Preparation method of butynediol diethoxy ether and butynediol polyethoxy ether

Abstract

The invention belongs to the technical field of organic compounds, and discloses a preparation method of butynediol diethoxy ether and butynediol polyethoxy ether. The preparation method of the butynediol polyethyoxyl ether comprises the following steps: mixing 1, 4-butynediol and a basic catalyst, then adding first ethylene oxide to carry out a first polymerization reaction, and after the reaction is finished, carrying out post-treatment to prepare butynediol diethyoxyl ether; and mixing the butynediol diethoxy ether with second ethylene oxide and a phosphazene salt catalyst, and carrying out a second polymerization reaction to prepare the butynediol polyethoxy ether. The butynediol diethoxy ether prepared by the method is light in color and narrow in molecular weight distribution. The polyethyoxyl butynediol with light color, narrow molecular weight distribution, low peroxide value and small 1, 4-butynediol residual quantity can be prepared by using the polyethyoxyl butynediol as a catalyst of a second polymerization reaction and using phosphazene salt as a catalyst of the second polymerization reaction by using the polyethyoxyl butynediol polyethyoxyl butynediol polyethyoxyl butynediol polyethyoxyl butynediol polyethyoxyl butynediol polyethyoxyl butynediol polyethyoxyl butynediol.

Description

Technical Field

[0001] The invention belongs to the technical field of organic compounds, and in particular relates to a preparation method of butynediol diethoxy ether and butynediol polyethoxy ether. Background Art

[0002] Butynediol polyethoxy ether is an important nonionic surfactant with a wide range of applications. For example, butynediol polyethoxy (10-20) ether is used as an antistatic agent in textile processing and production of synthetic fibers; it is used as a softener and lubricant for tanning leather on leather; butynediol polyethoxy (5-10) ether is used as a dyeing auxiliary in the dye industry; it is used as a pigment and ink grinding auxiliary in the coating and printing industry; it is used as a paper relubricant in the papermaking industry; it is used as a dispersant in the rubber industry; it is used as a plasticizer in the plastic industry, as an oilfield pipeline anticorrosion and corrosion inhibitor in the petroleum industry, and as a brightener and leveling agent in the electroplating industry. In summary, butynediol polyethoxy ether has a very broad application prospect and is of great development value.

[0003] At present, alkaline catalysts are used in the industry to synthesize butynediol polyethoxy ethers, mainly alkali metals or alkaline earth metals. Such catalysts are cheap and have a wide range of applications. However, due to the low activity of the catalyst, the prepared butynediol polyethoxy ethers will have problems such as substandard molecular weight and dark color. At the same time, due to the long reaction time, more by-products will be produced during the polymerization process and the product peroxide value is high, which affects the product performance. The prepared products are mainly concentrated in the low-end general market, not suitable for high-end and special chemical industries, and lack market competitiveness.

[0004] Therefore, there is an urgent need to provide a method for preparing butynediol polyethoxy ether, which can prepare high-quality butynediol polyethoxy ether with light color, low peroxide value, small amount of 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 above-mentioned prior art. To this end, the present invention provides a method for preparing butynediol diethoxy ether and butynediol polyethoxy ether. The butynediol diethoxy ether prepared by the present invention has light color and narrow molecular weight distribution; the butynediol polyethoxy ether prepared by the present invention has light color, low peroxide value, less 1,4-butynediol residue, and narrow molecular weight distribution.

[0006] The invention provides butynediol diethoxy ether.

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

[0008] Mixing 1,4-butynediol and a basic catalyst, then adding a first ethylene oxide to carry out a first polymerization reaction, and after the reaction is completed, post-processing is performed to obtain butynediol diethoxy ether;

[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. Further preferably, the alkaline catalyst is preferably potassium hydroxide and sodium butoxide.

[0011] Preferably, the mass ratio of the potassium hydroxide to the sodium butoxide is preferably 1:(1-10); further preferably, the mass ratio of the potassium hydroxide to the sodium butoxide is preferably 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; further 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 the 1,4-butynediol to the first ethylene oxide is 1:(1.8-2.2).

[0014] Preferably, the first polymerization reaction is carried out at a pressure of 0-0.4 MPa, a temperature of 50-100°C, and a time of 4-7 hours. More preferably, the first polymerization reaction is carried out at a pressure of 0.1-0.3 MPa, and a temperature of 60-80°C.

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

[0016] The invention also provides a method for preparing butynediol polyethoxy ether.

