogen atom or a C1-C4 hydrocarbon group.)

Step (II): a reaction raw material containing the glycerin and an acetalized product of glycerin using the reaction mixture obtained in the step (I), wherein the molar ratio of glycerin to the acetalized product of glycerin is 1.5 or more. Process for hydrocracking reaction raw materials

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method which can manufacture a monoalkyl glyceryl ether with high selectivity is provided.

<Process (I)>
In step (I), in the presence of an acidic catalyst, an acetalization reaction or a ketalization reaction between glycerin and a carbonyl compound represented by the following general formula (1) (hereinafter, unless otherwise specified, an acetalization reaction) Collectively). Thereby, the reaction mixture containing glycerin and an acetalized product of glycerin is obtained. When a ketone is used as the acetal raw material, a ketalized product is obtained by a ketalization reaction.

(In formula, R < ¹ > and R < ² > may be same or different, and are respectively a hydrogen atom or a C1-C4 hydrocarbon group.)

In the formula, the hydrocarbon of R ¹ and R ² is preferably an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. It is done. As the compound represented by the general formula (1) [hereinafter referred to as compound (1)], acetone, methyl ethyl ketone, acetaldehyde, propionaldehyde, and butyraldehyde are preferable.

  In step (I), the reaction between compound (1) and glycerin is an acetalization reaction, and the ratio of glycerin to compound (1) [glycerin / compound (1), molar ratio] is the mole of glycerin in step (II). Any ratio may be used since the ratio is adjusted, but 1.5 or more, more preferably 1.5 to 10, and further 2 to 5 are preferable in order to perform the step (II) without adjustment. That is, in step (I), it is a preferred method to react glycerin and compound (1) so that the molar ratio of glycerin to acetalized glycerin in the reaction mixture is 1.5 or more.

Examples of the acidic catalyst used in the acetalization reaction include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as paratoluenesulfonic acid and benzenesulfonic acid as homogeneous catalysts. The SiO ₂ · Al ₂ O ₃ as a solid acidic catalyst of a _{heterogeneous, SiO 2 · MgO, SiO 2} · ZrO 2, Al2O 3 · B 2 O 3, Al 2 O 3, various zeolites, heteropolyacid acid to various, various Examples include phosphate, various sulfates, H ₃ PO ₄ / diatomaceous earth (solid phosphoric acid), cation exchange resin (super strong acid), oxide-supported SbF ₆ , SO ₄ / ZrO _2, etc. However, a compound having an acid point on the solid surface can be used. Among them, acid clay (Galleon Earth series, manufactured by Mizusawa Chemical Co., Ltd.), silica alumina (Mizuka Ace series, manufactured by Mizusawa Chemical Co., Ltd.), Examples thereof include powdered silicic acid (manufactured by Shilton Series Mizusawa Chemical Co., Ltd.) and synthetic acid-treated zeolite (HSZ-640HOA, manufactured by Tosoh Corporation). The amount of the acidic catalyst to be added is preferably 0.001 to 50% by weight, more preferably 0.05 to 2.0% by weight, based on glycerin. After completion of the acetalization reaction, the homogeneous catalyst is neutralized and then removed by adsorption treatment or distillation. The removal of the heterogeneous solid acidic catalyst includes not only filtration but also a fixed bed in which the reaction solution is circulated or circulated through a column pre-filled with a solid acid.

  Acetalization reaction is carried out by equilibration without dehydration and at 10 to 200 ° C., preferably 20 to 100 ° C. and without solvent or xylene, toluene, benzene, octane, isooctane, heptane, hexane, cyclohexane, pentane, ligroin, In an inert solvent such as petroleum ether or a mixed solvent of these, it is carried out while removing water produced at a temperature of 40 to 130 ° C., preferably 70 to 100 ° C., depending on the boiling point of the ketone or aldehyde used. There is a way.

  After step (I), if necessary, a step of removing excess unreacted carbonyl compound and / or acidic catalyst from the obtained reaction mixture, for example, neutralization reaction of acidic catalyst or adsorption removal of acidic catalyst It can be performed.

