Preparation methods for butynediol diethoxy ether and butynediol polyethoxy ether

Abstract

The present invention belongs to the technical field of organic compounds. Disclosed are preparation methods for butynediol diethoxy ether and butynediol polyethoxy ether. The preparation method for butynediol polyethyoxyl ether comprises the following steps: mixing 1,4-butynediol and a basic catalyst, then adding a first ethylene oxide to perform a first polymerization reaction, and after the reaction is finished, conducting a post-treatment, so as to prepare butynediol diethyoxyl ether; and mixing the butynediol diethoxy ether with a second ethylene oxide and a phosphazene salt catalyst to perform a second polymerization reaction, so as to prepare butynediol polyethoxy ether. The butynediol diethoxy ether prepared in the present invention has a light color and a narrow molecular weight distribution. By using the butynediol diethoxy ether to prepare butynediol polyethoxy ether and using a phosphazene salt as a catalyst for the second polymerization reaction, butynediol polyethoxy ether having a light color, a narrow molecular weight distribution, a low peroxide value and a low residual quantity of 1,4-butynediol can be prepared.

Description

A method for preparing butynediol diethoxy ether and butynediol polyethoxy ether Technical Field

[0001] This invention belongs to the field of organic compound technology, specifically relating to a method for preparing butynediol diethoxy ether and butynediol polyethoxy ether. Background Technology

[0002] Butynediol polyethoxylates are important nonionic surfactants with a wide range of applications. For example, butynediol polyethoxylates (10-20) are used as antistatic agents in textile processing and synthetic fiber production; as softeners and lubricants in leather tanning; butynediol polyethoxylates (5-10) are used as dyeing auxiliaries in the dye industry; as grinding aids for pigments and inks in the coatings and printing industry; as paper relubricants in the paper industry; as dispersants in the rubber industry; as plasticizers in the plastics industry; as corrosion inhibitors and anti-corrosion agents for oilfield pipelines in the petroleum industry; and as brighteners and leveling agents in the electroplating industry. In conclusion, butynediol polyethoxylates have a very broad application prospect and are of great development value.

[0003] Currently, alkaline catalysts, primarily alkali metals or alkaline earth metals, are used in the industrial synthesis of butynediol polyethoxyethers. These catalysts are inexpensive and have a wide range of applications. However, due to their relatively low activity, the prepared butynediol polyethoxyethers often suffer from issues such as insufficient molecular weight and dark color. Furthermore, the long reaction time leads to the generation of numerous byproducts during polymerization, and the high peroxide value of the product negatively impacts its performance. The resulting products are mainly concentrated in the low-end general market and are not suitable for high-end or specialized chemical industries, resulting in insufficient market competitiveness.

[0004] Therefore, there is an urgent need to provide a method for preparing butynediol polyethoxy ethers that can produce high-quality butynediol polyethoxy ethers with light color, low peroxide value, low 1,4-butynediol residue, and narrow molecular weight distribution. 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 butynediol diethoxy ether and butynediol polyethoxy ether. The butynediol diethoxy ether prepared by the present invention has a light color and a narrow molecular weight distribution; the prepared butynediol polyethoxy ether has a light color, low peroxide value, low 1,4-butynediol residue, and a narrow molecular weight distribution.

[0006] This invention provides a butynediol diethoxy ether.

[0007] Specifically, a method for preparing butynediol diethoxy ether includes the following steps:

[0008] 1,4-Butynediol and a basic catalyst were mixed, and then a first ethylene oxide was added to carry out a first polymerization reaction. After the reaction was completed, butynediol diethoxy ether was obtained through post-treatment.

[0009] The alkaline catalyst is an alkali metal hydroxide and an alkoxide.

[0010] The alkaline alkali metal hydroxide includes one or more of potassium hydroxide, sodium hydroxide, calcium hydroxide, and magnesium hydroxide. The alkoxide includes one or more of potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, potassium propoxide, sodium propoxide, potassium butoxide, and sodium butoxide. More preferably, the alkaline catalyst is potassium hydroxide and sodium butoxide.

[0011] Preferably, the mass ratio of potassium hydroxide to sodium butoxide is 1:(1-10); more preferably, the mass ratio of potassium hydroxide to sodium butoxide is 1:(1-8).

[0012] Preferably, the mass of the alkaline catalyst is 1.0‰ to 5.0‰ of the total mass of the 1,4-butynediol and the first ethylene oxide; more preferably, the mass of the alkaline catalyst is 2.0‰ to 4.0‰ of the total mass of the 1,4-butynediol and the first ethylene oxide.

[0013] Preferably, the molar ratio of 1,4-butynediol to the first ethylene oxide is 1:(1.8-2.2).

[0014] Preferably, the pressure of the first polymerization reaction is 0–0.4 MPa, the temperature is 50–100 °C, and the time is 4–7 h. More preferably, the pressure of the first polymerization reaction is 0.1–0.3 MPa, and the temperature is 60–80 °C.

[0015] Preferably, the addition rate of the first ethylene oxide is: the mass of ethylene oxide added per hour accounts for 15% to 25% of the total mass of the first ethylene oxide.

[0016] The present invention also provides a method for preparing butynediol polyethoxylate.