[0017] Specifically, a method for preparing butynediol polyethoxy ether comprises the following steps:

[0018] (1) mixing 1,4-butynediol and a basic catalyst, then adding a first ethylene oxide to carry out a first polymerization reaction, and after the reaction is completed, post-treating to obtain butynediol diethoxy ether;

[0019] (2) mixing the butynediol diethoxy ether prepared in step (1) with a second ethylene oxide and a phosphazene salt catalyst, and performing a second polymerization reaction to obtain butynediol polyethoxy ether.

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

[0021] Preferably, in step (2), the phosphazene salt catalyst is a 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. Further 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 the butynediol diethoxy ether to the second ethylene oxide is 1:(1-30); further preferably, the molar ratio of the butynediol diethoxy ether to the second ethylene oxide is 1:(2-20).

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

[0025] Preferably, in step (2), before the second polymerization reaction, the reaction system is first dehydrated and impurity-removed by a falling film evaporator. Dehydration and impurity-removal by a falling film evaporator before the second polymerization reaction can effectively remove water and other low-molecular impurities in the reaction system, and can significantly improve the quality of the product of butynediol polyethoxy ether synthesized in the workshop.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

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

[0028] (2) The method for preparing butynediol polyethoxy ether provided by the present invention uses phosphazene salt as a catalyst to catalyze butynediol polyethoxy ether and ethylene oxide to carry out a second polymerization reaction. Since the phosphazene salt catalyst has high catalytic activity for epoxides, it can catalyze the polymerization of epoxides at low concentrations. Therefore, a small amount of the phosphazene salt catalyst is used in the synthesis of butynediol polyethoxy ether. The effect of a trace amount of the phosphazene salt catalyst on the performance of the product is almost negligible, and no post-treatment is required for removal. The butynediol polyethoxy ether synthesized by the present invention has a light color, a narrow molecular weight distribution, a low peroxide value, and a small amount of 1,4-butynediol residue, and has excellent application effects in many industrial fields. DETAILED DESCRIPTION

[0029] 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 pointed out that the following embodiments do not limit the protection scope of the present invention.

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

[0031] The embodiment of the present invention provides butynediol diethoxy ether.

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

[0033] Mixing 1,4-butynediol and a basic catalyst, then adding a first ethylene oxide to carry out a first polymerization reaction, and after the reaction is completed, post-processing is performed to obtain butynediol diethoxy ether;

[0034] The alkaline catalyst is an alkali metal hydroxide and an alkoxide. The present invention has no particular limitation on the order of adding the alkali metal hydroxide and the alkoxide, and they can be used by simply mixing them in the mass ratio, or by adding the alkali metal hydroxide and the alkoxide into the reaction system in the mass ratio.

[0035] In the present 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. Further preferably, the alkaline catalyst is preferably potassium hydroxide and sodium butoxide.

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

[0037] In the present 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 the present invention, the molar ratio of the 1,4-butynediol to the first ethylene oxide is 1:(1.8-2.2).

[0039] In the present invention, the first polymerization reaction is preferably carried out in a reactor, and the reactor is preferably equipped with a stirring device, an electric heating jacket and an internal water-cooling coil. The present invention has no special limitation on the source of the reactor, and any of the above-mentioned reactors with sources known in the art can be used.

[0040] The present invention preferably mixes 1,4-butynediol and a catalyst in a reactor, seals the reactor, replaces the air in the reactor with nitrogen three times, starts stirring, heats up and performs vacuum dehydration for 1 to 2 hours, and continuously introduces ethylene oxide after dehydration to perform a first polymerization reaction.

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

[0042] In the present 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 hours. 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 hours.

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

[0044] In the present invention, after the first polymerization reaction is completed, the obtained reaction product system is post-treated, and the post-treatment process preferably includes: the first polymerization reaction product system is aged at 65-75°C until the pressure in the reactor no longer changes, and then the reactor is vacuum degassed at 65-75°C, the degassed state is maintained at a pressure of -0.098MPa for 10-30 minutes, and then the temperature is lowered to below 50°C to obtain a crude product of butynediol diethoxy ether; deionized water and phosphoric acid are added to the crude product of butynediol diethoxy ether, neutralized for 30-50 minutes, and then an adsorbent and a diatomaceous earth filter aid are added, mixed for 30-50 minutes, heated, and dehydrated. After dehydration is completed, the temperature is 100-110°C, the pressure is -0.098Mpa, and the temperature is kept for 1-2 hours, and the temperature is lowered to below 70°C for filtration to obtain the post-treated butynediol diethoxy ether.