<Process (II)>
In the present invention, as the step (II), the reaction mixture obtained in the step (I), wherein the ratio of glycerin to glycerin acetalized product (glycerin / glycerin acetalized product) is 1.5 (molar ratio) or more. Hydrocracking something (reaction mixture).

  The ratio of glycerin to glycerin acetalized product in step (II) (glycerin / glycerin acetalized product, molar ratio) is preferably 1.5 to 10, more preferably 2 to 5. In this range, high selectivity of the desired monoalkyl glyceryl ether is obtained. In addition, when the amount of glycerin satisfies this molar ratio, the reaction mixture obtained by the step (I) can perform the step (II) as it is, and if necessary, glycerin is added to this molar ratio. You may adjust so that it may become.

  The hydrocracking reaction of the acetalized product of glycerin is carried out by adding a normal hydrocracking catalyst such as palladium, rhodium, ruthenium, platinum or the like to the acetalized product in an amount of 5 to 5000 mg / kg, the hydrogen pressure from normal pressure to 25 MPa, and the temperature of 50 It is achieved by reacting at ˜250 ° C. for 1 to 30 hours. As the hydrocracking catalyst, those obtained by supporting 0.1% to 20% on activated carbon, alumina, silica, diatomaceous earth, titanium oxide or the like may be used. Palladium is particularly preferable as the hydrocracking catalyst. If the reaction is inert to the reaction, a solvent may be further added. The reaction may be a closed system or a hydrogen flow system.

  Isolation of monoglyceryl ether from the reaction mixture can be carried out by distillation after filtration to remove the catalyst. The glycerin used as a solvent can be reused as a raw material for the acetalization reaction in step (I) or as a solvent.

  According to the method of the present invention, monoalkyl glyceryl ether can be efficiently synthesized from inexpensive aldehyde, ketone and glycerin. In the hydrocracking step (II), a monoalkyl glyceryl ether can be synthesized from acetal with a conversion of 95% or more and high selectivity of 85 (mol)% or more. Furthermore, unlike normal etherification reaction by which salt is a by-product, no waste is produced, which is excellent from the viewpoint of environmental problems. The monoalkyl glyceryl ether of the present invention has a lower viscosity than glycerin and is easy to handle. Further, since it has a diol structure, it has a high boiling point and a high affinity with water, so it is useful as a lubricant or a humectant. Furthermore, in the case of etherification, since the raw material containing organic halides, such as epichlorohydrin and an alkyl halide, is not used, the monoalkyl glyceryl ether obtained becomes excellent in stability which does not contain an organic halogen. Further, glyceryl ether obtained by hydrolyzing glycidyl ether may have an epoxy group remaining, but according to the present invention, it is excellent in safety without the concern.

  Monoalkyl glyceryl ether produced according to the present invention includes cosmetics such as humectants and cleansing agents, oily soil solubilizers, organic solvents soluble in water, paints, thinners, printing inks, antifreeze, lubricants, It is useful for an adhesive, an alkyd resin, a polyurethane resin composition, and the like.

Example 1
Add 350.0 g (3.801 mol) of glycerin and 133.5 g (2.300 mol) of acetone to a 1000 ml 4-neck round bottom flask, add 0.53 g of Amberlyst 15 ion-exchange resin (manufactured by SIGMA-ALDRICH) and stir at room temperature for 96 hours. did. Water and acetone were distilled off under reduced pressure from the reaction mixture obtained by filtering the reaction mixture, and analyzed by NMR, glycerol / 2,2-dimethyl-1,3-dioxolane-4-methanol was 2.005 / 1.000 (mol). It was. Of these, 150.0 g and 3.00 g of Pd / C (manufactured by NE Chemcat Pd 5.0%) were charged into a 500 ml autoclave and hydrocracked at 150 ° C. for 4 hours under a hydrogen pressure of 10 MPa. The obtained reaction mixture was filtered, and the filtrate was analyzed by GC and NMR. As a result, the conversion rate was 99.5%, and 1-isopropyl glyceryl ether / 1,3-diisopropyl glyceryl ether was obtained in a ratio of 89/11 (mol). It was.