[0017] Specifically, a method for preparing a butynediol polyethoxylate includes the following steps:

[0018] (1) Mix 1,4-butynediol and an alkaline catalyst, then add ethylene oxide to carry out the first polymerization reaction, and after the reaction is completed, the butynediol diethoxy ether is obtained through post-treatment.

[0019] (2) The butynediol diethoxy ether prepared in step (1) is mixed with the second ethylene oxide and phosphazene salt catalyst to carry out the second polymerization reaction to obtain butynediol polyethoxy ether.

[0020] Preferably, in step (2), the phosphazene salt catalyst includes at least one of organic phosphazene salt and inorganic phosphazene salt.

[0021] Preferably, in step (2), the phosphazene salt catalyst is bis(disubstituted amino)chlorophosphazene salt.

[0022] Preferably, in step (2), the mass of the phosphazene salt catalyst is 0.02‰ to 0.20‰ of the total mass of the butynediol diethoxy ether and the second ethylene oxide. More preferably, the mass of the phosphazene salt catalyst is 0.05‰ to 0.15‰ of the total mass of the butynediol diethoxy ether and the second ethylene oxide.

[0023] Preferably, in step (2), the molar ratio of butynediol diethoxy ether to the second ethylene oxide is 1:(1-30); more preferably, the molar ratio of butynediol diethoxy ether to the second ethylene oxide is 1:(2-20).

[0024] Preferably, in step (2), the pressure of the second polymerization reaction is 0–0.4 MPa, the temperature is 50–100 °C, and the time is 2–5 h. More preferably, the pressure of the second polymerization reaction is 0.1–0.3 MPa, the temperature is 60–80 °C, and the time is 3–4 h.

[0025] Preferably, in step (2), before the second polymerization reaction, the reaction system is first dehydrated and impurity removed using a falling film evaporator. Using a falling film evaporator for dehydration and impurity removal before the second polymerization reaction effectively removes moisture and other low-molecular-weight impurities from the reaction system, significantly improving the quality of the butyrynethiol polyethoxyether product synthesized in the workshop.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0027] (1) The method for preparing butynediol diethoxy ether provided by the present invention, by selecting a composite catalyst of alkali metal hydroxide and alkoxide and optimizing the process, can prepare butynediol diethoxy ether with light color and narrow molecular weight distribution, which lays a good foundation for the subsequent preparation of butynediol polyethoxy ether.

[0028] (2) The method for preparing butynediol polyethoxy ether provided by this invention uses phosphazene salt as a catalyst to catalyze the second polymerization reaction of butynediol polyethoxy ether and ethylene oxide. Because phosphazene salt catalysts have high catalytic activity towards epoxides, they can catalyze the polymerization of epoxides at low concentrations. Therefore, a small amount is used in the synthesis of butynediol polyethoxy ether, and the trace amount of phosphazene salt catalyst has almost negligible impact on the performance of the product, requiring no post-treatment removal. The butynediol polyethoxy ether synthesized by this invention has a light color, narrow molecular weight distribution, low peroxide value, and low 1,4-butynediol residue, showing excellent results in many industrial fields. Detailed Implementation

[0029] 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.

[0030] Unless otherwise specified, the raw materials, reagents or apparatus used in the following experimental examples are available from conventional commercial sources or can be obtained by existing known methods.

[0031] This invention provides a butynediol diethoxy ether.

[0032] Specifically, a method for preparing butynediol diethoxy ether includes the following steps:

[0033] 1,4-Butynediol and a basic catalyst were mixed, and then a first ethylene oxide was added to carry out a first polymerization reaction. After the reaction was completed, butynediol diethoxy ether was obtained through post-treatment.

[0034] The alkaline catalyst is an alkali metal hydroxide and an alkoxide. This invention does not impose any particular limitation on the order of addition of the alkali metal hydroxide and the alkoxide; they can be simply mixed according to the stated mass ratio before use, or the alkali metal hydroxide and the alkoxide can be added to the reaction system separately according to the mass ratio.

[0035] In this invention, the alkaline alkali metal hydroxide includes one or more of potassium hydroxide, sodium hydroxide, calcium hydroxide, and magnesium hydroxide. The alkoxide includes one or more of potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, potassium propoxide, sodium propoxide, potassium butoxide, and sodium butoxide. More preferably, the alkaline catalyst is potassium hydroxide and sodium butoxide.

[0036] In this invention, the mass ratio of potassium hydroxide to sodium butoxide is preferably 1:(1-10); more preferably, the mass ratio of potassium hydroxide to sodium butoxide is preferably 1:(1-8).

[0037] In this invention, the mass of the alkaline catalyst is 1.0‰ to 5.0‰ of the total mass of the 1,4-butynediol and the first ethylene oxide; preferably, the mass of the alkaline catalyst is 2.0‰ to 4.0‰ of the total mass of the 1,4-butynediol and the first ethylene oxide.

[0038] In this invention, the molar ratio of 1,4-butynediol to the first ethylene oxide is 1:(1.8-2.2).

[0039] In this invention, the first polymerization reaction is preferably carried out in a reactor, which is preferably equipped with a stirring device, an electric heating jacket and an internal water cooling coil. This invention does not have a special limitation on the source of the reactor, and any reactor from a source known in the art can be used.