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

[0046] In the present 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, the mass of the adsorbent is preferably 7‰ to 15‰ of the total mass of the crude butynediol polyethoxy ether, and the mass of the diatomaceous earth filter aid is preferably 3‰ to 7‰ of the total mass of the crude butynediol polyethoxy ether. The present invention has no special restrictions on the adsorbent and diatomaceous earth filter aid, and any commercially available product known in the art can be used. There is no special restriction on the cooling and filtering process in the post-treatment of the present invention, and it can be carried out according to the process known in the art.

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

[0048] The present invention also provides a method for preparing butynediol polyethoxy ether, comprising the following steps:

[0049] The butynediol diethoxy ether prepared above is mixed with a second ethylene oxide and a phosphazene salt catalyst, and a second polymerization reaction is carried out to obtain butynediol polyethoxy ether.

[0050] The present invention preferentially puts the post-treated butynediol diethoxy ether and phosphazene salt catalyst into a reactor, seals the reactor, then replaces the air in the reactor with nitrogen three times, starts stirring, heats to 50-100° C., performs vacuum dehydration for 1-2 hours, and continuously introduces 2-20 moles of the second ethylene oxide after the vacuum dehydration is completed to perform the second polymerization reaction. In the present invention, preferably, the mass of the ethylene oxide added per hour accounts for 20%-30% of the total mass of the second ethylene oxide.

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

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

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

[0054] In the present 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. Further 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 the present invention, the molar ratio of the butynediol diethoxy ether to the second ethylene oxide is 1:(1-30); preferably, the molar ratio of the butynediol diethoxy ether to the second ethylene oxide is 1:(2-20).

[0056] In the present invention, the second polymerization reaction is preferably carried out in a reactor, and the reactor is preferably equipped with a stirring device, an electric heating jacket and an internal water-cooling coil. The present invention has no special limitation on the source of the reactor, and any of the above-mentioned reactors with sources known in the art can be used.

[0057] In the present 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 hours. 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 hours. More preferably, the temperature of the second polymerization reaction is 65-75°C, and the time is 3-4 hours.

[0058] In the present invention, after completing the second polymerization reaction, the present invention preferably matures the obtained product system at 65-75°C until the pressure in the reactor no longer changes, then vacuum degassing the reactor, maintaining the degassed state at a pressure of -0.098MPa for 10-30 minutes, and then cooling to below 50°C to obtain butynediol polyethoxy ether.

[0059] When the method of synthesizing butynediol polyethoxy ether in the laboratory is applied to mass production in the workshop, the product often has quality fluctuations, which in turn affects the downstream application of the product. Through the improvement of the workshop process, in particular, in the workshop production process, it was found that the vacuum pump was used for dehydration before the second polymerization reaction, and then the second polymerization reaction was carried out, and the product had quality fluctuations, which affected the downstream products. Before the second polymerization reaction, a falling film evaporator was used for dehydration and removal of other low-molecular impurities, and then the second polymerization reaction was carried out, and the quality of the prepared butynediol polyethoxy ether product can be significantly improved. This method can be widely used in the workshop to synthesize butynediol polyethoxy ether.

[0060] Experimental Example 1-1

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

[0062] 430 g of 1,4-butynediol and 1.5 ‰ of potassium hydroxide and 1.5 ‰ of sodium butoxide (i.e., the catalyst composition is a mass ratio of potassium hydroxide to sodium butoxide of 1:1, and the amount of catalyst is 3.0 wt ‰ (relative to the total mass of 1,4-butynediol and ethylene oxide)) were added to a dry 2.5 L reactor equipped with stirring, an electric heating jacket and an internal water cooling coil, and the reactor was sealed; the air in the reactor was replaced with nitrogen 3 times, stirring was started, the temperature was raised to 70°C, and vacuum dehydration was performed for 1 hour, the dehydration pressure was -0.098 MPa, and the first polymerization reaction was performed after dehydration was completed, and ethylene oxide was continuously introduced for 4 40g (i.e., the molar ratio of 1,4-butynediol to ethylene oxide is 1:2). During the reaction, the rate of addition of ethylene oxide is controlled (the mass of ethylene oxide uniformly added in 1 hour accounts for 20% of the total mass of ethylene oxide added), the reaction temperature is maintained at 70°C and the reaction pressure is maintained at 0.25MPa, and the time for introducing the above amount of ethylene oxide is 5 hours (i.e., the first polymerization reaction time is 5h); the obtained reaction product system is aged at 70°C for about 4 hours until the pressure in the reactor no longer changes, the reactor is vacuum degassed, and the degassed state is maintained at a pressure of 0.098MPa for 15 minutes. After the degassed, the temperature is lowered to 50°C to obtain a crude product of butynediol diethoxy ether.

