Synthetic method of ethylhexylglycerin and ethylhexylglycerin

Abstract

The method comprises the following steps: adding 2-ethylhexyl glycidyl ether and deionized water into a high-pressure reactor according to a molar ratio of 1: (1.0-2.0), adding a Lewis acid catalyst according to a mass ratio of the Lewis acid catalyst to the deionized water of (0.1-1): 100, sealing the high-pressure reactor, carrying out a reaction at a temperature of 60-80 DEG C for 1-2 hours, and carrying out vacuum filtration to obtain the ethylhexyl glycerol. The method comprises the following steps: adding the 2-ethylhexyl glycidyl ether and the deionized water into the high-pressure reactor according to a molar ratio of 1: (1.0-2.0); the temperature of the materials in the high-pressure reactor is controlled to be 150-300 DEG C and the system pressure is controlled to be 0.47-8.70 Mpa under the stirring condition, after the heat preservation reaction is conducted for 10-120 min, the temperature is reduced to be 25-35 DEG C, the obtained product is moved to a separating funnel to be subjected to oil-water separation, a water phase is separated out, an organic phase product is obtained, the organic phase product is distilled through molecular distillation equipment under the condition that the vacuum degree is 30-40 Pa, and the product is obtained. Collecting a fraction at the temperature of 112-118 DEG C as a target product, wherein the target product is ethylhexylglycerin. The problems of high cost, difficulty in popularization and application, serious pollution, limited industrial production and the like in a traditional method can be solved.

Description

Technical Field

[0001] The present invention relates to the technical field of preparation technology of fine chemical products, and in particular to a synthesis method of ethylhexylglycerol and ethylhexylglycerol thereof. Background Art

[0002] Ethylhexylglycerin is a multifunctional cosmetic additive with high international recognition. It is safe and non-irritating to the human body and can be used in infant products. In recent years, it has been widely used in various daily chemical products, such as cleaning products, creams, deodorants, makeup, care products and sunscreen products, to enhance the moisturizing effect of the product, increase the smooth and comfortable skin feel, and help improve the skin's absorption of the product. Another important feature is that ethylhexylglycerin can effectively inhibit the growth of bacteria, yeasts, molds, etc. in the product, and has a preservative and synergistic effect. It has excellent preservative effects when used alone or in combination with other preservative substances. Among them, when used in combination with traditional preservatives, it can greatly reduce the dosage of traditional preservatives, reduce the irritation of the product to the skin and mucous membranes, and increase the safety of the product. In more cases, ethylhexylglycerin is compounded with polyols to construct a "no-additive" green preservative system.

[0003] Ethylhexyl glycerol has not been developed for a long time, so there are few reports on related synthesis processes. The Chinese invention patent with publication number CN104817436A discloses a method for preparing high-purity ethylhexyl glycerol, which generates an intermediate 4-alkoxymethyl-1,3-dioxoalkane by using 2-ethylhexyl glycidyl ether and acetone under the catalysis of boron trifluoride ether, adds a terminator to stop the reaction, then hydrolyzes and separates the oil phase, neutralizes and washes with sodium bicarbonate, adds a stabilizer, and finally obtains ethylhexyl glycerol by molecular distillation. This process has the disadvantages of many steps, high difficulty in operation, difficult purification, and high environmental pollution. The Chinese invention patent with publication number CN117447315A discloses a method for preparing ethylhexylglycerol, which involves a method for hydrolyzing 2-ethylhexyl glycidyl ether. First, an acidic catalyst such as sulfuric acid and p-toluenesulfonic acid is mixed with water, and then a water-soluble solvent such as dimethyl sulfoxide and dioxane is added to prepare an acidic aqueous solution. Then, 2-ethylhexyl glycidyl ether is added dropwise to the acidic aqueous solution. After a certain period of heat preservation reaction, the reaction solution is heated and decompressed to distill and recover the organic solvent. The obtained concentrated solution is separated into a water layer, washed with water, and distilled to obtain ethylhexylglycerol. In the hydrolysis process of this process, an acidic catalyst and a solvent are added to generate acidic waste water. Recovery of the solvent inevitably increases energy consumption and processes. These defects lead to high product costs, difficulty in large-scale promotion and application, large pollution, and limited industrial production. Summary of the invention

[0004] The disclosed embodiment provides a method for synthesizing ethylhexylglycerol and ethylhexylglycerol thereof, which can solve the problems of high product cost, difficulty in large-scale promotion and application, large pollution and limited industrial production in the traditional process of synthesizing ethylhexylglycerol. The technical solution is as follows:

[0005] According to a first aspect of an embodiment of the present disclosure, a method for synthesizing ethylhexylglycerol is provided, the method comprising:

[0006] Step S1: adding 2-ethylhexyl glycidyl ether and deionized water in a molar ratio of 1:1.0-2.0 into a high-pressure reactor, and then adding a Lewis acid catalyst, wherein the mass ratio of the Lewis acid catalyst to the deionized water is 0.1-1:100, sealing the high-pressure reactor, and controlling the temperature of the material in the high-pressure reactor to 150-300° C. under stirring conditions, the system pressure is 0.47-8.70 MPa, and after the reaction is kept warm for 10-120 minutes, the temperature is lowered to 25-35° C.;

[0007] Step S2: transferring the product obtained in step S1 to a separatory funnel for oil-water separation, separating the aqueous phase, and obtaining an organic phase product;

[0008] Step S3: distilling the organic phase product obtained in step S2 through a molecular distillation device under a vacuum degree of 30-40 Pa, collecting the fraction at a temperature of 112-118° C. as the target product, which is ethylhexylglycerol.

[0009] In one embodiment, in step S1, the molar ratio of the 2-ethylhexyl glycidyl ether to deionized water is 1:1.2-1.5.

[0010] In one embodiment, in step S1, the Lewis acid catalyst is any one of zinc chloride, aluminum chloride, ferrous chloride, cupric chloride, etc., or a combination of any two or more thereof, and the mass ratio of the Lewis acid catalyst to the deionized water is 0.2-0.8:100.

[0011] In one embodiment, in step S1, the temperature of the material in the high-pressure reactor under stirring conditions is 200-280° C., the system pressure is 1.55-6.50 MPa, and the insulation time is 15-60 min.

[0012] In one embodiment, in step S1, a coil condenser is provided in the high-pressure reactor.

[0013] In one embodiment, in step S1, a thermometer is provided in the high-pressure reactor.

[0014] In one embodiment, in step S1, a stirrer is provided in the high pressure reactor.

[0015] According to a second aspect of the embodiments of the present disclosure, there is provided an ethylhexylglycerol, wherein the ethylhexylglycerol is synthesized according to the synthesis method of ethylhexylglycerol described in any one of the above embodiments.

[0016] The implementation of this disclosure includes the following technical effects:

[0017] The present disclosure provides a method for synthesizing ethylhexyl glycerol, which uses 2-ethylhexyl glycidyl ether as a raw material, and directly hydrolyzes the target product under high temperature, high pressure, and Lewis acid catalysis conditions, and the reaction yield can reach more than 95%, and the product purity can reach 99.9%. At the same time, the method for synthesizing ethylhexyl glycerol provided by the present disclosure avoids the problems of complex separation and purification of product components, high cost, large pollution, and poor economy caused by traditional synthesis methods. In addition, the method for synthesizing ethylhexyl glycerol provided by the present disclosure directly hydrolyzes 2-ethylhexyl glycidyl ether under high temperature, high pressure, and Lewis acid catalysis conditions, without adding any solvent, with high yield, good selectivity, low energy consumption, easy purification, less pollution, low cost, and suitable for industrial large-scale production.

[0018] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present disclosure. DETAILED DESCRIPTION

[0019] Exemplary embodiments will be described in detail herein, examples of which are shown in the accompanying drawings. When the following description refers to the drawings, the same numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present disclosure. Instead, they are merely examples of devices and methods consistent with some aspects of the present disclosure as detailed in the appended claims.

[0020] The present disclosure provides a method for synthesizing ethylhexylglycerol, using 2-ethylhexyl glycidyl ether as a raw material, and directly hydrolyzing the target product under high temperature and high pressure and Lewis acid catalysis conditions. Specifically, the method comprises the following steps:

[0021] Step S1: adding 2-ethylhexyl glycidyl ether and deionized water in a molar ratio of 1:1.0-2.0 into a high-pressure reactor, adding Lewis acid as a catalyst, wherein the mass ratio of the Lewis acid to the deionized water is 0.1-1:100, sealing the high-pressure reactor, and controlling the temperature of the material in the high-pressure reactor to 150-300° C. under stirring conditions, the system pressure is 0.47-8.70 MPa, and after keeping the temperature for 10-120 minutes, cooling to 25-35° C.;

[0022] Step S2: transferring the product obtained in step S1 to a separatory funnel for oil-water separation, separating the aqueous phase, and obtaining an organic phase product;

[0023] Step S3: distilling the organic phase product obtained in step S2 through a molecular distillation device under a vacuum degree of 30-40 Pa, collecting the fraction at a temperature of 112-118° C. as the target product, which is ethylhexylglycerol.

