Method for preparing decynediol
By using methanol salt and tetrabutylammonium hydroxide as catalysts, combined with distillation technology, the problems of low conversion rate and selectivity of decynyl diol were solved, achieving a simple preparation process with high yield and reducing production costs.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- ZHEJIANG HUANGMA TECH CO LTD
- Filing Date
- 2025-11-10
- Publication Date
- 2026-06-11
AI Technical Summary
The existing technology has low reaction conversion rate and selectivity of decynediol, resulting in low product yield, and the preparation process is complex and costly.
Methanol salt and tetrabutylammonium hydroxide were used as co-catalysts. Their ratio and dosage were controlled, and the reaction conversion rate and selectivity were improved by controlling the reaction conditions and combining them with distillation technology.
It significantly improves the reaction conversion rate and selectivity of decynediol, reduces production costs, realizes a simple and efficient preparation process, and allows for 100% solvent reuse, making it safe and environmentally friendly.
Smart Images
Figure PCTCN2025133825-FTAPPB-I100001 
Figure PCTCN2025133825-FTAPPB-I100002 
Figure PCTCN2025133825-FTAPPB-I100003
Abstract
Description
A method for preparing decynediol Technical Field
[0001] This invention belongs to the field of fine chemical synthesis technology, specifically relating to a method for preparing decynyl diol. Background Technology
[0002] 2,4,7,9-Tetramethyl-5-decyn-4,7-diol surfactant is a water-based nonionic surfactant that significantly reduces the surface tension of water. This multifunctional surfactant is typically formulated into liquids with various solvents for ease of use. It is used in water-based coatings, dyes, water-based inks, pesticides, and other fields, serving as a wetting agent and defoamer in water-based coatings, improving the uniformity and flowability of the coatings.
[0003] Currently, industrial production of decynediol uses a one-step synthesis from methyl isobutyl ketone and acetylene. However, current processes still suffer from low reaction conversion and selectivity, resulting in low product yields. While some processes can improve product yields, their preparation procedures are complex and require strict condition control. For example, the synthesis process disclosed in patent CN201210517582.1 yields decynediol at only slightly over 70%, with significant raw material residue. Although patent CN202111133150.6 can significantly improve the product yield to 93%, its process is complex, employing high-temperature reaction tubes to accelerate the reaction, resulting in the formation of large amounts of dimethylhexynol, which is a co-production process.
[0004] Therefore, there is an urgent need to provide a simple preparation method that can effectively improve the reaction conversion rate and selectivity for the preparation of decynediol. Summary of the Invention
[0005] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a method for preparing decynyl diol. The preparation method provided by the present invention is simple in process and can effectively improve the reaction conversion rate and selectivity, thereby increasing the product yield.
[0006] This invention provides a method for preparing decynediol.
[0007] Specifically, a method for preparing decynediol includes the following steps:
[0008] After cooling the solvent, it is mixed with the catalyst, then acetylene is introduced and the temperature is raised to the reaction temperature; methyl isobutyl ketone is then added dropwise, and after the addition is complete, the reaction is maintained at the temperature to obtain the first product system; water is added to the first product system, and after separation by layers, crude decynediol is obtained; finally, the crude decynediol is distilled and the solvent is recovered to obtain decynediol.
[0009] The catalyst comprises methacrylate and tetrabutylammonium hydroxide; the mass ratio of the methacrylate 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 amount of catalyst added is 2.0%-7.5% of the mass of the solvent; more preferably, the amount of catalyst added is 3.0%-6.5% of the mass of the solvent.
[0013] Preferably, the amount of methoxide added is 2%-5% of the mass of the solvent; the amount of tetrabutylammonium hydroxide added is 1%-1.5% of the mass of the solvent.
[0014] Preferably, the cooling process involves cooling the solvent to a temperature of 0-10°C, such as 2, 5, 8, or 10°C. Controlling the solvent temperature to 0-10°C allows the methacrylate solid and the phase transfer catalyst tetrabutylammonium hydroxide to maintain good particulate properties. Introducing acetylene before heating further improves the reaction effect.
[0015] Preferably, the solvent is methyl tert-butyl ether. Methyl tert-butyl ether 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; more preferably, the mass of the methyl isobutyl ketone is 65%-75% of the mass of the solvent.
[0017] Preferably, a nitrogen purging process is included before the heating process, and the nitrogen purging is performed 3-5 times. The nitrogen purging process involves first pressurizing to 0.15-0.2 MPa and then depressurizing to 0.02-0.05 MPa.
[0018] Preferably, the pressure of the reaction system is 0.03-0.07 MPa after the acetylene is introduced; more preferably, the pressure of the reaction system is 0.05-0.07 MPa after the acetylene is introduced.
[0019] Preferably, the reaction temperature is 35-55℃, the time for adding methyl isobutyl ketone is 2.5-4.5h, and the time for maintaining the temperature is 0.1-0.5h; more preferably, the reaction temperature is 40-50℃, the time for adding methyl isobutyl ketone is 3-4h, and the time for maintaining the temperature is 0.2-0.5h.