GC analysis condition equipment; Hewlett Packard 4890A
Column: Agilent Technologies ULTRA 1, 25m, ID 0.2mm, Film 0.33μm
The sample was converted to TMS using ethylene glycol as an internal standard, and then GC measurement was performed.

¹ H NMR was measured using DMSO-d ₆ as a solvent and dinitrobenzene as an internal standard.

Example 2
Glycerin 373.37 g (4.054 mol) and acetone 123.72 g (2.130 mol) were placed in a 1000 ml four-necked round bottom flask, and Galleon Earth NV (manufactured by Mizusawa Chemical Co., Ltd.) 4.02 g was added and stirred at room temperature for 20 hours. Water and acetone were distilled off from the reaction solution obtained by filtering the reaction mixture under reduced pressure, and analysis by NMR revealed that glycerin / 2,2-dimethyl-1,3-dioxolane-4-methanol was 2.674 / 1.000 (mol). It was. 100.00 g of this mixture and 56.63 g of glycerin are charged into a 500 ml autoclave (the molar ratio of glycerin to 2,2-dimethyl-1,3-dioxolane-4-methanol is 5.00 / 1.00), and Pd / C (Pd 5.0 % Supported product manufactured by NE Chemcat) 3.13 g was added. Thereafter, hydrogenolysis was performed at 150 ° C. for 4 hours under a hydrogen pressure of 10 MPa. The obtained reaction mixture was filtered, and the filtrate was analyzed by GC and NMR. As a result, the conversion rate was 98.2%, and 1-isopropyl glyceryl ether / 1,3-diisopropyl glyceryl ether was obtained in a ratio of 92/8 (mol). It was.

Comparative Example 1
184.26 g (2.000 mol) of glycerin and 611.23 g (10.52 mol) of acetone were added to a 1000 ml four-necked round bottom flask, 5.02 g of Galleon Earth NV (manufactured by Mizusawa Chemical Co., Ltd.) was added and stirred at room temperature for 18 hours. Water and acetone were distilled off under reduced pressure from the reaction mixture obtained by filtering the reaction mixture, and analyzed by NMR, glycerin / 2,2-dimethyl-1,3-dioxolane-4-methanol was 0.530 / 1.000 (mol). It was. Charge 100.00 g of this mixture and 13.57 g of 2,2-dimethyl-1,3-dioxolane-4-methanol (Wako Pure Chemical Industries) into a 500 ml autoclave (at this time glycerin and 2,2-dimethyl-1,3-dioxolane) The molar ratio of -4-methanol was 0.447 / 1.00), and 2.27 g of Pd / C (Pd 5.0% supported product manufactured by NE Chemcat) was added. Thereafter, hydrogenolysis was performed at 150 ° C. for 4 hours under a hydrogen pressure of 10 MPa. The obtained reaction mixture was filtered, and the filtrate was analyzed by GC and NMR. As a result, the conversion was 99.9%, and 1-isopropyl glyceryl ether / 1,3-diisopropyl glyceryl ether was obtained in a ratio of 81/19 (mol). It was.

Claims (2)

The manufacturing method of monoalkyl glyceryl ether including following process (I) and (II).
Step (I): A step of reacting glycerin with a carbonyl compound represented by the following general formula (1) in the presence of an acidic catalyst to obtain a reaction mixture containing glycerin and an acetalized product of glycerin.

(In formula, R < ¹ > and R < ² > may be same or different, and are respectively a hydrogen atom or a C1-C4 hydrocarbon group.)
Step (II): a reaction raw material containing the glycerin and an acetalized product of glycerin using the reaction mixture obtained in the step (I), wherein the molar ratio of the glycerin to the acetalized product is 1.5 or more. Process for hydrocracking a reaction raw material   The method for producing a monoalkyl glyceryl ether according to claim 1, wherein in the step (I), glycerol and a carbonyl compound are reacted so that a molar ratio of glycerol to an acetalized product of glycerol in the reaction mixture is 1.5 or more.