[0063] The crude butynediol diethoxy ether is transferred to a post-processing device, and deionized water of 10wt% of the total mass of the crude butynediol diethoxy ether and phosphoric acid of 80wt% of the total mass of the catalyst are added thereto, and the neutralization is carried out for 30 minutes, and the neutralization temperature is controlled at 75°C. Then, magnesium aluminum silicate of 10wt% of the total mass of the crude butynediol diethoxy ether and 5wt% of diatomaceous earth filter aid are added, and after mixing for 30 minutes, the adsorption temperature is controlled at 75°C. After the adsorption is completed, the temperature is increased and dehydrated (the heating rate is 20°C / h), and the temperature is increased and dehydrated for 3 hours. Finally, a second dehydration is carried out at a dehydration temperature of 110°C and a dehydration pressure of 0.098MPa for 1 hour. After the dehydration is completed, the temperature is lowered to 70°C, and filtered to obtain the post-treated butynediol diethoxy ether.

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

[0065] In Experimental Examples 1-2 to 1-12, except for the polymerization reaction catalyst composition, catalyst dosage, and reaction temperature, other operating conditions are the same as those in Experimental Example 1-1. Specific changes in conditions are shown in Table 1.

[0066] The performance test of butynediol diethoxy ether prepared in Experimental Examples 1-2 to 1-12 was carried out. Among them, the color test method was determined by the Pt-Co method, and the measuring instrument was Lovibond colorimeter (PFXI 995). The molecular weight distribution of butynediol diethoxy ether was expressed by the distribution coefficient (abbreviated as D). The smaller D is, the narrower the molecular weight distribution is and the better the technical effect is. The number average molecular weight Mn and distribution coefficient D of butynediol diethoxy ether were measured by waters ultra-high performance gel chromatograph (ACQUITYAPC), and the specific results are shown in Table 1.

[0067] Table 1 Condition parameters of experimental examples 1-2 to 1-12 and test data of butynediol diethoxy ether

[0068]

[0069] From the comparison of experimental examples 1-1 to 1-12, it can be seen that alkaline catalysts can participate in the reaction, but the color of butynediol diethoxy ether synthesized by a single strong alkali metal hydroxide is dark. In particular, rubidium hydroxide, strontium hydroxide, cesium hydroxide, barium hydroxide and the second polymerization catalyst bis (disubstituted amino) chlorophosphazene salt are stronger in alkalinity and dimethylamine, trimethylamine, diethylamine, triethylamine, n-propylamine, tripropylamine, N-toluidine and triphenylamine are amino groups, which will cause the synthesized butynediol diethoxy ether to be darker in color; while the butynediol diethoxy ether synthesized by a single potassium alcoholate or sodium alcoholate catalyst performs poorly in terms of molecular weight and distribution coefficient. Through experimental comparison, the method of selecting an alkali metal hydroxide catalyst and a potassium alcoholate or sodium alcoholate catalyst compound to synthesize butynediol. Due to the molecular structure of butynediol, when potassium alcoholate or sodium alcoholate does not use potassium butoxide or sodium butoxide, it will also lead to an increase in product side reactions, which is not conducive to downstream applications. Therefore, in the subsequent experimental examples, a composite catalyst of potassium hydroxide and sodium butoxide was selected.

[0070] Experimental Examples 2-1 to 2-12

[0071] Except for the amount of potassium hydroxide and sodium butoxide composite catalyst and the catalyst composite ratio, and the reaction temperature, the other operating conditions of Experimental Examples 2-1 to 2-12 are the same as those of Experimental Example 1-1. The specific changes in conditions are shown in Table 2.

[0072] The performance test of butynediol diethoxy ether prepared in Experimental Examples 2-1 to 2-12 was carried out, wherein the color test method was determined by the Pt-Co method, and the measuring instrument was Lovibond colorimeter (PFXI 995). The molecular weight distribution of butynediol diethoxy ether was represented by the distribution coefficient (abbreviated as D). The smaller D is, the narrower the molecular weight distribution is, and the better the technical effect is. The number average molecular weight Mn and the distribution coefficient D of butynediol diethoxy ether were measured by the waters ultra-high performance gel chromatograph (ACQUITYAPC), and the specific results are shown in Table 2.