[0040] In this invention, 1,4-butynediol and the catalyst are mixed in a reactor, the reactor is sealed, and then the air in the reactor is replaced with nitrogen three times. Stirring is started, and the temperature is raised to perform vacuum dehydration for 1 to 2 hours. After dehydration is completed, ethylene oxide is continuously introduced to carry out the first polymerization reaction.

[0041] In this invention, the vacuum dehydration temperature is preferably 50-100°C, more preferably 60-80°C, and even more preferably 65-75°C; the vacuum dehydration pressure is preferably -0.098 MPa.

[0042] In this invention, the pressure of the first polymerization reaction is 0–0.4 MPa, the temperature is 50–100°C, and the time is 4–7 h. More preferably, the pressure of the first polymerization reaction is 0.1–0.3 MPa, and the temperature is 60–80°C. More preferably, the temperature of the first polymerization reaction is 65–75°C, and the time is 5–6 h.

[0043] In this invention, the addition rate of the first ethylene oxide is: the mass of ethylene oxide added per hour accounts for 15% to 25% of the total mass of the first ethylene oxide.

[0044] In this invention, after the first polymerization reaction is completed, the resulting reaction product system is post-treated. The post-treatment process preferably includes: maturing the first polymerization product system at 65–75°C until the pressure inside the reactor no longer changes; then vacuum degassing the reactor at 65–75°C, maintaining the degassing state at -0.098 MPa for 10–30 minutes; then cooling to below 50°C to obtain crude butynediol diethoxy ether; adding deionized water and phosphoric acid to the crude butynediol diethoxy ether, neutralizing for 30–50 minutes, then adding an adsorbent and diatomaceous earth filter aid, mixing for 30–50 minutes, and heating for dehydration; after dehydration, maintaining the temperature at 100–110°C and -0.098 MPa for 1–2 hours, then cooling to below 70°C and filtering to obtain the post-treated butynediol diethoxy ether.

[0045] In this invention, the temperature is controlled at 70-80°C during the post-treatment process of adding deionized water and neutralizing phosphoric acid, and the temperature is also controlled at 70-80°C during the mixing process of adding adsorbent and diatomaceous earth filter aid.

[0046] In this invention, the mass of the deionized water is preferably 5% to 15% of the total mass of the crude butynediol diethoxy ether, the mass of the phosphoric acid is 80% of the total mass of the catalyst, the adsorbent is preferably one or more of aluminum silicate, magnesium silicate, and magnesium aluminum silicate, and the mass of the adsorbent is preferably 7‰ to 15‰ of the total mass of the crude butynediol polyethoxy ether. The mass of the diatomaceous earth filter aid is preferably 3‰ to 7‰ of the total mass of the crude butynediol polyethoxy ether. This invention does not impose any special limitations on the adsorbent or diatomaceous earth filter aid; commercially available products well-known in the art are acceptable. The post-treatment process of this invention does not impose any special limitations on the cooling and filtration processes; well-known processes in the art can be followed.

[0047] In this invention, the catalyst is easy to use and remove: after the first polymerization reaction is completed, it can be easily separated from the product by post-treatment adsorption, and the process is simple.

[0048] This invention also provides a method for preparing butynediol polyethoxylate, comprising the following steps:

[0049] The butynediol diethoxy ether prepared above was mixed with a second ethylene oxide and a phosphazene salt catalyst to carry out a second polymerization reaction, thereby obtaining butynediol polyethoxy ether.

[0050] In this invention, the post-treated butynediol diethoxy ether and phosphazene salt catalyst are first added to a reaction vessel, which is then sealed. The air in the reaction vessel is then purged three times with nitrogen, stirring is initiated, and the temperature is raised to 50–100°C for vacuum dehydration for 1–2 hours. After vacuum dehydration, 2–20 moles of second ethylene oxide are continuously introduced to carry out the second polymerization reaction. Preferably, the mass of ethylene oxide added per hour is 20%–30% of the total mass of the second ethylene oxide.

[0051] In this invention, the vacuum dehydration temperature is preferably 50-100°C, more preferably 60-80°C, and even more preferably 65-75°C; the vacuum dehydration pressure is preferably -0.098 MPa.

[0052] In this invention, the phosphazene salt catalyst includes at least one of organic phosphazene salts and inorganic phosphazene salts.

[0053] In this invention, the phosphazene salt catalyst is a bis(disubstituted amino)chlorophosphazene salt. Its preparation is described in US2487859 and is also commercially available.

[0054] In this invention, the mass of the phosphazene salt catalyst is 0.02‰ to 0.20‰ of the total mass of the butynediol diethoxy ether and the second ethylene oxide. More preferably, the mass of the phosphazene salt catalyst is 0.05‰ to 0.15‰ of the total mass of the butynediol diethoxy ether and the second ethylene oxide.

[0055] In this invention, the molar ratio of butynediol diethoxy ether to the second ethylene oxide is 1:(1-30); preferably, the molar ratio of butynediol diethoxy ether to the second ethylene oxide is 1:(2-20).

[0056] In this invention, the second polymerization reaction is preferably carried out in a reactor, which is preferably equipped with a stirring device, an electric heating jacket and an internal water cooling coil. This invention does not have a special limitation on the source of the reactor, and any reactor from a source known in the art can be used.

