Dedecyne diol and synthesis method thereof

Abstract

The invention discloses decyne diol and a synthesis method thereof, and belongs to the technical field of fine chemistry. The synthesis method of the decynediol comprises the following steps: S1, adding a potassium isobutoxide-xylene suspension or a potassium isobutoxide-toluene suspension into a reactor; and S2, maintaining the temperature in the reactor at 30-60 DEG C, introducing acetylene into the reactor, then dropwise adding methyl isobutyl ketone, and after dropwise adding, carrying out heat preservation reaction to obtain a decynediol crude product. In addition, the invention also provides the decyne diol which is prepared by the synthetic method. According to the synthesis method provided by the invention, the dosage of potassium hydroxide is greatly reduced, the reaction efficiency is improved, and the decynediol is simply and efficiently synthesized.

Description

Technical Field

[0001] The invention relates to the technical field of fine chemicals, and in particular to decynediol and a synthesis method thereof. Background Art

[0002] Decynediol is a type of nonionic surfactant with a special structure. It has good wettability, low foaming and defoaming properties, excellent corrosion inhibition, good dispersibility, etc. It is widely used in paints, coatings, pharmaceutical intermediates, pesticides, metal materials, petrochemicals and other fields. At present, the main methods for synthesizing decynediol are: (1) low-temperature pressure synthesis method with liquid ammonia as solvent; (2) synthesis method with general organic solvents as solvents and alkali metals and their hydroxides as catalysts; (3) Grignard reagent synthesis method. The above methods have the following disadvantages when synthesizing decynediol products: (1) the catalyst is expensive and cannot be recycled, which increases the production cost; (2) the alkali metal hydroxide solution is difficult to recover, which increases the processing cost; (3) the conversion rate of the acetylene diol product is not high, and there are more by-products, which increases the difficulty and cost of subsequent processing of the acetylene diol product; and the traditional distillation method has high energy consumption for purifying the product, and has certain requirements on the vacuum degree of the equipment, which greatly increases the production cost.

[0003] The yield of acetylene glycol synthesized in Chinese patent CN103304376A is higher than 85%, but the amount of catalyst used is relatively large; Chinese patent CN103242140A uses liquid ammonia as a catalyst, the reaction pressure is high, and there is a great risk; Chinese patent CN113880690A uses a segmented method to synthesize acetylene glycol, and the product yield is not high. How to simply and efficiently synthesize decynediol is a technical problem that needs to be solved in the prior art. Summary of the invention

[0004] The purpose of the present invention is to overcome the above technical deficiencies, provide a decynediol and a synthesis method thereof, and solve the technical problem of how to simply and efficiently synthesize decynediol in the prior art.

[0005] In order to achieve the above technical purpose, the technical solution of the present invention provides a method for synthesizing decynediol, comprising the following steps:

[0006] S1, adding potassium isobutoxide-xylene suspension or potassium isobutoxide-toluene suspension into a reactor;

[0007] S2. Maintain the temperature in the reactor at 30-60° C., introduce acetylene into the reactor, and then drop methyl isobutyl ketone. After the dropwise addition is completed, keep the temperature to react and obtain a crude decynediol product.

[0008] In any embodiment, after step S2, the method further includes: S3, continuing to add water to the reactor and stirring to obtain a hydrolyzate, discharging the hydrolyzate in layers to obtain a water layer, acidifying the oil phase organic layer with acid to obtain an acidified product, and melt crystallizing the acidified product to obtain a decynediol finished product.

[0009] In any embodiment, in step S1, the potassium isobutoxide-xylene suspension or the potassium isobutoxide-toluene suspension is prepared by the following steps:

[0010] S11, mixing isobutanol, potassium hydroxide aqueous solution and toluene or mixing isobutanol, potassium hydroxide aqueous solution and xylene, and then heating to 85-95° C. to remove the aqueous phase;

[0011] S12, then continue to raise the temperature, extract the isobutanol-xylene azeotrope or the isobutanol-toluene azeotrope, and continue to add xylene or toluene to replace the isobutanol to obtain a potassium isobutoxide-xylene suspension or a potassium isobutoxide-toluene suspension.