[0073] Table 2 Condition parameters of experimental examples 1 to 12 and test data of butynediol diethoxy ether

[0074]

[0075]

[0076] According to the test data in Table 2, when the proportion of potassium hydroxide is higher than that of sodium butoxide, the color of the synthesized butynediol diethoxy ether is darker, and when the proportion of sodium butoxide is higher than that of potassium hydroxide, the synthesized butynediol diethoxy ether is poor in Mn and molecular weight distribution. At the same time, increasing the reaction temperature and the amount of catalyst also have a great influence on the quality of the synthesized butynediol diethoxy ether. In summary, how to choose a suitable catalyst and a suitable process route have an important influence on the prepared butynediol diethoxy ether, and are very critical to the quality of the finally prepared butynediol polyethoxy ether.

[0077] Experimental Example 3-1

[0078] A method for preparing butynediol polyethoxy ether comprises the following steps:

[0079] 350 g of butynediol diethoxy ether prepared in Experimental Example 1-1 and bis(disubstituted amino)chlorophosphazene salt with a catalyst amount of 0.1 wt‰ (i.e., the total mass of butynediol diethoxy ether and ethylene oxide) were added to a dry 2.5 L reactor equipped with stirring, an electric heating jacket and an internal water cooling coil, and the reactor was sealed; the air in the reactor was replaced with nitrogen 3 times, stirring was turned on, the temperature was raised to 70°C, vacuum treated at a pressure of 0.098 MPa for 1 hour, vacuum dehydration was performed for 1 hour, the dehydration pressure was -0.098 MPa, and the second polymerization reaction was performed after the dehydration was completed, and 708 g of ethylene oxide (i.e., butynediol diethoxy ether) was continuously introduced. The molar ratio of glycol diethoxy ether to ethylene oxide is 1:8) during the reaction, the rate of addition of ethylene oxide is controlled (the mass of ethylene oxide uniformly added in 1 hour accounts for 25% of the total mass of ethylene oxide added), the reaction temperature is maintained at 70° C. and the reaction pressure is maintained at 0.20 MPa, and the above amount of ethylene oxide is introduced for 4 hours (i.e., the second polymerization reaction time is 4 hours); the obtained reaction product system is aged at 70° C. for about 30 minutes until the pressure in the reactor no longer changes, the reactor is vacuum degassed, and the degassed state is maintained at a pressure of 0.098 MPa for 15 minutes. After the degassed, the temperature is lowered to 50° C. to obtain butynediol polyethoxy ether.

[0080] Experimental Examples 3-2 to 3-6

[0081] Except for butynediol diethoxy ether (prepared using Experimental Examples 1-3, 1-5, 1-7, 1-9, and 1-11, respectively), the other operating conditions of Experimental Examples 3-2 to 3-6 are the same as those of Experimental Example 3-1. The specific parameters are shown in Table 3.

[0082] Experimental Examples 3-7 to 3-16

[0083] Except for the different catalyst dosage and reaction temperature, the other operating conditions of Experimental Examples 3-7 to 3-16 are the same as those of Experimental Example 3-1. The specific parameters are shown in Table 4.

[0084] Experimental Example 4-1

[0085] Experimental Example 4-1 provides a method for preparing butynediol polyethoxy ether. Compared with Experimental Example 3-1, except for the catalyst and catalyst amount used in the second polymerization reaction, other conditions are the same as those in Experimental Example 4-1. The specific process is as follows:

[0086] 350g of butynediol diethoxy ether of Experimental Example 1-1 and potassium hydroxide with a catalyst dosage of 1wt‰ (i.e., the total mass of butynediol diethoxy ether and ethylene oxide) were added to a dry 2.5L reactor with stirring, electric heating jacket and internal water-cooling coil, and the reactor was sealed; the air in the reactor was replaced with nitrogen 3 times, stirring was turned on, the temperature was raised to 70°C, and vacuum treatment was carried out at a pressure of 0.098MPa for 1 hour, the dehydration pressure was -0.098Mpa, and the second polymerization reaction was carried out after dehydration was completed, and 708g of ethylene oxide (i.e., 1wt‰ of butynediol diethoxy ether and ethylene oxide) was continuously introduced. The molar ratio is 1:8) during the reaction, the addition rate of ethylene oxide is controlled (the mass of ethylene oxide uniformly added in 1 hour accounts for 25% of the total mass of ethylene oxide added), the reaction temperature is maintained at 70°C 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 obtained reaction product system is aged at 70°C for about 30 minutes until the pressure in the reactor no longer changes, the reactor is vacuum degassed, and the degassed state is maintained at a pressure of 0.098MPa for 15 minutes. After the degassing is completed, the temperature is lowered to 50°C to obtain butynediol polyethoxy ether.