[0057] In this invention, the pressure of the second polymerization reaction is 0–0.4 MPa, the temperature is 50–100°C, and the time is 2–5 h. Preferably, the pressure of the second polymerization reaction is 0.1–0.3 MPa, the temperature is 60–80°C, and the time is 3–4 h. More preferably, the temperature of the second polymerization reaction is 65–75°C, and the time is 3–4 h.

[0058] In this invention, after the second polymerization reaction is completed, the resulting product system is preferably aged at 65-75°C until the pressure inside the reactor no longer changes. Then, the reactor is degassed under vacuum and kept in a degassed state at a pressure of -0.098 MPa for 10-30 minutes. Finally, the temperature is lowered to below 50°C to obtain butynediol polyethoxy ether.

[0059] When the laboratory synthesis method for butynediol polyethoxyether is applied to mass production in a workshop, product quality fluctuations often occur, affecting downstream applications. Through process improvements, specifically in the workshop production process, it was found that using a vacuum pump for dehydration before the second polymerization reaction resulted in product quality fluctuations, impacting downstream products. However, by using a falling film evaporator for dehydration and removal of other low-molecular-weight impurities before the second polymerization reaction, the quality of the prepared butynediol polyethoxyether product was significantly improved. This method can be widely applied to the workshop synthesis of butynediol polyethoxyether.

[0060] Experimental Example 1-1

[0061] A method for preparing butynediol diethoxy ether includes the following steps:

[0062] 430g of 1,4-butynediol, 1.5‰ potassium hydroxide, and 1.5‰ sodium butoxide (i.e., the catalyst composition is a 1:1 mass ratio of potassium hydroxide to sodium butoxide, and the catalyst dosage is 3.0wt‰ (relative to the total mass of 1,4-butynediol and ethylene oxide) were added to a dry 2.5L reactor equipped with a stirrer, an electrically heated jacket, and an internal water-cooled coil. The reactor was then sealed. The air in the reactor was replaced with nitrogen three times. The stirrer was then turned on, and the temperature was raised to 70℃. Vacuum dehydration was carried out for 1 hour at a dehydration pressure of -0.098 MPa. After dehydration, the first polymerization reaction was carried out, and 4g of ethylene oxide was continuously introduced. 40g (i.e., the molar ratio of 1,4-butynediol to ethylene oxide is 1:2) was added during the reaction. The addition rate of ethylene oxide was controlled (the mass of ethylene oxide added uniformly over 1 hour accounted for 20% of the total mass of ethylene oxide added). The reaction temperature was maintained at 70℃ and the reaction pressure at 0.25MPa. The above amount of ethylene oxide was introduced over 5 hours (i.e., the first polymerization reaction time was 5h). The resulting reaction product system was matured at 70℃ for about 4 hours until the pressure inside the reactor no longer changed. The reactor was then degassed under vacuum and maintained at a pressure of -0.098MPa for 15 minutes. After degassed, the temperature was lowered to 50℃ to obtain crude butynediol diethoxy ether.

[0063] The crude butynediol diethoxy ether was transferred to a post-treatment unit, where 10 wt% of the crude butynediol diethoxy ether and 80 wt% of the catalyst (phosphoric acid) were added. Neutralization was carried out for 30 minutes at a controlled temperature of 75°C. Then, 10 wt% of magnesium aluminum silicate and 5 wt% diatomaceous earth filter aid were added, and the mixture was stirred for 30 minutes, maintaining the adsorption temperature at 75°C. After adsorption, dehydration was carried out at a heating rate of 20°C / h for 3 hours. Finally, a second dehydration was performed at a dehydration temperature of 110°C and a dehydration pressure of -0.098 MPa for 1 hour. After dehydration, the temperature was lowered to 70°C, and the mixture was filtered to obtain the post-treated butynediol diethoxy ether.

[0064] Experimental Examples 1-2 to 1-12

[0065] In Experiments 1-2 to 1-12, except for the composition of the polymerization catalyst, the amount of catalyst used, and the reaction temperature, all other operating conditions were the same as in Experiment 1-1. The specific changes in conditions are shown in Table 1.

[0066] The performance of butynediol diethoxy ethers prepared in Examples 1-2 to 1-12 was tested. Color was determined using the Pt-Co method, and the instrument used was a Lovibond colorimeter (PFXI 995). The molecular weight distribution of butynediol diethoxy ethers was expressed as the distribution coefficient (D). A smaller D indicates a narrower molecular weight distribution and better technical performance. The number-average molecular weight Mn and distribution coefficient D of butynediol diethoxy ethers were determined using a Waters ultra-high performance gel electrophoresis (ACQUITY APC), and the specific results are shown in Table 1.

[0067] Table 1. Condition parameters and test data of butynediol diethoxy ether for Experiments 1-2 to 1-12

[0068] Comparison of Experiments 1-1 to 1-12 shows that all alkaline catalysts can participate in the reaction, but the butynediol diethoxy ether synthesized by a single strong alkali metal hydroxide has a darker color. Specifically, rubidium hydroxide, strontium hydroxide, cesium hydroxide, barium hydroxide, and the second polymerization catalyst, bis(disubstituted amino)chlorophosphine salt, due to their stronger alkalinity, and dimethylamine, trimethylamine, diethylamine, triethylamine, n-propylamine, tripropylamine, N-toluidine, and triphenylamine, due to their amino groups, result in a darker color for the synthesized butynediol diethoxy ether. Meanwhile, butynediol diethoxy ether synthesized by a single potassium alkoxide or sodium alkoxide catalyst exhibits poor performance in terms of molecular weight and distribution coefficient. Through comparative experiments, a combination of alkali metal hydroxide catalysts and potassium alkoxide or sodium alkoxide catalysts was chosen for the synthesis of butynediol. Due to the molecular structure of butynediol, the use of potassium alkoxide or sodium alkoxide instead of potassium butoxide or sodium butoxide can lead to increased side reactions, which is detrimental to downstream applications. Therefore, in subsequent experimental examples, a composite catalyst of potassium hydroxide and sodium butoxide was selected.

