Preparation method of 1, 4-butynediol block polyether

Abstract

The invention provides a preparation method of 1, 4-butynediol block polyether, which comprises the following steps: in the presence of a basic catalyst, mixing 1, 4-butynediol with ethylene oxide, heating to 70 DEG C, carrying out ring-opening polymerization reaction, preserving heat and curing until the pressure is not reduced any more to obtain an intermediate; adding an H-type ZSM-5 molecular sieve catalyst into the intermediate, heating to 70-100 DEG C, dropwise adding epoxypropane, and after dropwise adding, carrying out heat preservation and curing until the pressure is not reduced any more, so as to obtain a 1, 4-butynediol block polyether crude product. According to the preparation method provided by the invention, the hydroxyl value of the 1, 4-butynediol block polyether is closer to a theoretical hydroxyl value, and in addition, no additional step is needed for adsorbing and removing metal ions, so that the operation convenience is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of block polyether, and particularly relates to a preparation method of 1,4-butynediol block polyether. BACKGROUND

[0002] Currently, the preparation of polyether is generally to catalyze the ring-opening polymerization of an epoxy compound by using an alkaline catalyst, and generally needs to be treated by using an adsorbent after polymerization, so as to reduce the residual metal ions of the alkaline catalyst, which is easy to cause the technical problem of complicated operation. In addition, due to the catalytic performance of the alkaline catalyst, the hydroxyl value of the obtained polyether is greatly different from the theoretical hydroxyl value. SUMMARY

[0003] In order to overcome the deficiencies of the prior art, the purpose of the present application is to provide a preparation method of 1,4-butynediol block polyether, by using the combination of an alkaline catalyst and an H-type ZSM-5 molecular sieve catalyst, the overall catalytic activity is improved, which is conducive to making the hydroxyl value of the obtained 1,4-butynediol block polyether closer to the theoretical hydroxyl value, and additionally, the metal ions do not need to be removed by an additional step, which is conducive to improving the operation convenience.

[0004] To solve the above problems, the technical scheme adopted by the present application is as follows: A preparation method of 1,4-butynediol block polyether, comprising the following steps: Under the action of an alkaline catalyst, 1,4-butynediol is mixed with ethylene oxide, and then the mixture is heated to 70 DEG C to perform ring-opening polymerization reaction, and the mixture is incubated until the pressure no longer decreases, to obtain an intermediate; The H-type ZSM-5 molecular sieve catalyst is added into the intermediate, and then the mixture is heated to 70-100 DEG C, and then propylene oxide is added dropwise, and after the addition is completed, the mixture is incubated until the pressure no longer decreases, to obtain 1,4-butynediol block polyether crude product.

[0005] In some possible embodiments, the amount of the alkaline catalyst is 0.5‰-1‰ of the total mass of the 1,4-butynediol and the ethylene oxide, the alkaline catalyst is selected from potassium hydroxide or sodium hydroxide, and the amount of the ethylene oxide is 1.02-5.2 times the mass of the 1,4-butynediol.

[0006] In some possible embodiments, the amount of the H-type ZSM-5 molecular sieve catalyst is 5‰-10‰ of the total mass of the 1,4-butynediol, the ethylene oxide and the propylene oxide.

[0007] In some possible embodiments, the amount of the propylene oxide is 1.35-6.8 times the mass of the 1,4-butynediol.

[0008] In some possible embodiments, the preparation of the H-type ZSM-5 molecular sieve catalyst includes the following steps: Sodium-type ZSM-5 molecular sieves were acid-washed with an acidic aqueous solution at a temperature of 80°C for 2 hours. The mass fraction of acid in the acidic aqueous solution was 2.5%-15%, and the ratio of the volume (mL) of the acidic aqueous solution to the mass (g) of the sodium-type ZSM-5 molecular sieve was 5-20:1. After pickling, wash repeatedly with deionized water until neutral; After washing, the catalyst was dried at 120°C for 4 hours to obtain the H-type ZSM-5 molecular sieve catalyst.