[0024] The present disclosure provides a method for synthesizing ethylhexyl glycerol, which uses 2-ethylhexyl glycidyl ether as a raw material, and directly hydrolyzes the target product under high temperature, high pressure, and Lewis acid catalysis conditions, and the reaction yield can reach more than 95%, and the product purity can reach 99.9%. At the same time, the method for synthesizing ethylhexyl glycerol provided by the present disclosure avoids the problems of complex separation and purification of product components, high cost, large pollution, and poor economy caused by traditional synthesis methods. In addition, the method for synthesizing ethylhexyl glycerol provided by the present disclosure directly hydrolyzes 2-ethylhexyl glycidyl ether under high temperature, high pressure, and Lewis acid catalysis conditions, without adding any solvent, with high yield, good selectivity, low energy consumption, easy purification, less pollution, low cost, and suitable for industrial large-scale production.

[0025] In one embodiment, in step S1, the molar ratio of the 2-ethylhexyl glycidyl ether to deionized water is 1:1.2-1.5.

[0026] In one embodiment, in step S1, the Lewis acid catalyst is any one of zinc chloride, aluminum chloride, ferrous chloride, cupric chloride, etc., or a combination of any two or more thereof, and the mass ratio of the Lewis acid catalyst to the deionized water is 0.2-0.8:100.

[0027] In one embodiment, in step S1, the temperature of the material in the high-pressure reactor under stirring conditions is 200-280° C., the system pressure is 1.55-6.50 MPa, and the insulation time is 15-60 min.

[0028] In one embodiment, in step S1, a coil condenser is provided in the high-pressure reactor.

[0029] In one embodiment, in step S1, a thermometer is provided in the high-pressure reactor.

[0030] In one embodiment, in step S1, a stirrer is provided in the high pressure reactor.

[0031] The present disclosure also provides ethylhexylglycerol, which is synthesized according to the synthesis method of ethylhexylglycerol described in any of the above embodiments.

[0032] The synthesis method of ethylhexylglycerol provided in the present disclosure will be described in detail with reference to specific examples below.

[0033] Example 1

[0034] 744.0 g (4.0 mol) of 2-ethylhexyl glycidyl ether, 72.0 g (4.0 mol) of deionized water, and 0.36 g of zinc chloride were added to a 1000 mL autoclave equipped with an agitator, a built-in coil condenser, and a thermometer. After the autoclave was sealed, the agitator was turned on, the temperature of the materials in the autoclave was raised to 280° C., the pressure in the autoclave was set to 6.50 MPa, and after the reaction was kept warm for 20 minutes, the temperature was lowered to 30° C.; the reaction product was transferred to a separating funnel for oil-water separation, and the water phase was removed to obtain an organic phase product; the organic phase product was distilled by a molecular distillation device at a vacuum pressure of 30 to 40 Pa, and the fraction at a temperature of 112 to 118° C. was collected as a target product, which was ethylhexyl glycerol in a colorless transparent liquid state with a mass of 757.3 g. Gas chromatography analysis of the target product revealed that the purity of ethylhexylglycerol synthesized according to the synthesis method of ethylhexylglycerol provided in the embodiment of the present disclosure was 99.9%, and the yield was 92.8%.

[0035] Example 2

[0036] 744.0 g (4.0 mol) of 2-ethylhexyl glycidyl ether, 86.4 g (4.8 mol) of deionized water, and 0.69 g of zinc chloride were added to a 1000 mL autoclave equipped with an agitator, a built-in coil condenser, and a thermometer. After the autoclave was sealed, the agitator was turned on, the temperature of the materials in the autoclave was raised to 210° C., the pressure in the autoclave was set to 1.95 MPa, and after the reaction was kept warm for 120 minutes, the temperature was lowered to 30° C., the reaction product was transferred to a separating funnel for oil-water separation, and the water phase was removed to obtain an organic phase product; the organic phase product was distilled by a molecular distillation device under a vacuum pressure of 30 to 40 Pa, and the fraction at a temperature of 112 to 118° C. was collected as the target product, which was 776.0 g of colorless transparent liquid ethylhexyl glycerol. Gas chromatography analysis of the target product revealed that the purity of ethylhexylglycerol synthesized according to the synthesis method of ethylhexylglycerol provided in the embodiment of the present disclosure was 99.9%, and the yield was 95.1%.