[0087] Experimental Examples 4-2 to 4-5

[0088] Experimental Examples 4-2 to 4-5 are the same as Experimental Example 3-1 except for the catalyst used for the second polymerization reaction (each catalyst reacts under optimal conditions of its own dosage and reaction temperature). At the same time, the data of Experimental Example 3-1 are listed in Table 5 for easy comparison.

[0089] The performance tests were conducted on the butynediol polyethoxy ethers prepared in Experimental Examples 3-1 to 3-16 and Experimental Examples 4-1 to 4-5, wherein the color test method was determined by the PtCo method, and the measuring instrument was Lovibond colorimeter (PFXI 995). The free 1,4-butynediol content was determined by Shimadzu liquid chromatograph (LC-20A). The molecular weight distribution of butynediol polyethoxy ether was expressed by the distribution coefficient (abbreviated as D). The smaller D is, the narrower the molecular weight distribution is, and the better the technical effect is. The number average molecular weight Mn and distribution coefficient D of butynediol polyethoxy ether were determined by waters ultra-high performance gel chromatograph (ACQUITY APC). The test data are shown in Tables 3, 4, and 5.

[0090] Table 3 Condition parameters of experimental examples 3-1 to 3-6 and test data of butynediol polyethoxy ether

[0091]

[0092] It can be seen from Table 3 that the product quality of butynediol diethoxy ether is closely related to the quality of the butynediol polyethoxy ether finally prepared. Among them, the lighter the color of butynediol diethoxy ether and the narrower the molecular weight distribution, the better the product quality of the butynediol polyethoxy ether obtained.

[0093] Table 4 Condition parameters of experimental examples 3-1, 3-7 to 3-16 and test data of butynediol polyethoxy ether

[0094]

[0095] It can be seen from Table 4 that when the catalyst dosage is ≥0.15wt‰, the color of butynediol polyethoxy ether begins to darken and the peroxide value begins to increase; when the catalyst dosage is ≤0.05wt‰, the residual 1,4-butynediol in butynediol polyethoxy ether begins to increase, the molecular weight is small, and the molecular weight distribution becomes wider; when the reaction temperature is greater than 75°C, the color of butynediol polyethoxy ether begins to darken and the peroxide value begins to increase; when the reaction temperature is less than 65°C, the residual 1,4-butynediol in butynediol polyethoxy ether begins to increase, the molecular weight is small, and the molecular weight distribution becomes wider.

[0096] Table 5 Condition parameters and test data of butynediol polyethoxy ether of Experimental Examples 3-1 and 4-1 to 4-5

[0097]

[0098] It can be seen from Table 5 that the catalyst bis(disubstituted amino)chlorophosphazene salt has obvious advantages in synthesizing butynediol polyethoxy ether. When a base catalyst or an acid catalyst is used, and each catalyst is used at a relatively optimal amount and reaction temperature, the effect of the catalyst used in the present invention cannot be achieved.

[0099] Experimental Example 5-1

[0100] Experimental Example 5-1 is a method for preparing butynediol polyethoxy ether in a workshop, which is as follows:

[0101] Dry 8m with stirring, steam heating jacket and internal water cooling coil 31720kg 1,4-butynediol and 1.5‰ potassium hydroxide and 1.5‰ sodium butoxide (i.e., the catalyst composition is a mass ratio of potassium hydroxide to sodium butoxide of 1:1, and the amount of catalyst is 3.0wt‰ (i.e., the total mass of 1,4-butynediol and ethylene oxide)) are added to the reactor, and the reactor is sealed; the air in the reactor is replaced with nitrogen twice, stirring is started, the temperature is raised to 70°C, and vacuum dehydration is carried out for 1 hour, the dehydration pressure is -0.098Mpa, and the first polymerization reaction is carried out after dehydration is completed, and 1760kg ethylene oxide (i.e., 1,4-butynediol and ethylene oxide) is continuously introduced. The molar ratio is 1:2) during the reaction, the addition rate of ethylene oxide is controlled (the mass of ethylene oxide uniformly added in 1 hour accounts for 20% of the total mass of ethylene oxide added), the reaction temperature is maintained at 70°C and the reaction pressure is 0.25MPa, and the time for passing the above amount of ethylene oxide is 5 hours (i.e., the first polymerization reaction time is 5h); the obtained reaction product system is aged at 70°C for about 4 hours until the pressure in the reactor no longer changes, the reactor is vacuum degassed, and the degassed state is maintained at a pressure of 0.098MPa for 15 minutes. After the degassed, the temperature is lowered to 50°C to obtain a crude butynediol diethoxy ether.