[0020] Preferably, the distillation process is as follows: the crude decynediol is distilled using a distillation column, and the material at the top of the distillation column at 115-120°C is collected 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 beneficial effects of the present invention are as follows:
[0023] (1) The method for preparing decynediol provided by the present invention uses methanol salt and phase transfer catalyst tetrabutylammonium hydroxide as co-catalysts. By controlling the ratio and amount of the two, the reaction conversion rate and selectivity can be significantly improved, thereby increasing the product yield. Among them, the phase transfer catalyst tetrabutylammonium hydroxide can effectively increase the reaction rate of acetylene and ketone and reduce the formation of polymers; and the use of methanol salt (such as potassium methoxide) can effectively improve the conversion of monoacetylene salt to decynediol. 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 this invention is simple in process, has low equipment requirements, can achieve 100% reuse of the recovered solvent, and can still maintain excellent conversion rate and selectivity even after 10 consecutive reuses to prepare decynyl diol. The preparation method provided by this invention is a low-cost, safe and green production method. Detailed Implementation
[0025] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.
[0026] Unless otherwise specified, the raw materials, reagents or apparatus used in the following examples and comparative examples are available from conventional commercial sources or can be obtained by existing known methods.
[0027] Example 1
[0028] A method for preparing decynediol includes the following steps:
[0029] 300g of methyl tert-butyl ether was added to the reactor as a solvent. After stirring, the reactor temperature was lowered to 5°C. Then, 6g of potassium methoxide solid (2%) and 3.6g of tetrabutylammonium hydroxide phase transfer catalyst (1.2%) were added. The reactor was pressurized with nitrogen to 0.2MPa and then depressurized to 0.03MPa. The nitrogen was purged five times. Acetylene was then introduced into the reactor while the temperature was raised to 40°C. The pressure inside the reactor was maintained at 0.05MPa. After the pressure was reached, 225g of methyl isobutyl ketone was slowly added dropwise to the reactor over a period of 4 hours. After the addition was completed, the reactor was kept at the temperature for 0.3 hours to complete the reaction.
[0030] Add 165g of deionized water to the reaction vessel and stir. After stirring for 30 minutes, allow the mixture to stand and separate into layers to obtain crude decynediol.
[0031] The crude decynediol was purified by distillation. The material at the top of the distillation column at 115℃-120℃ was collected under a pressure of -0.0990MPa to obtain the product decynediol. The solvent was recovered 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] Examples 12-21
[0036] Examples 12-21 provide a method for preparing decynediol, in which the solvent recovered in Example 1 is continuously recycled 10 times to prepare decynediol, with any slight solvent loss replenished. The specific process is as follows:
[0037] 300g of recovered methyl tert-butyl ether was added to the reactor as a solvent. After stirring, the reactor temperature was lowered to 5°C, and then 6g of potassium methoxide solid and 3.6g of tetrabutylammonium hydroxide phase transfer catalyst were added. The reactor was pressurized with nitrogen to 0.2MPa and then depressurized to 0.03MPa. The nitrogen was purged five times. Acetylene was then introduced into the reactor while the temperature was raised to the reaction temperature of 40°C. The pressure inside the reactor was maintained at 0.05MPa. After the pressure was reached, 225g of methyl isobutyl ketone was slowly added dropwise to the reactor over a period of 4 hours. After the addition was completed, the reactor was kept at this temperature for 0.3 hours, and the reaction was then complete.
[0038] Add 165g of deionized water to the reaction vessel and stir. After stirring for 30 minutes, allow the mixture to stand and separate into layers to obtain crude decynyl diol.
[0039] The crude decynediol was purified by distillation. The material at the top of the distillation column at 115°C-120°C was collected under a pressure of -0.0990 MPa to obtain the product decynediol. The solvent was recovered simultaneously.
[0040] The conversion rate and selectivity of the prepared decynediol after the solvent was continuously recycled 10 times are shown in Table 2.
[0041] Table 2
[0042] As shown in Table 2, the conversion rate and selectivity of decynediol prepared by continuously reusing the solvent recovered in Example 1 ten times were high, with no obvious downward trend. The preparation method provided by this invention can achieve 100% reuse of the recovered solvent, which is a safe and green production method.
[0043] Comparative Examples 1-5
[0044] Comparative Examples 1-5 provide a method for preparing decynediol, and the specific process parameters and test data are shown in Table 3.
[0045] Table 3
[0046] Comparative Example 6
[0047] A method for preparing decynediol includes the following steps:
[0048] 300g of methyl tert-butyl ether was added to the reactor as a solvent. After stirring, 6g of potassium methoxide solid (2%) and 3.6g of tetrabutylammonium hydroxide phase transfer catalyst (1.2%) were added. The reactor was pressurized with nitrogen to 0.2MPa and then depressurized to 0.03MPa. The nitrogen was purged five times. Acetylene was then introduced into the reactor while the temperature was raised to the reaction temperature of 40℃. The pressure inside the reactor was maintained at 0.05MPa. After the pressure was reached, 225g of methyl isobutyl ketone was slowly added dropwise to the reactor over a period of 4 hours. After the addition was completed, the reactor was kept at the temperature for 0.3 hours to complete the reaction.