[0012] In any embodiment, in step S11, the mass fraction of the potassium hydroxide aqueous solution is 30-35%, and the mass ratio of the isobutanol, the xylene and the potassium hydroxide aqueous solution is 1:(2-2.5):(1-1.5); or the mass ratio of the isobutanol, the toluene and the potassium hydroxide aqueous solution is 1:(2-2.5):(1-1.5); and / or, in step S12, the mass ratio of the xylene or toluene to be added further to the isobutanol is (2-2.5):1.

[0013] In any embodiment, in step S1, the mass fraction of the potassium isobutoxide-xylene suspension or the potassium isobutoxide-toluene suspension is 30-35%; in step S2, the added amount of the methyl isobutyl ketone is 40-45% of the mass of the potassium isobutoxide-xylene suspension or the potassium isobutoxide-toluene suspension.

[0014] In any embodiment, in step S2, the time required for dropwise addition of methyl isobutyl ketone is 1 to 2 hours; and / or the time for the heat preservation reaction is 0.5 to 1.5 hours.

[0015] In any embodiment, in step S3, the mass of the added water is 2 to 5 times the mass of the methyl isobutyl ketone; and / or, in step S3, the stirring time is 20 to 40 minutes.

[0016] In any embodiment, in step S3, the oil phase organic layer is acidified to a pH of 6-7 by adding acid.

[0017] In any embodiment, in step S3, the temperature of the melt crystallization is 0-5°C.

[0018] In addition, the present invention also provides decynediol, which is prepared by the above synthesis method.

[0019] Compared with the prior art, the invention has the following beneficial effects: the method for synthesizing decynediol provided by the invention comprises the following steps: S1, adding a potassium isobutoxide-xylene suspension or a potassium isobutoxide-toluene suspension into a reactor; S2, maintaining the temperature in the reactor at 30-60° C., introducing acetylene into the reactor, then dripping methyl isobutyl ketone, and after the dripping is completed, carrying out a heat preservation reaction to obtain a crude decynediol product; the potassium isobutoxide-xylene suspension or the potassium isobutoxide-toluene suspension is used as a catalyst, thereby greatly reducing the amount of potassium hydroxide used, improving the reaction efficiency, and synthesizing decynediol simply and efficiently. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is the gas chromatogram of decynediol prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0021] The "range" disclosed in the present application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of the particular range. The range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that a range of 60 to 110 and 80 to 120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following ranges can all be expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5. In the present application, unless otherwise specified, the numerical range "a to b" represents an abbreviation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0022] If there is no special explanation, the "include" and "comprising" mentioned in this application represent open-ended or closed-ended expressions. For example, the "include" and "comprising" may represent that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0023] If not specifically stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0024] This specific embodiment provides a method for synthesizing decynediol, comprising the following steps:

[0025] S1. Adding a potassium isobutoxide-xylene suspension or a potassium isobutoxide-toluene suspension into a reactor; the potassium isobutoxide-xylene suspension or the potassium isobutoxide-toluene suspension is prepared by the following steps: the mass fraction of the potassium isobutoxide-xylene suspension or the potassium isobutoxide-toluene suspension is 30-35%; in some embodiments, the reactor is a flask, preferably a four-necked flask;

[0026] S11, mixing isobutyl alcohol, potassium hydroxide aqueous solution and toluene or mixing isobutyl alcohol, potassium hydroxide aqueous solution and xylene, and then heating to 85-95° C. to remove the aqueous phase; the mass fraction of the potassium hydroxide aqueous solution is 30-35%, and the mass ratio of the isobutyl alcohol, the xylene and the potassium hydroxide aqueous solution is 1:(2-2.5):(1-1.5); or the mass ratio of the isobutyl alcohol, the toluene and the potassium hydroxide aqueous solution is 1:(2-2.5):(1-1.5);

[0027] S12, then continue to raise the temperature, extract isobutanol-xylene azeotrope or isobutanol-toluene azeotrope, and continue to add xylene or toluene to replace isobutanol to obtain potassium isobutoxide-xylene suspension or potassium isobutoxide-toluene suspension; the mass ratio of xylene or toluene to be added is (2-2.5):1;

[0028] S2. Maintaining the temperature in the reactor at 30-60° C., introducing acetylene into the reactor, and then dripping methyl isobutyl ketone for 1-2 hours, and then keeping the temperature for reaction for 0.5-1.5 hours to obtain a crude decynediol product; the amount of methyl isobutyl ketone added is 40-45% of the mass of the potassium isobutoxide-xylene suspension or the potassium isobutoxide-toluene suspension.