[0009] In some possible implementations, the acidic aqueous solution contains 5%-10% by mass of acid.

[0010] In some possible implementations, the acid in the acidic aqueous solution is selected from at least one of phosphoric acid, nitric acid, and sulfuric acid.

[0011] In some possible implementations, the acid in the acidic aqueous solution has a mass fraction of 5%-7.5%, and the acid in the acidic aqueous solution is phosphoric acid.

[0012] In some possible implementations, the volume (mL) of the acidic aqueous solution is 5-15 times the mass (g) of the sodium-type ZSM-5 molecular sieve.

[0013] In some possible implementations, the following steps are also included: After cooling the obtained crude 1,4-butynediol block polyether to 60°C, deionized water was added and the mixture was stirred for at least 60 minutes. The amount of deionized water used was 5%-10% of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide. The molecular sieve catalyst was filtered out, and the moisture in the crude product was removed to obtain the 1,4-butynediol block polyether product.

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows: In this application, the combined use of an alkaline catalyst and an H-type ZSM-5 molecular sieve catalyst improves the overall catalytic activity, thereby making the hydroxyl value of the obtained 1,4-butynediol block polyether closer to the theoretical hydroxyl value. In addition, the H-type ZSM-5 molecular sieve catalyst can also adsorb the metal ions of the alkaline catalyst, thus eliminating the need for additional adsorption and removal steps, which improves the ease of operation.

[0015] The present invention will be further described in detail below with reference to specific embodiments. Detailed Implementation

[0016] The technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0018] The following describes some embodiments of the present invention in detail. Unless otherwise specified, the following embodiments and features can be combined with each other.

[0019] One embodiment of this application provides a method for preparing 1,4-butynediol block polyether, comprising the following steps.

[0020] Under alkaline catalyst, 1,4-butynediol and ethylene oxide are mixed and heated to 70°C for ring-opening polymerization. The mixture is then aged until the pressure no longer decreases to obtain an intermediate.

[0021] In some embodiments, the amount of alkaline catalyst is 0.5‰-1‰ of the total mass of the 1,4-butynediol and the ethylene oxide, the alkaline catalyst is selected from potassium hydroxide or sodium hydroxide, and the amount of ethylene oxide is 1.02-5.2 times the mass of the 1,4-butynediol.

[0022] H-type ZSM-5 molecular sieve catalyst was added to the intermediate, and after heating to 70°C, propylene oxide was added dropwise. After the addition was completed, the mixture was kept at the temperature and allowed to mature until the pressure no longer decreased, thus obtaining crude 1,4-butynediol block polyether.

[0023] In some embodiments, the amount of the H-type ZSM-5 molecular sieve catalyst is 5‰-10‰ of the total mass of the 1,4-butynediol, the ethylene oxide, and the propylene oxide.

[0024] In some embodiments, the amount of propylene oxide used is 1.35-6.8 times the mass of 1,4-butynediol.

[0025] In some embodiments, the preparation of the H-type ZSM-5 molecular sieve catalyst includes the following steps.

[0026] The sodium-type ZSM-5 molecular sieve was acid-washed with an acidic aqueous solution at a temperature of 80°C for 2 hours. The acid mass fraction of the acid in the acidic aqueous solution was 5%-10%, and the ratio of the volume (mL) of the acidic aqueous solution to the mass (g) of the sodium-type ZSM-5 molecular sieve was 5-20:1.

[0027] After pickling, wash repeatedly with deionized water until neutral.

[0028] After washing, the catalyst was dried at 120°C for 4 hours to obtain the H-type ZSM-5 molecular sieve catalyst.

[0029] In some embodiments, the acid in the acidic aqueous solution is selected from at least one of phosphoric acid, nitric acid, and sulfuric acid.

[0030] Preferably, the acid in the acidic aqueous solution has a mass fraction of 5%-7.5%, and the acid in the acidic aqueous solution is phosphoric acid.

