Preparation method of decynediol

Abstract

The invention belongs to the technical field of fine chemical synthesis, and discloses a preparation method of decynediol. The preparation method comprises the following steps: cooling a solvent, mixing with a catalyst, introducing acetylene, and heating to a reaction temperature; dropwise adding methyl isobutyl ketone, and after dropwise adding is finished, carrying out heat preservation reaction to obtain a first product system; adding water, and carrying out layering separation to obtain a decynediol crude product; and finally, rectifying, and recovering the solvent to prepare the decynediol. The catalyst comprises a methoxide and tetrabutyl ammonium hydroxide. According to the preparation method of the decynediol, provided by the invention, the reaction conversion rate and selectivity can be remarkably improved, so that the product yield is improved; the method is simple in process and low in equipment requirement, 100% application of the recovered solvent can be achieved, the recovered solvent is continuously applied for 10 times to prepare the decynediol, and the method still has excellent conversion rate and selectivity, and is a safe and green production method which is low in raw material cost.

Description

Technical Field

[0001] The invention belongs to the technical field of fine chemical synthesis, and particularly relates to a method for preparing decynediol. Background Art

[0002] 2,4,7,9-Tetramethyl-5-decyne-4,7-diol surfactant is a nonionic surfactant in water-based systems that can significantly reduce the surface tension of water. 2,4,7,9-Tetramethyl-5-decyne-4,7-diol multifunctional surfactant is usually compounded with various solvents into liquids for easy use. It is used in water-based coatings, dyes, water-based inks, pesticides and other fields. It can be used as a wetting agent and defoaming agent for water-based coatings to improve the uniformity and fluidity of coatings.

[0003] At present, the industrial production of decynediol is synthesized in a one-step process using methyl isobutyl ketone and acetylene as raw materials. However, the current process still has the problem of low reaction conversion rate and selectivity, which leads to low product yield; although some processes can improve the product yield, their preparation process is complicated and the conditions are strictly controlled. For example, the yield of decynediol in the synthesis process disclosed in patent CN201210517582.1 is low, only reaching more than 70%, and there are many raw material residues. Although patent CN202111133150.6 can improve the product yield to 93%; however, its process is complicated, and a high-temperature reaction tube is used to promote the reaction. A large amount of dimethylhexynol is generated, which belongs to a co-production process.

[0004] Therefore, there is an urgent need to provide a preparation method that has a simple process and can effectively improve the reaction conversion rate and selectivity for preparing decynediol. Summary of the invention

[0005] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a preparation method of decynediol. The preparation method provided by the present invention has a simple process and can effectively improve the reaction conversion rate and selectivity, thereby improving the product yield.

[0006] The invention provides a method for preparing decynediol.

[0007] Specifically, a method for preparing decynediol comprises the following steps:

[0008] The solvent is cooled and mixed with a catalyst, and then acetylene is introduced and the temperature is raised to a reaction temperature; methyl isobutyl ketone is added dropwise, and after the addition is completed, the temperature is kept for reaction to obtain a first product system; water is added to the first product system, and a crude decynediol product is obtained after layer separation; finally, the crude decynediol product is distilled and the solvent is recovered to obtain decynediol;

[0009] The catalyst comprises methoxide and tetrabutylammonium hydroxide; the mass ratio of the methoxide to the tetrabutylammonium hydroxide is 1:(0.1-0.8).

[0010] Preferably, the mass ratio of the methoxide to the tetrabutylammonium hydroxide is 1:(0.3-0.75).

[0011] Preferably, the methoxide comprises potassium methoxide and / or sodium methoxide.

[0012] Preferably, the added amount of the catalyst is 2.0%-7.5% of the mass of the solvent; further preferably, the added amount of the catalyst is 3.0%-6.5% of the mass of the solvent.

[0013] Preferably, the added amount of the methoxide is 2%-5% of the mass of the solvent; and the added amount of the tetrabutylammonium hydroxide is 1%-1.5% of the mass of the solvent.

[0014] Preferably, the cooling process is to cool the solvent to a temperature of 0-10°C, such as 2, 5, 8, 10°C, etc. The temperature of the solvent is controlled to be 0-10°C, and the methanolate solid and the phase transfer catalyst tetrabutylammonium hydroxide can maintain good particle properties under low temperature conditions, and the temperature is raised when acetylene is introduced, which will make the reaction effect better.