[0029] In some embodiments, after step S2, the process further includes: S3, continuing to add water to the reactor and stirring for 20 to 40 minutes to obtain a hydrolyzate, discharging the hydrolyzate in layers to obtain a water layer, acidifying the oil phase organic layer to a pH of 6 to 7 to obtain an acidified product, and melt crystallizing the acidified product at 0 to 5° C. to obtain a decynediol product; the mass of the added water is 2 to 5 times the mass of methyl isobutyl ketone.

[0030] This specific embodiment also provides a decynediol, which is prepared by the above-mentioned synthesis method.

[0031] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0032] In the present invention, reference is made to “some embodiments”, “this embodiment”, examples, etc., which describe a subset of all possible embodiments, but it can be understood that “some embodiments” may be the same subset or different subsets of all possible embodiments and may be combined with each other without conflict.

[0033] If similar descriptions of "first / second" appear in the application documents, the following instructions are added. In the following description, the terms "first\second\third" involved are merely used to distinguish similar objects and do not represent a specific ordering of the objects. It can be understood that "first\second\third" can be interchanged in a specific order or sequence where permitted, so that the embodiments described herein can be implemented in an order other than that illustrated or described herein.

[0034] In this embodiment, the term "and / or" is merely a description of the association relationship between associated objects, indicating that three relationships may exist. For example, object A and / or object B may represent three situations: object A exists alone, object A and object B exist at the same time, and object B exists alone.

[0035] Hereinafter, the embodiments of the present application will be described. The embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If no specific techniques or conditions are indicated in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. If the manufacturer is not indicated in the reagents or instruments used, they are all conventional products that can be obtained commercially.

[0036] The potassium isobutoxide-xylene suspension in the following example has a mass fraction of 30% and is prepared by the following steps:

[0037] 100g of isobutanol, 200g of xylene and 100g of a 30% potassium hydroxide aqueous solution are added to a four-necked flask, which is sealed and high-purity nitrogen is passed to remove the air in the flask. When the temperature is raised to about 90°C (within the temperature range of 85-95°C), an isobutanol-water azeotrope is generated, the water phase is removed, the isobutanol is refluxed, and the water content of the system is measured every 20 minutes. When the water content of the system is reduced to less than 0.1% by mass, the potassium hydroxide has basically reacted and the water in the system is basically removed. Continue to heat up, extract the isobutanol-xylene azeotrope, and add 200g of xylene to replace the isobutanol; when the temperature reaches about 135°C (within the temperature range of 130-140°C), the replacement is completed, and the heating is stopped to obtain a potassium isobutoxide-xylene suspension, which is sealed under high-purity nitrogen and cooled.

[0038] The potassium isobutoxide-toluene suspension in the following example has a mass fraction of 30% and is prepared by the following steps:

[0039] 100g of isobutanol, 200g of toluene and 100g of a 30% potassium hydroxide aqueous solution are added to a four-necked flask, which is sealed and high-purity nitrogen is passed to remove the air in the flask. When the temperature is raised to about 90°C (within the temperature range of 85-95°C), an isobutanol-water azeotrope is generated, the water phase is removed, the isobutanol is refluxed, and the water content of the system is measured every 20 minutes. When the water content of the system is reduced to less than 0.1% by mass, the potassium hydroxide has basically reacted and the water in the system is basically removed. Continue to heat up, extract the isobutanol-toluene azeotrope, and add 200g of toluene to replace the isobutanol; when the temperature reaches about 135°C (within the temperature range of 130-140°C), the replacement is completed, and the heating is stopped to obtain a potassium isobutoxide-toluene suspension, which is sealed under high-purity nitrogen and cooled.

[0040] Example 1

[0041] This embodiment provides a method for efficiently synthesizing a decynediol product, comprising the following steps:

[0042] S1. Add 500 g of potassium isobutoxide-xylene suspension into a four-necked flask and seal it;

[0043] S2, maintaining the temperature in the four-necked flask at 30-40° C., slowly introducing acetylene, and then dripping methyl isobutyl ketone, 200 g of methyl isobutyl ketone was dripped in 1 hour, and after the dripping was completed, the reaction was continued at a temperature of 1 hour to obtain a crude decynediol;

[0044] S3. After the reaction is completed, the flask is emptied, 500 g of water is added to the flask, and the flask is stirred for 30 min to obtain a hydrolyzate. The hydrolyzate is poured into a container and allowed to stand for 40 min, separated, and the water layer is discharged. The oil phase is acidified with glacial acetic acid to a pH of 6.5; the acidified oil phase is melt-crystallized at 0-5° C. to obtain a decynediol product with a yield of 95.8% and a purity of 99.21%.