[0031] Preferably, the volume (mL) of the acidic aqueous solution is 5-15 times the mass (g) of the sodium-type ZSM-5 molecular sieve.

[0032] In some embodiments, the preparation method further includes the steps of: cooling the obtained crude 1,4-butynediol block polyether to 60°C, adding deionized water and stirring for at least 60 minutes, wherein the amount of deionized water is 5%-10% of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide; filtering out the molecular sieve catalyst; and then removing water from the crude product to obtain the finished 1,4-butynediol block polyether. In some embodiments, the filtered molecular sieve catalyst can be sequentially washed with water, filtered, and the treated catalyst can be added to an intermediate, thereby facilitating catalyst recycling.

[0033] In this application, the combined use of an alkaline catalyst and an H-type ZSM-5 molecular sieve catalyst improves the overall catalytic activity, thereby making the hydroxyl value of the obtained 1,4-butynediol block polyether closer to the theoretical hydroxyl value. In addition, the H-type ZSM-5 molecular sieve catalyst can also adsorb the metal ions of the alkaline catalyst, thus eliminating the need for additional adsorption and removal steps, which improves the ease of operation.

[0034] The following is a detailed description of the embodiments.

[0035] Example 1 Preparation of H-type ZSM-5 molecular sieve catalysts First, 2g of sodium-type ZSM-5 molecular sieve was acid-washed with a 5% (w / w) phosphoric acid aqueous solution at 80℃ for 2 hours. The volume of the phosphoric acid aqueous solution used was 10mL, meaning the ratio of the volume (mL) of the acidic aqueous solution to the mass (g) of the sodium-type ZSM-5 molecular sieve was 5:1. After acid washing, the sieve was repeatedly washed with deionized water until neutral. After washing, the sieve was dried at 120℃ for 4 hours to remove moisture, thus obtaining the H-type ZSM-5 molecular sieve catalyst.

[0036] Preparation of 1,4-Butynediol Block Polyether 86g of molten 1,4-butynediol was added to a reaction vessel, followed by 0.09g of potassium hydroxide. After the addition was complete, the air inside the vessel was purged twice with nitrogen. Stirring was then started to ensure thorough mixing of the materials. The temperature was raised to 70°C, and 88g of ethylene oxide was slowly added dropwise. After the addition was complete, the reaction continued until the pressure no longer changed, yielding a 1,4-butynediol polyethoxylate intermediate. The amount of alkaline catalyst used was 0.5‰ of the total mass of the 1,4-butynediol and ethylene oxide. The amount of ethylene oxide used was 1.02 times the mass of the 1,4-butynediol.

[0037] Add 1.47g of H-type ZSM-5 molecular sieve catalyst to the intermediate, heat to 70℃, and then add 120g of propylene oxide dropwise. After the addition is complete, continue the ripening reaction until the pressure no longer changes. Control the reaction temperature to maintain 70±2℃ to obtain crude 1,4-butynediol block polyether. The amount of the H-type ZSM-5 molecular sieve catalyst is 5‰ of the total mass of the 1,4-butynediol, the ethylene oxide, and the propylene oxide. The amount of propylene oxide is 1.40 times the mass of the 1,4-butynediol.

[0038] The crude polyether was cooled to 60°C, and 15g of deionized water was added. The mixture was stirred for 60 minutes. The molecular sieve catalyst was first filtered out (collected and reused), and then the water in the crude product was removed to obtain the 1,4-butynediol block polyether product. The amount of deionized water used was 5% of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide.

[0039] The finished product of Example 1 was tested, and the results were: hydroxyl value 384.2 mg KOH / g, and potassium and sodium ion content 10.1 ppm.

[0040] Example 2 Preparation of H-type ZSM-5 molecular sieve catalysts First, 2g of sodium-type ZSM-5 molecular sieve was acid-washed with a 5% (w / w) sulfuric acid aqueous solution at 80℃ for 2 hours, using 10mL of sulfuric acid aqueous solution. Therefore, the volume (mL) of the acidic aqueous solution was 5:1 compared to the mass (g) of the sodium-type ZSM-5 molecular sieve. After acid washing, the sieve was repeatedly washed with deionized water until neutral. Following washing, it was dried at 120℃ for 4 hours to remove moisture, yielding the H-type ZSM-5 molecular sieve catalyst.