[0102] The crude butynediol diethoxy ether was transferred to a dry 8m3 / 3 t / 4 ... 3 In a post-treatment kettle, 10wt% of deionized water and 80wt% of phosphoric acid were added to the crude product of butynediol diethoxy ether, and the mixture was neutralized for 30 minutes. Then, 10wt% of magnesium aluminum silicate and 5wt% of diatomaceous earth filter aid were added to the crude product of butynediol diethoxy ether, and the mixture was mixed for 30 minutes. The mixture was heated and dehydrated (at a heating rate of 10°C / h) for 6 hours. Finally, the mixture was dehydrated for 1 hour at a dehydration temperature of 110°C and a dehydration pressure of 0.098MPa. After the dehydration was completed, the mixture was cooled to 70°C and filtered to obtain the post-treated butynediol diethoxy ether.

[0103] A dry 8m2 boiler with agitation, steam heating jacket and internal water cooling coils 31760 kg of the above-mentioned butynediol diethoxy ether and a catalyst amount of 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 with nitrogen twice, stirring was started, the temperature was raised to 70°C, and vacuum treatment was performed with a vacuum pump at a pressure of 0.098 MPa for 1 hour, the dehydration pressure was -0.098 MPa, and the second polymerization reaction was carried out after dehydration was completed, and 3520 kg of ethylene oxide (i.e., the molar ratio of butynediol diethoxy ether to ethylene oxide was 1: 8) During the reaction, the rate of addition of ethylene oxide was controlled (the mass of ethylene oxide uniformly added in 1 hour accounted for 25% of the total mass of ethylene oxide added), the reaction temperature was maintained at 70° C., the reaction pressure was maintained at 0.20 MPa, and the above amount of ethylene oxide was introduced for 4 hours (i.e., the second polymerization reaction time was 4 hours); the obtained reaction product system was aged at 70° C. for about 30 minutes until the pressure in the reactor no longer changed, the reactor was vacuum degassed, and the degassed state was maintained at a pressure of 0.098 MPa for 15 minutes. After the degassed state was completed, the temperature was lowered to 50° C. to obtain butynediol polyethoxy ether.

[0104] Experimental Examples 5-2 to 5-3

[0105] Experimental Examples 5-2 to 5-3 are all about preparing butynediol polyethoxy ether in a workshop. Except for the molar ratio of butynediol diethoxy ether to ethylene oxide, other operating conditions are the same as those of Experimental Example 5-1. Specific changes in conditions are shown in Table 6.

[0106] Experimental Example 6-1

[0107] Experimental Example 6-1 is a method for preparing butynediol polyethoxy ether in a workshop. Except that a falling film evaporator is used instead of a vacuum pump for dehydration before the second polymerization reaction, other operating conditions are the same as those of Experimental Example 5-1. The details are as follows:

[0108] Dry 8m with stirring, steam heating jacket and internal water cooling coil 31720kg 1,4-butynediol and 1.5‰ potassium hydroxide and 1.5‰ sodium butoxide (i.e., the catalyst composition is a mass ratio of potassium hydroxide to sodium butoxide of 1:1, and the amount of catalyst is 3.0wt‰ (i.e., the total mass of 1,4-butynediol and ethylene oxide)) are added to the reactor, and the reactor is sealed; the air in the reactor is replaced with nitrogen twice, stirring is started, the temperature is raised to 70°C, and vacuum dehydration is carried out for 1 hour, the dehydration pressure is -0.098Mpa, and the first polymerization reaction is carried out after dehydration is completed, and 1760kg ethylene oxide (i.e., 1,4-butynediol and ethylene oxide) is continuously introduced. The molar ratio is 1:2) during the reaction, the addition rate of ethylene oxide is controlled (the mass of ethylene oxide uniformly added in 1 hour accounts for 20% of the total mass of ethylene oxide added), the reaction temperature is maintained at 70°C and the reaction pressure is 0.25MPa, and the time for passing the above amount of ethylene oxide is 5 hours (i.e., the first polymerization reaction time is 5h); the obtained reaction product system is aged at 70°C for about 4 hours until the pressure in the reactor no longer changes, the reactor is vacuum degassed, and the degassed state is maintained at a pressure of 0.098MPa for 15 minutes. After the degassed, the temperature is lowered to 50°C to obtain a crude butynediol diethoxy ether.