[0015] Preferably, the solvent is methyl tert-butyl ether, which can not only completely dissolve the generated decynediol product, but also has good solubility for potassium acetylene.

[0016] Preferably, the mass of the methyl isobutyl ketone is 60%-80% of the mass of the solvent; further preferably, the mass of the methyl isobutyl ketone is 65%-75% of the mass of the solvent.

[0017] Preferably, a nitrogen replacement process is also included before the heating process, the number of nitrogen replacements is 3-5 times, and the nitrogen replacement process is first pressurized to 0.15-0.2MPa, and then depressurized to 0.02-0.05MPa.

[0018] Preferably, after the acetylene is introduced, the pressure of the reaction system is 0.03-0.07 MPa; further preferably, after the acetylene is introduced, the pressure of the reaction system is 0.05-0.07 MPa.

[0019] Preferably, the reaction temperature is 35-55°C, the time for adding methyl isobutyl ketone is 2.5-4.5 hours, and the time for the insulation reaction is 0.1-0.5 hours; further preferably, the reaction temperature is 40-50°C, the time for adding methyl isobutyl ketone is 3-4 hours, and the time for the insulation reaction is 0.2-0.5 hours.

[0020] Preferably, the distillation process is: using a distillation tower to distill the crude decynediol, collecting the material at 115-120° C. at the top of the distillation tower under a pressure of -0.0990 MPa to obtain the product decynediol.

[0021] Preferably, the amount of water added is 10%-50% of the mass of the first product system.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] (1) The preparation method of decynediol provided by the present invention uses methoxide and phase transfer catalyst tetrabutylammonium hydroxide as co-catalysts, and by controlling the ratio and dosage of the two, the reaction conversion rate and selectivity can be significantly improved, thereby improving the product yield. The phase transfer catalyst tetrabutylammonium hydroxide can effectively increase the reaction rate of acetylene and ketone and reduce the formation of polymers; the use of methoxide (such as potassium methoxide) can effectively increase the conversion of monoacetylene salt to generate decynediol, and the combination of the two can effectively improve the reaction conversion rate and selectivity; and the reaction conditions are mild, less catalyst is required, and the production cost is lower.

[0024] (2) The preparation method provided by the present invention has a simple process, low requirements on equipment, can achieve 100% reuse of the recovered solvent, and can be used 10 times to prepare decynediol with excellent conversion rate and selectivity. The preparation method provided by the present invention is a production method with low raw material cost, safety and greenness. DETAILED DESCRIPTION

[0025] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be noted that the following embodiments do not limit the protection scope of the present invention.

[0026] Unless otherwise specified, the raw materials, reagents or devices used in the following examples and comparative examples can be obtained from conventional commercial sources or by existing known methods.

[0027] Example 1

[0028] A method for preparing decynediol comprises the following steps:

[0029] 300g of methyl tert-butyl ether was added into the reactor as solvent. After stirring was started, the reactor temperature was first lowered to 5°C, and then 6g (2%) of potassium methoxide solid and 3.6g (1.2%) of tetrabutylammonium hydroxide as a phase transfer catalyst were added respectively. The nitrogen was pressurized to 0.2MPa, and then the pressure was discharged to 0.03MPa. The nitrogen was replaced 5 times, and acetylene was then introduced into the reactor and the temperature was raised to the reaction temperature of 40°C at the same time. The pressure in the reactor was maintained at 0.05MPa. After the pressure was reached, 225g of methyl isobutyl ketone was slowly added dropwise into the reactor for 4h. After the addition was completed, the reaction was kept warm for 0.3h and the reaction was completed.

[0030] Add 165 g of deionized water into the reaction kettle and stir for 30 min, then stand and separate the layers to obtain crude decynediol;

[0031] The crude decynediol is distilled and purified, and the material at 115°C-120°C at the top of the distillation tower is collected under a pressure of -0.0990 MPa to obtain the product decynediol. Meanwhile, the solvent is recycled and reused.

[0032] Example 2-11

[0033] Example 2-11 provides a method for preparing decynediol, and the specific process parameters and test data are shown in Table 1.