[0069] Experimental Examples 2-1 to 2-12

[0070] Except for the amount and ratio of potassium hydroxide and sodium butoxide composite catalyst, and the reaction temperature, the operating conditions in Experiments 2-1 to 2-12 were the same as those in Experiment 1-1. The specific changes in conditions are shown in Table 2.

[0071] The performance of butynediol diethoxy ethers prepared in Examples 2-1 to 2-12 was tested. Color was determined using the Pt-Co method, and the instrument used was a Lovibond colorimeter (PFXI 995). The molecular weight distribution of butynediol diethoxy ethers was expressed as the distribution coefficient (D). A smaller D indicates a narrower molecular weight distribution and better technical performance. The number-average molecular weight Mn and distribution coefficient D of butynediol diethoxy ethers were determined using a Waters ultra-high performance gel electrophoresis (ACQUITY APC). Specific results are shown in Table 2.

[0072] Table 2 shows the condition parameters and test data of butynediol diethoxy ether for Experiments 1-12.

[0073] Table 2 shows that when the proportion of potassium hydroxide is higher than that of sodium butoxide, the synthesized butynediol diethoxy ether has a darker color. Conversely, when the proportion of sodium butoxide is higher than that of potassium hydroxide, the synthesized butynediol diethoxy ether exhibits poorer Mn and molecular weight distribution. Furthermore, increasing the reaction temperature and catalyst dosage also significantly affects the quality of the synthesized butynediol diethoxy ether. In conclusion, the selection of a suitable catalyst and a suitable process route has a crucial impact on the prepared butynediol diethoxy ether and is critical to the final quality of the prepared butynediol polyethoxy ether.

[0074] Experimental Example 3-1

[0075] A method for preparing butynediol polyethoxylate includes the following steps:

[0076] 350g of butynediol diethoxy ether prepared in Example 1-1 and 0.1wt‰ (i.e., the total mass of butynediol diethoxy ether and ethylene oxide) of bis(disubstituted amino)chlorophosphazene salt were added to a dry 2.5L reactor equipped with a stirrer, an electrically heated outer jacket, and an internal water-cooled coil. The reactor was then sealed. The air in the reactor was purged with nitrogen three times. The stirrer was turned on, the temperature was raised to 70°C, and vacuum treatment was carried out for 1 hour at a pressure of -0.098 MPa. Vacuum dehydration was then carried out for 1 hour at a dehydration pressure of -0.098 MPa. After dehydration, the second polymerization reaction was carried out, and 708g of ethylene oxide (i.e., butynediol) was continuously introduced. The molar ratio of glycol diethoxy ether to ethylene oxide is 1:8. During the reaction, the addition rate of ethylene oxide is controlled (the mass of ethylene oxide added uniformly over 1 hour accounts for 25% of the total mass of ethylene oxide added), the reaction temperature is maintained at 70℃ and the reaction pressure is 0.20MPa, and the above amount of ethylene oxide is introduced for 4 hours (i.e., the second polymerization reaction time is 4h). The resulting reaction product system is aged at 70℃ for about 30 minutes until the pressure inside the reactor no longer changes. The reactor is then degassed under vacuum and maintained at a pressure of -0.098MPa for 15 minutes. After degassed, the temperature is lowered to 50℃ to obtain butyrynethyl glycol polyethoxy ether.

[0077] Experimental Examples 3-2 to 3-6

[0078] Except for the butynediol diethoxy ether (prepared using Experiments 1-3, 1-5, 1-7, 1-9, and 1-11 respectively), the operating conditions of Experiments 3-2 to 3-6 were the same as those of Experiment 3-1. The specific parameters are shown in Table 3.

[0079] Experimental Examples 3-7 to 3-16

[0080] Except for the amount of catalyst and the reaction temperature, the operating conditions of Experiments 3-7 to 3-16 were the same as those of Experiment 3-1. The specific parameters are shown in Table 4.