[0109] The crude butynediol diethoxy ether was transferred to a dry 8m3 / 3 tumble dryer equipped with stirring, steam heating jacket and internal water cooling coil. 3 In a post-treatment kettle, 10wt% of deionized water and 80wt% of phosphoric acid were added to the crude product of butynediol diethoxy ether, and the mixture was neutralized for 30 minutes. Then, 10wt% of magnesium aluminum silicate and 5wt% of diatomaceous earth filter aid were added to the crude product of butynediol diethoxy ether, and the mixture was mixed for 30 minutes. The mixture was heated and dehydrated (at a heating rate of 10°C / h) for 6 hours. Finally, the mixture was dehydrated for 1 hour at a dehydration temperature of 110°C and a dehydration pressure of 0.098MPa. After the dehydration was completed, the mixture was cooled to 70°C and filtered to obtain the post-treated butynediol diethoxy ether.

[0110] A dry 8m2 boiler with agitation, steam heating jacket and internal water cooling coils 31760 kg of the above-mentioned butynediol diethoxy ether and a catalyst amount of 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 with nitrogen twice, stirring was started, the temperature was raised to 70°C, and a falling film evaporator was used for vacuum treatment at a pressure of 0.098 MPa for 1 hour, the dehydration pressure was -0.098 MPa, and the second polymerization reaction was carried out after dehydration was completed, and 3520 kg of ethylene oxide (i.e., the molar ratio of butynediol diethoxy ether to ethylene oxide was 1) was continuously introduced. :8) During the reaction, the rate of addition of ethylene oxide is controlled (the mass of ethylene oxide uniformly added in 1 hour accounts for 25% of the total mass of ethylene oxide added), the reaction temperature is maintained at 70° C., the reaction pressure is maintained at 0.20 MPa, and the above amount of ethylene oxide is introduced for 4 hours (i.e., the second polymerization reaction time is 4 hours); the resulting reaction product system is aged at 70° C. for about 30 minutes until the pressure in the reactor no longer changes, the reactor is vacuum degassed, and the degassed state is maintained at a pressure of 0.098 MPa for 15 minutes. After the degassed state is completed, the temperature is lowered to 50° C. to obtain butynediol polyethoxy ether.

[0111] Experimental Examples 6-2 to 6-3

[0112] Experimental Examples 6-2 to 6-3 are for preparing butine diol polyethoxy ether in a workshop, wherein, Experimental Example 6-2 is the same as Experimental Example 5-2 except that a falling film evaporator is used instead of a vacuum pump for dehydration before the second polymerization reaction, and the other operating conditions are the same as Experimental Example 5-2; Experimental Example 6-3 is the same as Experimental Example 5-3 except that a falling film evaporator is used instead of a vacuum pump for dehydration before the second polymerization reaction, and the other operating conditions are the same as Experimental Example 5-3, as shown in Table 6 for details.

[0113] Table 6 Experimental Examples 5-1 to 5-3, 6-1 to 6-3 Condition Parameters and Test Data of Butynediol Polyethoxy Ether

[0114]

[0115]

[0116] From the comparison in Table 6, it can be seen that in the workshop production process, the vacuum pump is used for dehydration before the second polymerization reaction, and then the second polymerization reaction is carried out, the product has quality fluctuations, affecting downstream applications. At the same time, before the second polymerization reaction, the falling film evaporator is used for dehydration and removal of other low molecular weight impurities, and then the second polymerization reaction is carried out, the product quality is significantly improved.

[0117] 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 butynediol diethoxy ether, characterized in that: The following steps are involved: Mixing 1,4-butynediol and a basic catalyst, then adding a first ethylene oxide to carry out a first polymerization reaction, and after the reaction is completed, post-processing is performed to obtain butynediol diethoxy ether; 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 mass ratio of the potassium hydroxide to the sodium butoxide is preferably 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 first polymerization reaction is carried out under a pressure of 0 to 0.4 MPa, at a temperature of 50 to 100° C., for a time of 4 to 7 hours.

6. A method for preparing butynediol polyethoxy ether, characterized in that: The following steps are involved: (1) mixing 1,4-butynediol and a basic catalyst, then adding a first ethylene oxide to carry out a first polymerization reaction, and after the reaction is completed, post-treating to obtain butynediol diethoxy ether; (2) mixing the butynediol diethoxy ether prepared in step (1) with a second ethylene oxide and a phosphazene salt catalyst, and performing a 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 an organic phosphazene salt and an inorganic phosphazene salt.

8. The preparation method according to claim 6 or 7, characterized in that: In step (2), the phosphazene salt catalyst is a 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 first dehydrated and decontaminated by using a falling film evaporator.

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