[0037] Figure 1 This is the IR graph of ethylhexylglycerol prepared according to the synthesis method of ethylhexylglycerol provided in Example 2 of the present disclosure.

[0038] Figure 2 This is the 1HNMR chart of ethylhexylglycerol prepared according to the synthesis method of ethylhexylglycerol provided in Example 2 of the present disclosure.

[0039] Figure 3 This is a GC chart of ethylhexylglycerol prepared according to the synthesis method of ethylhexylglycerol provided in Example 2 of the present disclosure.

[0040] Example 3

[0041] 744.0 g (4.0 mol) of 2-ethylhexyl glycidyl ether, 108.0 g (6.0 mol) of deionized water, 0.324 g of copper chloride and 0.324 g of aluminum chloride were added to a 1000 mL autoclave equipped with an agitator, a built-in coil condenser and a thermometer, and after the autoclave was sealed, the agitator was turned on, the material in the autoclave was heated to 240° C., the pressure in the autoclave was set to 3.41 MPa, and after the reaction was kept warm for 60 minutes, the temperature was lowered to 30° C.; the reaction product was transferred to a separating funnel for oil-water separation, and the water phase was removed to obtain an organic phase product; the organic phase product was distilled by a molecular distillation device under a vacuum pressure of 30 to 40 Pa, and the fraction at a temperature of 112 to 118° C. was collected as a target product, which was 749.9 g of ethylhexyl glycerol in the form of a colorless transparent liquid. Gas chromatography analysis of the target product revealed that the purity of ethylhexylglycerol synthesized according to the synthesis method of ethylhexylglycerol provided in the embodiment of the present disclosure was 99.9%, and the yield was 91.9%.

[0042] Those skilled in the art will readily appreciate other embodiments of the present disclosure after considering the specification and practicing the disclosure disclosed herein. This application is intended to cover any variations, uses, or adaptations of the present disclosure that follow the general principles of the present disclosure and include common knowledge or customary techniques in the art that are not disclosed in the present disclosure. The description and examples are intended to be exemplary only, and the true scope and spirit of the present disclosure are indicated by the following claims.

Claims

1. A method for synthesizing ethylhexylglycerol, characterized in that: The method comprises: Step S1: adding 2-ethylhexyl glycidyl ether and deionized water in a molar ratio of 1:1.0-2.0 into a high-pressure reactor, adding Lewis acid as a catalyst, wherein the mass ratio of the Lewis acid to the deionized water is 0.1-1:100, sealing the high-pressure reactor, and controlling the temperature of the material in the high-pressure reactor to 150-300° C. under stirring conditions, the system pressure is 0.47-8.70 MPa, and after keeping the temperature for 10-120 minutes, cooling to 25-35° C.; Step S2: transferring the product obtained in step S1 to a separatory funnel for oil-water separation, separating the aqueous phase, and obtaining an organic phase product; Step S3: distilling the organic phase product obtained in step S2 through a molecular distillation device under a vacuum degree of 30-40 Pa, collecting the fraction at a temperature of 112-118° C. as the target product, which is ethylhexylglycerol.

2. The method for synthesizing ethylhexylglycerol according to claim 1, characterized in that: In step S1, the molar ratio of the 2-ethylhexyl glycidyl ether to deionized water is 1:1.2-1.

5.

3. The method for synthesizing ethylhexylglycerol according to claim 1, characterized in that: In step S1, the Lewis acid catalyst is any one of zinc chloride, aluminum chloride, ferrous chloride, cupric chloride, etc., or a combination of any two or more thereof, and the mass ratio of the Lewis acid catalyst to the deionized water is 0.2-0.8:

100.

4. The method for synthesizing ethylhexylglycerol according to claim 1, characterized in that: In step S1, under stirring conditions, the temperature of the material in the high-pressure reactor is 200-280° C., the system pressure is 1.55-6.50 MPa, and the insulation time is 15-60 min.

5. The method for synthesizing ethylhexylglycerol according to claim 1, characterized in that: In step S1, a coil condenser is provided in the high-pressure reactor.

6. The method for synthesizing ethylhexylglycerol according to claim 1, characterized in that: In step S1, a thermometer is provided in the high-pressure reactor.

7. The method for synthesizing ethylhexylglycerol according to claim 1, characterized in that: In step S1, a stirrer is provided in the high-pressure reactor.

8. An ethylhexylglycerin, characterized in that: The ethylhexylglycerol is synthesized according to the synthesis method of ethylhexylglycerol according to any one of claims 1 to 7.

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