[0081] Experimental Example 4-1

[0082] Example 4-1 provides a method for preparing butynediol polyethoxylate. Compared with Example 3-1, except for the catalyst and catalyst amount used in the second polymerization reaction, all other conditions are the same as in Example 4-1. The specific process is as follows:

[0083] 350g of butynediol diethoxy ether (Example 1-1) and 1wt‰ (i.e., the total mass of butynediol diethoxy ether and ethylene oxide) of potassium hydroxide were added to a dry 2.5L reactor equipped with a stirrer, an electrically heated outer jacket, and an internal water-cooled coil. The reactor was then sealed. The air in the reactor was purged with nitrogen three times. The stirrer was then turned on, and the temperature was raised to 70°C. Vacuum treatment was carried out for 1 hour at a pressure of -0.098 MPa, with a dehydration pressure of -0.098 MPa. After dehydration, the second polymerization reaction was carried out, with 708g of ethylene oxide (i.e., the total mass of butynediol diethoxy ether and ethylene oxide) continuously introduced. (Molar ratio 1:8) During the reaction, the addition rate of ethylene oxide was controlled (the mass of ethylene oxide added uniformly over 1 hour accounted for 25% of the total mass of ethylene oxide added), the reaction temperature was maintained at 70℃ and the reaction pressure at 0.20MPa, and the above amount of ethylene oxide was introduced for 4 hours (i.e., the second polymerization reaction time was 4h); the resulting reaction product system was matured at 70℃ for about 30 minutes until the pressure inside the reactor no longer changed, the reactor was degassed under vacuum, and the degassed state was maintained at -0.098MPa pressure for 15 minutes. After degassed, the temperature was lowered to 50℃ to obtain butynediol polyethoxylate.

[0084] Experimental Examples 4-2 to 4-5

[0085] Except for the catalysts used in the second polymerization reaction (each catalyst was reacted under optimal conditions of its own dosage and reaction temperature), Experimental Examples 4-2 to 4-5 and Experimental Example 3-1 were the same as Experimental Example 3-1. The data of Experimental Example 3-1 are listed in Table 5 for easy comparison.

[0086] The performance of butynediol polyethoxylates prepared in Examples 3-1 to 3-16 and Examples 4-1 to 4-5 was tested. Color was determined using the Pt-Co method, and the instrument used was a Lovibond colorimeter (PFXI 995). The free 1,4-butynediol content was determined using a Shimadzu liquid chromatograph (LC-20A). The molecular weight distribution of butynediol polyethoxylates was expressed using the distribution coefficient (D). A smaller D indicates a narrower molecular weight distribution and better technical performance. The number-average molecular weight Mn and distribution coefficient D of butynediol polyethoxylates were determined using a Waters ultra-high performance gel electrophoresis (ACQUITY APC). The test data are shown in Tables 3, 4, and 5.

[0087] Table 3 shows the condition parameters and test data of butyrynethiol polyethoxylates for Experiments 3-1 to 3-6.

[0088] As shown in Table 3, the product quality of butynediol diethoxy ether is closely related to the quality of the final prepared butynediol polyethoxy ether. Specifically, the lighter the color and the narrower the molecular weight distribution of the butynediol diethoxy ether, the better the quality of the obtained butynediol polyethoxy ether product.

[0089] Table 4 shows the condition parameters and test data of butynediol polyethoxylates for Experiments 3-1, 3-7 to 3-16.

[0090] As shown in Table 4, when the catalyst dosage is ≥0.15 wt‰, the color of butynediol polyethoxyether begins to darken and the peroxide value begins to increase; when the catalyst dosage is ≤0.05 wt‰, the residual 1,4-butynediol in butynediol polyethoxyether begins to increase, the molecular weight is smaller, and the molecular weight distribution becomes wider; when the reaction temperature is >75℃, the color of butynediol polyethoxyether begins to darken and the peroxide value begins to increase; when the reaction temperature is <65℃, the residual 1,4-butynediol in butynediol polyethoxyether begins to increase, the molecular weight is smaller, and the molecular weight distribution becomes wider.

[0091] Table 5 shows the condition parameters and test data of butynediol polyethoxylate for Experiments 3-1 and 4-1 to 4-5.

[0092] As shown in Table 5, the catalyst bis(disubstituted amino)chlorophosphazene salt has a significant advantage in the synthesis of butynediol polyethoxylate. When using alkaline or acid catalysts, and even when each catalyst is used under optimal conditions in terms of dosage and reaction temperature, the effect of the catalyst used in this invention cannot be achieved.

[0093] Experimental Example 5-1

[0094] Experimental Example 5-1 describes a method for preparing butynediol polyethoxylates in a workshop, as detailed below:

[0095] To the 8m dryer equipped with a stirring, steam-heated jacket and internal water-cooled coils 31720 kg of 1,4-butynediol, potassium hydroxide (1.5‰ of the total mass of 1,4-butynediol and ethylene oxide), and sodium butoxide (1.5‰ of the total mass of 1,4-butynediol and ethylene oxide) were added to the reactor (i.e., the catalyst composition was 1:1 in mass ratio of potassium hydroxide to sodium butoxide, and the catalyst dosage was 3.0 wt‰ (i.e., the total mass of 1,4-butynediol and ethylene oxide)). The reactor was sealed. The air in the reactor was replaced twice with nitrogen. The stirring was started, and the temperature was raised to 70°C for vacuum dehydration for 1 hour at a dehydration pressure of -0.098 MPa. After dehydration, the first polymerization reaction was carried out by continuously introducing 1760 kg of ethylene oxide (i.e., the total mass of 1,4-butynediol and ethylene oxide). (Molar ratio 1:2) During the reaction, the addition rate of ethylene oxide was controlled (the mass of ethylene oxide added uniformly in 1 hour accounted for 20% of the total mass of ethylene oxide added), the reaction temperature was maintained at 70℃ and the reaction pressure at 0.25MPa, and the above amount of ethylene oxide was introduced for 5 hours (i.e., the first polymerization reaction time was 5h); the resulting reaction product system was matured at 70℃ for about 4 hours until the pressure in the reactor no longer changed, the reactor was degassed under vacuum, and the degassed state was maintained at -0.098MPa pressure for 15 minutes. After degassed, the temperature was lowered to 50℃ to obtain crude butyryne glycol diethoxy ether.