[0049] Add 165g of deionized water to the reaction vessel and stir. After stirring for 30 minutes, allow the mixture to stand and separate into layers to obtain crude decynediol.
[0050] The crude decynediol was purified by distillation. The material at the top of the distillation column at 115℃-120℃ was collected under a pressure of -0.0990MPa to obtain the product decynediol. The solvent was recovered and reused.
[0051] Comparative Example 7
[0052] A method for preparing decynediol includes the following steps:
[0053] 300g of methyl tert-butyl ether was added to the reactor as a solvent. After stirring, the reactor temperature was lowered to 5°C, and then 9.6g (3.2%) of tetrabutylammonium hydroxide, a phase transfer catalyst, was added. The reactor was pressurized with nitrogen to 0.2MPa, and then depressurized to 0.03MPa. The nitrogen was purged five times. The temperature was then raised to the reaction temperature of 40°C. Acetylene was introduced into the reactor to maintain the pressure inside the reactor at 0.05MPa. After the pressure was reached, 225g of methyl isobutyl ketone was slowly added dropwise to the reactor over a period of 4 hours. After the addition was completed, the reactor was kept at the temperature for 0.3 hours to complete the reaction.
[0054] Add 165g of deionized water to the reaction vessel and stir. After stirring for 30 minutes, allow the mixture to stand and separate into layers to obtain crude decynediol.
[0055] The crude decynediol was purified by distillation. The material at the top of the distillation column at 115℃-120℃ was collected under a pressure of -0.0990MPa to obtain the product decynediol. The solvent was recovered and reused.
[0056] Comparative Example 8
[0057] A method for preparing decynediol includes the following steps:
[0058] 300g of methyl tert-butyl ether was added to the reactor as a solvent. After stirring, the reactor temperature was lowered to 5°C, and then 9.6g of potassium methoxide solid (3.2%) was added. Nitrogen gas was pressurized to 0.2MPa, and then depressurized to 0.03MPa. The nitrogen was purged 5 times. The temperature was then raised to the reaction temperature of 40°C, and acetylene was introduced into the reactor to maintain the pressure inside the reactor at 0.05MPa. After the pressure was reached, 225g of methyl isobutyl ketone was slowly added dropwise to the reactor over a period of 4 hours. After the addition was completed, the reaction was maintained at the temperature for 0.3 hours, and the reaction was then complete.
[0059] Add 165g of deionized water to the reaction vessel and stir. After stirring for 30 minutes, allow the mixture to stand and separate into layers to obtain crude decynediol.
[0060] The crude decynediol was purified by distillation. The material at the top of the distillation column at 115℃-120℃ was collected under a pressure of -0.0990MPa to obtain the product decynediol. The solvent was recovered and reused.
[0061] The specific process parameters and test data for Comparative Examples 6-8 are shown in Table 4.
[0062] Table 4
[0063] Comparing the data in Tables 1, 3, and 4, it is evident that using potassium methoxide and the phase transfer catalyst tetrabutylammonium hydroxide as catalysts, and controlling their ratio and dosage, 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. Furthermore, when the dosage or ratio of both catalysts is outside the scope of protection of this invention, its effectiveness will also be somewhat affected. In addition, the control of process conditions is crucial during the preparation process.
[0064] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.
Claims
1. A method for preparing decynediol, characterized in that, Includes the following steps: After cooling the solvent, it is mixed with the catalyst, then acetylene is introduced and the temperature is raised to the reaction temperature; methyl isobutyl ketone is then added dropwise, and after the addition is complete, the reaction is maintained at the temperature to obtain the first product system; water is added to the first product system, and after separation by layers, crude decynediol is obtained; finally, the crude decynediol is subjected to distillation and the solvent is recovered to obtain decynediol. The catalyst comprises methacrylate and tetrabutylammonium hydroxide; the mass ratio of the methacrylate to the tetrabutylammonium hydroxide is 1:(0.1-0.8); The amount of catalyst added 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 methacrylate to the tetrabutylammonium hydroxide is 1:(0.3-0.75).
3. The preparation method according to claim 1 or 2, characterized in that, The methoxides include potassium methoxide and / or sodium methoxide.
4. The preparation method according to claim 1 or 2, characterized in that, The amount of catalyst added 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 involves cooling 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℃, the time for adding methyl isobutyl ketone is 2.5-4.5h, and the time for maintaining the temperature during the reaction is 0.1-0.5h.
9. The preparation method according to any one of claims 1, 2, 5 or 7, characterized in that, The distillation process is as follows: the crude decynediol is distilled using a distillation column, and the material at the top of the distillation column at 115-120℃ is collected under a pressure of -0.0990MPa 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.