[0034] Table 1

[0035]

[0036]

[0037] Examples 12-21

[0038] Examples 12-21 provide a method for preparing decynediol, wherein the solvent recovered in Example 1 is continuously recovered and reused 10 times to prepare decynediol, wherein if there is a slight loss of solvent, it is replenished. The specific process is as follows:

[0039] 300g of recovered methyl tert-butyl ether was added into the reactor as solvent. After stirring was started, the reactor temperature was first lowered to 5°C, and then 6g of potassium methoxide solid and 3.6g of tetrabutylammonium hydroxide as a phase transfer catalyst were added respectively. The nitrogen was pressurized to 0.2MPa, and then the pressure was discharged to 0.03MPa. The nitrogen was replaced 5 times, and acetylene was then introduced into the reactor and the temperature was raised to the reaction temperature of 40°C at the same time. The pressure in the reactor was maintained at 0.05MPa. After the pressure was reached, 225g of methyl isobutyl ketone was slowly added dropwise into the reactor for 4h. After the addition was completed, the reaction was kept warm for 0.3h and the reaction was completed.

[0040] 165 g of deionized water was added to the reaction kettle and stirred for 30 min. The reaction kettle was allowed to stand for separation of the layers to obtain crude decynediol.

[0041] The crude decynediol is purified by distillation, and the material at 115°C to 120°C at the top of the distillation tower is collected under a pressure of -0.0990 MPa to obtain the product decynediol. Meanwhile, the solvent is recovered.

[0042] After the solvent was recycled and reused continuously for 10 times, the conversion rate and selectivity of the prepared decynediol are shown in Table 2.

[0043] Table 2

[0044]

[0045] As shown in Table 2, the solvent recovered in Example 1 was used ten times to prepare decynediol, and the conversion rate and selectivity were high, with no obvious downward trend. The preparation method provided by the present invention can achieve 100% reuse of the recovered solvent, and is a safe and green production method.

[0046] Comparative Examples 1-5

[0047] Comparative Examples 1-5 provide a method for preparing decynediol, and the specific process parameters and test data are shown in Table 3.

[0048] Table 3

[0049]

[0050] Comparative Example 6

[0051] A method for preparing decynediol comprises the following steps:

[0052] 300g of methyl tert-butyl ether was added into the reactor as solvent. After stirring was started, 6g (2%) of potassium methoxide solid and 3.6g (1.2%) of tetrabutylammonium hydroxide as a phase transfer catalyst were added respectively. The nitrogen was pressurized to 0.2MPa and then discharged to 0.03MPa. The nitrogen was replaced 5 times. Then acetylene was introduced into the reactor and the temperature was raised to the reaction temperature of 40°C. The pressure in the reactor was maintained at 0.05MPa. After the pressure was reached, 225g of methyl isobutyl ketone was slowly added dropwise into the reactor for 4h. After the addition was completed, the reaction was kept warm for 0.3h and the reaction was completed.

[0053] Add 165 g of deionized water into the reaction kettle and stir for 30 min, then stand and separate the layers to obtain crude decynediol;

[0054] The crude decynediol is distilled and purified, and the material at 115°C-120°C at the top of the distillation tower is collected under a pressure of -0.0990 MPa to obtain the product decynediol. Meanwhile, the solvent is recycled and reused.

[0055] Comparative Example 7

[0056] A method for preparing decynediol comprises the following steps:

[0057] 300g of methyl tert-butyl ether was added into the reactor as solvent. After stirring was started, the reactor temperature was first lowered to 5°C, and then 9.6g (3.2%) of tetrabutylammonium hydroxide as a phase transfer catalyst was added. The nitrogen was pressurized to 0.2MPa, and then the pressure was discharged to 0.03MPa. The nitrogen was replaced 5 times. After the temperature was raised to the reaction temperature of 40°C, acetylene was introduced into the reactor, and the pressure in the reactor was maintained at 0.05MPa. After the pressure was reached, 225g of methyl isobutyl ketone was slowly added dropwise into the reactor for 4h. After the addition was completed, the reaction was kept warm for 0.3h and the reaction was completed.