[0096] The crude butynediol diethoxy ether was transferred to an 8m dryer equipped with stirring, a steam-heated jacket, and internal water-cooled coils. 3 In the post-treatment vessel, 10 wt% of deionized water and 80 wt% of phosphoric acid (total mass of catalyst) of crude butynediol diethoxy ether were added and neutralized for 30 minutes. Then, 10 wt% of magnesium aluminum silicate and 5 wt% diatomaceous earth filter aid of crude butynediol diethoxy ether were added and mixed for 30 minutes. The mixture was then heated and dehydrated (heating rate of 10℃ / h) for 6 hours. Finally, a second dehydration was carried out at a dehydration temperature of 110℃ and a dehydration pressure of -0.098MPa for 1 hour. After dehydration, the temperature was lowered to 70℃ and filtered to obtain the post-treated butynediol diethoxy ether.

[0097] The 8m dryer will be equipped with a stirring, steam-heated jacket and internal water-cooled coils. 31760 kg of the above-mentioned butynediol diethoxy ether and 0.1 wt‰ (i.e., the total mass of butynediol diethoxy ether and ethylene oxide) of bis(disubstituted amino)chlorophosphazene salt were added to the reactor, and the reactor was sealed. The air in the reactor was replaced twice with nitrogen, the stirring was started, the temperature was raised to 70°C, and vacuum treatment was carried out for 1 hour at a pressure of -0.098 MPa using a vacuum pump. The dehydration pressure was -0.098 MPa. After dehydration was completed, the second polymerization reaction was carried out, and 3520 kg of ethylene oxide (i.e., the molar ratio of butynediol diethoxy ether to ethylene oxide was 1:1) was continuously introduced. 8) During the reaction, control the rate of ethylene oxide addition (the mass of ethylene oxide added uniformly over 1 hour should be 25% of the total mass of ethylene oxide added), maintain the reaction temperature at 70℃ and the reaction pressure at 0.20MPa, and introduce the above amount of ethylene oxide for 4 hours (i.e., the second polymerization reaction time is 4h); mature the resulting reaction product system at 70℃ for about 30 minutes until the pressure inside the reactor no longer changes, perform vacuum degassing on the reactor, maintain the degassing state at -0.098MPa pressure for 15 minutes, and after degassing is completed, cool down to 50℃ to obtain butynediol polyethoxylate.

[0098] Experimental Examples 5-2 to 5-3

[0099] Experiments 5-2 to 5-3 involved the preparation of butynediol diethoxylates in the workshop. Except for the molar ratio of butynediol diethoxylate to ethylene oxide, the operating conditions were the same as in Experiment 5-1. Specific changes in conditions are shown in Table 6.

[0100] Experimental Example 6-1

[0101] Example 6-1 describes a method for preparing butynediol polyethoxylates in a workshop. Except for the use of a falling film evaporator instead of a vacuum pump for dehydration before the second polymerization reaction, all other operating conditions are the same as in Example 5-1. Details are as follows:

[0102] To the 8m dryer equipped with a stirring, steam-heated jacket and internal water-cooled coils 31720 kg of 1,4-butynediol, potassium hydroxide (1.5‰ of the total mass of 1,4-butynediol and ethylene oxide), and sodium butoxide (1.5‰ of the total mass of 1,4-butynediol and ethylene oxide) were added to the reactor (i.e., the catalyst composition was 1:1 in mass ratio of potassium hydroxide to sodium butoxide, and the catalyst dosage was 3.0 wt‰ (i.e., the total mass of 1,4-butynediol and ethylene oxide)). The reactor was sealed. The air in the reactor was replaced twice with nitrogen. The stirring was started, and the temperature was raised to 70°C for vacuum dehydration for 1 hour at a dehydration pressure of -0.098 MPa. After dehydration, the first polymerization reaction was carried out by continuously introducing 1760 kg of ethylene oxide (i.e., the total mass of 1,4-butynediol and ethylene oxide). (Molar ratio 1:2) During the reaction, the addition rate of ethylene oxide was controlled (the mass of ethylene oxide added uniformly in 1 hour accounted for 20% of the total mass of ethylene oxide added), the reaction temperature was maintained at 70℃ and the reaction pressure at 0.25MPa, and the above amount of ethylene oxide was introduced for 5 hours (i.e., the first polymerization reaction time was 5h); the resulting reaction product system was matured at 70℃ for about 4 hours until the pressure in the reactor no longer changed, the reactor was degassed under vacuum, and the degassed state was maintained at -0.098MPa pressure for 15 minutes. After degassed, the temperature was lowered to 50℃ to obtain crude butyryne glycol diethoxy ether.