[0041] Preparation of 1,4-Butynediol Block Polyether 86g of molten 1,4-butynediol was added to a reaction vessel, followed by 0.09g of potassium hydroxide. After the addition was complete, the air inside the vessel was purged twice with nitrogen. Stirring was then started to ensure thorough mixing of the materials. The temperature was raised to 70°C, and 88g of ethylene oxide was slowly added dropwise. After the addition was complete, the reaction continued until the pressure no longer changed, yielding a 1,4-butynediol polyethoxylate intermediate. The amount of alkaline catalyst used was 0.5‰ of the total mass of the 1,4-butynediol and ethylene oxide. The amount of ethylene oxide used was 1.02 times the mass of the 1,4-butynediol.

[0042] Add 1.47g of H-type ZSM-5 molecular sieve catalyst to the intermediate, heat to 70℃, and then add 120g of propylene oxide dropwise. After the addition is complete, continue the aging reaction until the pressure no longer changes, to obtain crude 1,4-butynediol block polyether. The amount of the H-type ZSM-5 molecular sieve catalyst is 5‰ of the total mass of the 1,4-butynediol, the ethylene oxide, and the propylene oxide. The amount of propylene oxide is 1.40 times the mass of the 1,4-butynediol.

[0043] The crude polyether was cooled to 60°C, and 15g of deionized water was added. The mixture was stirred for 60 minutes. The molecular sieve catalyst was first filtered out (collected and reused), and then the water in the crude product was removed to obtain the 1,4-butynediol block polyether product. The amount of deionized water used was 5% of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide.

[0044] The finished product of Example 2 was tested, and the results were: hydroxyl value 386.2 mgKOH / g, potassium and sodium ion content 15.3ppm.

[0045] Example 3 Preparation of H-type ZSM-5 molecular sieve catalysts First, 2g of sodium-type ZSM-5 molecular sieve was acid-washed with a 5% (by mass) nitric acid aqueous solution at a temperature of 80℃ for 2 hours. The volume of the nitric acid aqueous solution was 10mL, meaning the ratio of the volume (mL) of the acidic aqueous solution to the mass (g) of the sodium-type ZSM-5 molecular sieve was 5:1. After acid washing, the sieve was repeatedly washed with deionized water until neutral. After washing, the sieve was dried at 120℃ for 4 hours to remove moisture and obtain the H-type ZSM-5 molecular sieve catalyst.

[0046] Preparation of 1,4-Butynediol Block Polyether 86g of molten 1,4-butynediol was added to a reaction vessel, followed by 0.09g of potassium hydroxide. After the addition was complete, the air inside the vessel was purged twice with nitrogen. Stirring was then started to ensure thorough mixing of the materials. The temperature was raised to 70°C, and 88g of ethylene oxide was slowly added dropwise. After the addition was complete, the reaction continued until the pressure no longer changed, yielding a 1,4-butynediol polyethoxylate intermediate. The amount of alkaline catalyst used was 0.5‰ of the total mass of the 1,4-butynediol and ethylene oxide. The amount of ethylene oxide used was 1.02 times the mass of the 1,4-butynediol.

[0047] 1.47 g of H-type ZSM-5 molecular sieve catalyst was added to the intermediate, the temperature was raised to 70°C, and then 120 g of propylene oxide was added dropwise. After the addition was complete, the reaction was allowed to continue until the pressure no longer changed, yielding crude 1,4-butynediol block polyether. The amount of the H-type ZSM-5 molecular sieve catalyst was 5‰ of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide. The amount of propylene oxide was 1.40 times the mass of the 1,4-butynediol.