[0045] Combination Figure 1 The retention time is 9.530min, which is the peak of the decynediol product, indicating that the decynediol product is prepared.

[0046] Example 2

[0047] This embodiment provides a method for efficiently synthesizing a decynediol product, comprising the following steps:

[0048] S1. Add 500 g of potassium isobutoxide-xylene suspension into a four-necked flask and seal it;

[0049] S2, maintaining the temperature in the four-necked flask at 30-40° C., slowly introducing acetylene, and then dripping methyl isobutyl ketone, 200 g of methyl isobutyl ketone was added dropwise within 0.5 hour, and after the addition was completed, the reaction was continued at the temperature for 1 hour to obtain a crude decynediol;

[0050] After the reaction of S3 is completed, 500g of water is added to the flask, and the mixture is stirred for 40min to obtain a hydrolyzate. The hydrolyzate is poured into a container and allowed to stand for 30min, separated into layers, and the water layer is discharged. The oil phase is acidified with glacial acetic acid to a pH of 7; the acidified oil phase is melt-crystallized at 0-5°C to obtain a finished decynediol product with a yield of 94% and a purity of 99.92%.

[0051] Example 3

[0052] This embodiment provides a method for efficiently synthesizing a decynediol product, comprising the following steps:

[0053] S1. Add 500 g of potassium isobutoxide-xylene suspension into a four-necked flask and seal it;

[0054] S2, maintaining the temperature in the four-necked flask at 30-40° C., slowly introducing acetylene, and then dripping methyl isobutyl ketone, 200 g of methyl isobutyl ketone was dripped over 0.5 hour, and after the dripping was completed, the reaction was continued at the temperature for 0.5 hour to obtain a crude decynediol;

[0055] After the reaction of S3 is completed, 500g of water is added to the flask, and the mixture is stirred for 20min to obtain a hydrolyzate. The hydrolyzate is poured into a container and allowed to stand for 30min, separated into layers, and the water layer is discharged. The oil phase is acidified with glacial acetic acid to a pH of 6; the acidified oil phase is melt-crystallized at 0-5°C to obtain a finished decynediol product with a yield of 93.7% and a purity of 99.53%.

[0056] Example 4

[0057] This embodiment provides a method for efficiently synthesizing a decynediol product, comprising the following steps:

[0058] S1. Add 500 g of potassium isobutoxide-toluene suspension into a four-necked flask and seal it;

[0059] S2, maintaining the temperature in the four-necked flask at 30-40° C., slowly introducing acetylene, and then dripping methyl isobutyl ketone, 200 g of methyl isobutyl ketone was dripped in 1 hour, and after the dripping was completed, the reaction was continued at a temperature of 1 hour to obtain a crude decynediol;

[0060] After the reaction of S3 is completed, 500g of water is added to the flask, and the mixture is stirred for 40min to obtain a hydrolyzate. The hydrolyzate is poured into a container and allowed to stand for 60min, separated into layers, and the water layer is discharged. The oil phase is acidified with glacial acetic acid to a pH of 7; the acidified oil phase is melt-crystallized at 0-5°C to obtain a finished decynediol product with a yield of 95.1% and a purity of 99.83%.

[0061] Comparative Example 1

[0062] This comparative example proposes a method for efficiently synthesizing a decynediol product, comprising the following steps:

[0063] S1. Add 500 g of cyclohexane and 200 g of potassium hydroxide powder (content 90%) into a four-necked flask and seal it;

[0064] S2, the temperature in the flask is maintained at 30-40°C, acetylene is slowly introduced, and then methyl isobutyl ketone is added dropwise, and 200 g of methyl isobutyl ketone is added dropwise within 1 hour. After the addition is completed, the reaction is continued at a temperature of 1 hour to obtain a crude decynediol product;

[0065] S3, after the reaction is completed, evacuate the flask, add 500g of water into the flask, stir for 30min to obtain a hydrolyzate, pour the hydrolyzate into a container and let it stand for 40min, separate the layers, release the water layer, and acidify the oil phase with glacial acetic acid to a pH of 6.5;

[0066] S4. The acidified oil phase is distilled to obtain a decynediol product with a yield of 85% and a purity of 97.78%.