[0103] The crude butynediol diethoxy ether was transferred to an 8m drying chamber equipped with a stirring, steam-heated jacket, and internal water-cooled coils. 3 In the post-treatment vessel, 10 wt% of deionized water and 80 wt% of phosphoric acid (total mass of catalyst) of crude butynediol diethoxy ether were added and neutralized for 30 minutes. Then, 10 wt% of magnesium aluminum silicate and 5 wt% diatomaceous earth filter aid of crude butynediol diethoxy ether were added and mixed for 30 minutes. The mixture was then heated and dehydrated (heating rate of 10℃ / h) for 6 hours. Finally, a second dehydration was carried out at a dehydration temperature of 110℃ and a dehydration pressure of -0.098MPa for 1 hour. After dehydration, the temperature was lowered to 70℃ and filtered to obtain the post-treated butynediol diethoxy ether.

[0104] The 8m dryer will be equipped with a stirring, steam-heated jacket and internal water-cooled coils. 31760 kg of the above-mentioned butynediol diethoxy ether and 0.1 wt‰ (i.e., the total mass of butynediol diethoxy ether and ethylene oxide) of bis(disubstituted amino)chlorophosphazene salt were added to the reactor, and the reactor was sealed. The air in the reactor was replaced twice with nitrogen, the stirring was started, the temperature was raised to 70°C, and vacuum treatment was carried out for 1 hour using a falling film evaporator at a pressure of -0.098 MPa. The dehydration pressure was -0.098 MPa. After dehydration was completed, the second polymerization reaction was carried out, and 3520 kg of ethylene oxide (i.e., the molar ratio of butynediol diethoxy ether to ethylene oxide was 1:1) was continuously introduced. 8) During the reaction, control the rate of ethylene oxide addition (the mass of ethylene oxide added uniformly in 1 hour accounts for 25% of the total mass of ethylene oxide added), maintain the reaction temperature at 70℃ and the reaction pressure at 0.20MPa, and introduce the above amount of ethylene oxide for 4 hours (i.e., the second polymerization reaction time is 4h); mature the obtained reaction product system at 70℃ for about 30 minutes until the pressure in the reactor no longer changes, perform vacuum degassing on the reactor, maintain the degassing state at a pressure of -0.098MPa for 15 minutes, and after degassing is completed, cool down to 50℃ to obtain butynediol polyethoxylate.

[0105] Experimental Examples 6-2 to 6-3

[0106] Experiments 6-2 to 6-3 were for the preparation of butynediol polyethoxylates in the workshop. Among them, Experiments 6-2 and 5-2 were the same as Experiment 5-2 except that a falling film evaporator was used instead of a vacuum pump for dehydration before the second polymerization reaction. Experiments 6-3 and 5-3 were the same as Experiment 5-3 except that a falling film evaporator was used instead of a vacuum pump for dehydration before the second polymerization reaction. See Table 6 for details.

[0107] Table 6. Condition parameters and test data of butynediol polyethoxylates in Experiments 5-1 to 5-3 and 6-1 to 6-3.

[0108] As shown in Table 6, during the workshop production process, using a vacuum pump for dehydration before the second polymerization reaction resulted in product quality fluctuations, affecting downstream applications. Conversely, using a falling film evaporator for dehydration and removal of other low-molecular-weight impurities before the second polymerization reaction significantly improved product quality.

[0109] 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 butynediol diethoxy ether, characterized in that, Includes the following steps: 1,4-Butynediol and a basic catalyst were mixed, and then a first ethylene oxide was added to carry out a first polymerization reaction. After the reaction was completed, butynediol diethoxy ether was obtained through post-treatment. The alkaline catalyst is an alkali metal hydroxide and an alkoxide.

2. The preparation method according to claim 1, characterized in that, The alkaline catalyst is preferably potassium hydroxide and sodium butoxide.

3. The preparation method according to claim 2, characterized in that, The preferred mass ratio of potassium hydroxide to sodium butoxide is 1:(1-10).

4. The preparation method according to any one of claims 1 to 3, characterized in that, The mass of the alkaline catalyst is 1.0‰ to 5.0‰ of the total mass of the 1,4-butynediol and the first ethylene oxide.

5. The preparation method according to any one of claims 1 to 3, characterized in that, The pressure of the first polymerization reaction is 0-0.4 MPa, the temperature is 50-100℃, and the time is 4-7 h.

6. A method for preparing butynediol polyethoxylate, characterized in that, Includes the following steps: (1) Mix 1,4-butynediol and an alkaline catalyst, then add ethylene oxide to carry out the first polymerization reaction, and after the reaction is completed, the butynediol diethoxy ether is obtained through post-treatment. (2) The butynediol diethoxy ether prepared in step (1) is mixed with the second ethylene oxide and phosphazene salt catalyst to carry out the second polymerization reaction to obtain butynediol polyethoxy ether.

7. The preparation method according to claim 6, characterized in that, In step (2), the phosphazene salt catalyst includes at least one of organic phosphazene salt and inorganic phosphazene salt.

8. The preparation method according to claim 6 or 7, characterized in that, In step (2), the phosphazene salt catalyst is bis(disubstituted amino)chlorophosphazene salt.

9. The preparation method according to claim 8, characterized in that, In step (2), the mass of the phosphazene salt catalyst is 0.02‰ to 0.20‰ of the total mass of the butynediol diethoxy ether and the second ethylene oxide.

10. The preparation method according to claim 6, characterized in that, In step (2), before the second polymerization reaction is carried out, the reaction system is dehydrated and impurities are removed using a falling film evaporator.

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