[0048] The crude polyether was cooled to 60°C, and 15g of deionized water was added. The mixture was stirred for 60 minutes. The molecular sieve catalyst was first filtered out (collected and reused), and then the water in the crude product was removed to obtain the 1,4-butynediol block polyether product. The amount of deionized water used was 5% of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide.

[0049] The finished product of Example 3 was tested, and the results were: hydroxyl value 390 mgKOH / g, potassium and sodium ion content 20.2ppm.

[0050] Comparing Examples 1 to 3, it can be seen that, under the same conditions, the hydroxyl value of the polyether product treated with phosphoric acid is closer to the theoretical hydroxyl value (381.6 mgKOH / g), and the potassium and sodium ion content is lower.

[0051] Example 4 Preparation of H-type ZSM-5 molecular sieve catalysts First, 4g of sodium-type ZSM-5 molecular sieve was acid-washed with a 5% (phosphoric acid) aqueous solution at a temperature of 80℃ for 2 hours. The volume of the acidic aqueous solution was 40mL, meaning the ratio of the volume (mL) of the acidic aqueous solution to the mass (g) of the sodium-type ZSM-5 molecular sieve was 10:1. After acid washing, the sieve was repeatedly washed with deionized water until neutral. After washing, the sieve was dried at 120℃ for 4 hours to remove moisture and obtain H-type ZSM-5 molecular sieve catalyst.

[0052] Preparation of 1,4-Butynediol Block Polyether 86g of molten 1,4-butynediol was added to a reaction vessel, followed by 0.20g of potassium hydroxide. After the addition was complete, the air inside the vessel was purged twice with nitrogen. Stirring was then started to ensure thorough mixing of the materials. The temperature was raised to 70°C, and 176g of ethylene oxide was slowly added dropwise. After the addition was complete, the reaction was continued until the pressure no longer changed, yielding a 1,4-butynediol polyethoxylate intermediate. The amount of alkaline catalyst used was 0.7‰ of the total mass of the 1,4-butynediol and ethylene oxide. The amount of ethylene oxide used was 2.04 times the mass of the 1,4-butynediol.

[0053] Add 3.7g of H-type ZSM-5 molecular sieve catalyst to the intermediate, heat to 80℃, and then add 232g of propylene oxide dropwise. After the addition is complete, continue the aging reaction until the pressure no longer changes, to obtain crude 1,4-butynediol block polyether. The amount of the H-type ZSM-5 molecular sieve catalyst is 7‰ of the total mass of the 1,4-butynediol, the ethylene oxide, and the propylene oxide. The amount of propylene oxide is 2.70 times the mass of the 1,4-butynediol.

[0054] The crude polyether was cooled to 60°C, and 37g of deionized water was added. The mixture was stirred for 60 minutes. The molecular sieve catalyst was first filtered out (and collected for reuse), and then the water in the crude product was removed to obtain the 1,4-butynediol block polyether product. The amount of deionized water used was 7.5% of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide.

[0055] The finished product of Example 4 was tested, and the results were: hydroxyl value 383.0 mg KOH / g, and potassium and sodium ion content 5.1 ppm.

[0056] Example 5 Preparation of H-type ZSM-5 molecular sieve catalysts First, 4g of sodium-type ZSM-5 molecular sieve was acid-washed with a 7.5% (by mass) phosphoric acid aqueous solution at 80℃ for 2 hours. The volume of the phosphoric acid aqueous solution used was 40mL, meaning the ratio of the volume (mL) of the acidic aqueous solution to the mass (g) of the sodium-type ZSM-5 molecular sieve was 10:1. After acid washing, the sieve was repeatedly washed with deionized water until neutral. After washing, it was dried at 120℃ for 4 hours to remove moisture, thus obtaining the H-type ZSM-5 molecular sieve catalyst.