[0058] Add 165 g of deionized water into the reaction kettle and stir for 30 min, then stand and separate the layers to obtain crude decynediol;

[0059] The crude decynediol is distilled and purified, and the material at 115°C-120°C at the top of the distillation tower is collected under a pressure of -0.0990 MPa to obtain the product decynediol. Meanwhile, the solvent is recycled and reused.

[0060] Comparative Example 8

[0061] A method for preparing decynediol comprises the following steps:

[0062] 300g of methyl tert-butyl ether was added into the reactor as solvent. After stirring was started, the reactor temperature was first lowered to 5°C, and then 9.6g (3.2%) of potassium methoxide solid was added. The nitrogen was pressurized to 0.2MPa, and then the pressure was discharged to 0.03MPa. The nitrogen was replaced 5 times. After the temperature was raised to the reaction temperature of 40°C, acetylene was introduced into the reactor to maintain the pressure in the reactor at 0.05MPa. After the pressure was reached, 225g of methyl isobutyl ketone was slowly added dropwise into the reactor for 4h. After the addition was completed, the reaction was kept warm for 0.3h and the reaction was completed.

[0063] Add 165 g of deionized water into the reaction kettle and stir for 30 min, then stand and separate the layers to obtain crude decynediol;

[0064] The crude decynediol is distilled and purified, and the material at 115°C-120°C at the top of the distillation tower is collected under a pressure of -0.0990 MPa to obtain the product decynediol. Meanwhile, the solvent is recycled and reused.

[0065] The specific process parameters and test data of Comparative Examples 6-8 are shown in Table 4.

[0066] Table 4

[0067]

[0068] Comparing the data of Table 1 and Table 3 and Table 4, it can be seen that potassium methoxide and phase transfer catalyst tetrabutylammonium hydroxide are used as catalysts, and the ratio and dosage of the two are controlled, which can effectively improve the conversion rate and selectivity of the reaction. When only one catalyst is used, the reaction cannot proceed smoothly, and its conversion rate and selectivity will be significantly affected, and when the dosage or ratio of the two is not within the scope of protection of the present invention, its effect will also be affected to a certain extent. In addition, in the preparation process, the control of process conditions is also crucial.

[0069] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing decynediol, characterized in that: The following steps are involved: The solvent is cooled and mixed with a catalyst, and then acetylene is introduced and the temperature is raised to a reaction temperature; methyl isobutyl ketone is added dropwise, and after the addition is completed, the temperature is kept for reaction to obtain a first product system; water is added to the first product system, and a crude decynediol product is obtained after layer separation; finally, the crude decynediol product is distilled and the solvent is recovered to obtain decynediol; The catalyst comprises methoxide and tetrabutylammonium hydroxide; the mass ratio of the methoxide to the tetrabutylammonium hydroxide is 1:(0.1-0.8); The added amount of the catalyst is 2.0%-7.5% of the mass of the solvent.

2. The preparation method according to claim 1, characterized in that: The mass ratio of the methoxide to the tetrabutylammonium hydroxide is 1:(0.3-0.75).

3. The preparation method according to claim 1 or 2, characterized in that: The methoxide includes potassium methoxide and / or sodium methoxide.

4. The preparation method according to claim 1 or 2, characterized in that: The added amount of the catalyst is 3.0%-6.5% of the mass of the solvent.

5. The preparation method according to claim 1, characterized in that: The cooling process is to cool the solvent to a temperature of 0-10°C.

6. The preparation method according to claim 1 or 2, characterized in that: The solvent is methyl tert-butyl ether.

7. The preparation method according to claim 6, characterized in that: The mass of the methyl isobutyl ketone is 60%-80% of the mass of the solvent.

8. The preparation method according to any one of claims 1, 2, 5 or 7, characterized in that: The reaction temperature is 35-55° C., the time for dropwise addition of methyl isobutyl ketone is 2.5-4.5 h, and the time for heat preservation reaction is 0.1-0.5 h.

9. The preparation method according to any one of claims 1, 2, 5 or 7, characterized in that: The distillation process is: using a distillation tower to distill the crude decynediol, collecting the material at 115-120° C. at the top of the distillation tower under a pressure of -0.0990 MPa, to obtain the product decynediol.

10. The preparation method according to claim 8, characterized in that: The amount of water added is 10%-50% of the mass of the first product system.

Images