[0067] The present invention provides a method for synthesizing a decynediol product. The catalyst adopts an alkaline solvent such as potassium isobutoxide-xylene suspension or potassium isobutoxide-toluene suspension, which has high acetylene adsorption efficiency, significantly reduces the amount of catalyst, and improves the reaction efficiency. The purification process adopts melt crystallization, which has the following advantages: (1) simple operation, no excessive requirements on equipment, and reduced production costs; (2) low energy consumption, and improved purification efficiency of the decynediol product; (3) low-temperature operation reduces the risk of discoloration of the decynediol product, and the energy consumption is only 20% of distillation, which reduces the production cost, and the obtained decynediol product has high yield, low chroma and high purity.

[0068] The specific implementation of the present invention described above does not constitute a limitation on the protection scope of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A method for synthesizing decynediol, characterized in that: The following steps are involved: S1, adding potassium isobutoxide-xylene suspension or potassium isobutoxide-toluene suspension into a reactor; S2. Maintain the temperature in the reactor at 30-60° C., introduce acetylene into the reactor, and then drop methyl isobutyl ketone. After the dropwise addition is completed, keep the temperature to react and obtain a crude decynediol product.

2. The method for synthesizing decynediol according to claim 1, characterized in that: After step S2, the method further includes: S3, continuing to add water to the reactor and stirring to obtain a hydrolyzate, discharging the hydrolyzate in layers to obtain a water layer, acidifying the oil phase organic layer with acid to obtain an acidified product, and melt crystallizing the acidified product to obtain a decynediol finished product.

3. The method for synthesizing decynediol according to claim 1, characterized in that: In step S1, the potassium isobutoxide-xylene suspension or the potassium isobutoxide-toluene suspension is prepared by the following steps: S11, mixing isobutanol, potassium hydroxide aqueous solution and toluene, or mixing isobutanol, potassium hydroxide aqueous solution and xylene, and then heating to 85-95° C. to remove the aqueous phase; S12, then continue to raise the temperature, extract the isobutanol-xylene azeotrope or the isobutanol-toluene azeotrope, and continue to add xylene or toluene to replace the isobutanol to obtain a potassium isobutoxide-xylene suspension or a potassium isobutoxide-toluene suspension.

4. The method for synthesizing decynediol according to claim 3, characterized in that: In step S11, the mass fraction of the potassium hydroxide aqueous solution is 30-35%, and the mass ratio of the isobutanol, the xylene and the potassium hydroxide aqueous solution is 1:(2-2.5):(1-1.5); or the mass ratio of the isobutanol, the toluene and the potassium hydroxide aqueous solution is 1:(2-2.5):(1-1.5); and / or, in step S12, the mass ratio of the xylene or toluene added further to the isobutanol is (2-2.5):

1.

5. The method for synthesizing decynediol according to claim 1, characterized in that: In step S1, the mass fraction of the potassium isobutoxide-xylene suspension or the potassium isobutoxide-toluene suspension is 30-35%; in step S2, the added amount of the methyl isobutyl ketone is 40-45% of the mass of the potassium isobutoxide-xylene suspension or the potassium isobutoxide-toluene suspension.

6. The method for synthesizing decynediol according to claim 5, characterized in that: In step S2, the time required for dropwise addition of methyl isobutyl ketone is 1 to 2 hours; and / or the time for the heat preservation reaction is 0.5 to 1.5 hours.

7. The method for synthesizing decynediol according to claim 2, characterized in that: In step S3, the mass of the added water is 2 to 5 times the mass of the methyl isobutyl ketone; and / or, in step S3, the stirring time is 20 to 40 minutes.

8. The method for synthesizing decynediol according to claim 2, characterized in that: In step S3, the oil phase organic layer is acidified to a pH of 6-7 by adding acid.

9. The method for synthesizing decynediol according to claim 2, characterized in that: In step S3, the temperature of the melt crystallization is 0-5°C.

10. A decynediol, characterized in that The compound is prepared by the synthesis method according to any one of claims 1 to 9.

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