[0057] Preparation of 1,4-Butynediol Block Polyether 86g of molten 1,4-butynediol was added to a reaction vessel, followed by 0.20g of potassium hydroxide. After the addition was complete, the air inside the vessel was purged twice with nitrogen. Stirring was then started to ensure thorough mixing of the materials. The temperature was raised to 70°C, and 176g of ethylene oxide was slowly added dropwise. After the addition was complete, the reaction was continued until the pressure no longer changed, yielding a 1,4-butynediol polyethoxylate intermediate. The amount of alkaline catalyst used was 0.7‰ of the total mass of the 1,4-butynediol and ethylene oxide. The amount of ethylene oxide used was 2.04 times the mass of the 1,4-butynediol.

[0058] Add 3.7g of H-type ZSM-5 molecular sieve catalyst to the intermediate, heat to 80℃, and then add 232g of propylene oxide dropwise. After the addition is complete, continue the aging reaction until the pressure no longer changes, to obtain crude 1,4-butynediol block polyether. The amount of the H-type ZSM-5 molecular sieve catalyst is 7‰ of the total mass of the 1,4-butynediol, the ethylene oxide, and the propylene oxide. The amount of propylene oxide is 2.70 times the mass of the 1,4-butynediol.

[0059] The crude polyether was cooled to 60°C, and 37g of deionized water was added. The mixture was stirred for 60 minutes. The molecular sieve catalyst was first filtered out (and collected for reuse), and then the water in the crude product was removed to obtain the 1,4-butynediol block polyether product. The amount of deionized water used was 7.5% of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide.

[0060] The finished product of Example 5 was tested, and the results were: hydroxyl value 382.8 mg KOH / g, and potassium and sodium ion content 3.5 ppm.

[0061] Example 6 Preparation of H-type ZSM-5 molecular sieve catalysts First, 4g of sodium-type ZSM-5 molecular sieve was acid-washed with a 10% (phosphoric acid) aqueous solution at a temperature of 80℃ for 2 hours. The volume of the acidic aqueous solution was 40mL, meaning the ratio of the volume (mL) of the acidic aqueous solution to the mass (g) of the sodium-type ZSM-5 molecular sieve was 10:1. After acid washing, the solution was repeatedly washed with deionized water until neutral. After washing, the solution was dried at 120℃ for 4 hours to remove moisture, thus obtaining the H-type ZSM-5 molecular sieve catalyst for later use.

[0062] Preparation of H-type ZSM-5 molecular sieve catalysts 86g of molten 1,4-butynediol was added to a reaction vessel, followed by 0.20g of potassium hydroxide. After the addition was complete, the air inside the vessel was purged twice with nitrogen. Stirring was then started to ensure thorough mixing of the materials. The temperature was raised to 70°C, and 176g of ethylene oxide was slowly added dropwise. After the addition was complete, the reaction was continued until the pressure no longer changed, yielding a 1,4-butynediol polyethoxylate intermediate. The amount of alkaline catalyst used was 0.7‰ of the total mass of the 1,4-butynediol and ethylene oxide. The amount of ethylene oxide used was 2.04 times the mass of the 1,4-butynediol.

[0063] Add 3.7g of H-type ZSM-5 molecular sieve catalyst to the intermediate, heat to 80℃, and then add 232g of propylene oxide dropwise. After the addition is complete, continue the aging reaction until the pressure no longer changes, to obtain crude 1,4-butynediol block polyether. The amount of the H-type ZSM-5 molecular sieve catalyst is 7‰ of the total mass of the 1,4-butynediol, the ethylene oxide, and the propylene oxide. The amount of propylene oxide is 2.70 times the mass of the 1,4-butynediol.

[0064] The crude polyether was cooled to 60°C, and 37g of deionized water was added. The mixture was stirred for 60 minutes. The molecular sieve catalyst was first filtered out (and collected for reuse), and then the water in the crude product was removed to obtain the 1,4-butynediol block polyether product. The amount of deionized water used was 7.5% of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide.

[0065] The finished product of Example 6 was tested, and the results were: hydroxyl value 390.6 mg KOH / g, and potassium and sodium ion content 12.0 ppm.

[0066] Comparing the test results of Examples 4 to 6, it can be seen that when the mass fraction of acid in the acidic aqueous solution is 5%-7.5%, the hydroxyl value of the corresponding polyether is closer to the theoretical value, and the potassium and sodium ion content in the polyether product is lower.

[0067] Examples 7 and 8 By changing the mass fraction of acid in the phosphoric acid aqueous solution in Example 4 to 2.5% and 15% respectively, while keeping other conditions unchanged, Examples 7 and 8 were obtained.

[0068] The finished products from Examples 7 and 8 were tested, and the results were as follows: Example 7, hydroxyl value 392.3 mg KOH / g, potassium and sodium ion content 13.6 ppm; Example 8, hydroxyl value 395.6 mg KOH / g, potassium and sodium ion content 16.2 ppm. Comparing the above examples, it can be seen that excessively high or low acid concentrations may reduce the catalytic activity of the H-type ZSM-5 molecular sieve catalyst, and may also increase the potassium and sodium ion content. Therefore, to achieve optimal adsorption of metal ions and improved catalytic activity, the acid concentration needs to be limited to a predetermined range.

[0069] Example 9 Preparation of H-type ZSM-5 molecular sieve catalysts First, 8g of sodium-type ZSM-5 molecular sieve was acid-washed with a 7.5% (phosphoric acid) aqueous solution at a temperature of 80℃ for 2 hours. The volume of the acidic aqueous solution was 120mL, meaning the ratio of the volume (mL) of the acidic aqueous solution to the mass (g) of the sodium-type ZSM-5 molecular sieve was 15:1. After acid washing, the solution was repeatedly washed with deionized water until neutral. After washing, the solution was dried at 120℃ for 4 hours to remove moisture and obtain the H-type ZSM-5 molecular sieve catalyst.

[0070] Preparation of 1,4-Butynediol Block Polyether 86g of molten 1,4-butynediol was added to a reaction vessel, followed by 0.43g of sodium hydroxide. After the addition was complete, the air inside the vessel was purged twice with nitrogen. Stirring was then started to ensure thorough mixing of the materials. The temperature was raised to 70°C, and 352g of ethylene oxide was slowly added dropwise. After the addition was complete, the reaction continued until the pressure no longer changed, yielding a 1,4-butynediol polyethoxylate intermediate. The amount of alkaline catalyst used was 1‰ of the total mass of the 1,4-butynediol and ethylene oxide. The amount of ethylene oxide used was 4.09 times the mass of 1,4-butynediol.

[0071] Add 7.8g of H-type ZSM-5 molecular sieve catalyst to the intermediate, heat to 90℃, and then add 348g of propylene oxide dropwise. After the addition is complete, continue the aging reaction until the pressure no longer changes, to obtain crude 1,4-butynediol block polyether. The amount of the H-type ZSM-5 molecular sieve catalyst is 10‰ of the total mass of the 1,4-butynediol, the ethylene oxide, and the propylene oxide. The amount of propylene oxide is 4.05 times the mass of the 1,4-butynediol.

[0072] The crude polyether was cooled to 60°C, and 78g of deionized water was added. The mixture was stirred for 60 minutes. The molecular sieve catalyst was first filtered out (collected and reused), and then the water in the crude product was removed to obtain the 1,4-butynediol block polyether product. The amount of deionized water used was 10% of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide.

[0073] The finished product of Example 9 was tested, and the results were: hydroxyl value 382.6 mg KOH / g, and potassium and sodium ion content 6.8 ppm.

[0074] Example 10 Preparation of H-type ZSM-5 molecular sieve catalysts First, 8g of sodium-type ZSM-5 molecular sieve was acid-washed with a 10% (mass fraction) phosphoric acid aqueous solution at 80℃ for 2 hours. The volume of the phosphoric acid aqueous solution used was 160mL, meaning the ratio of the volume (mL) of the acidic aqueous solution to the mass (g) of the sodium-type ZSM-5 molecular sieve was 20:1. After acid washing, the sieve was repeatedly washed with deionized water until neutral. After washing, it was dried at 120℃ for 4 hours to remove moisture, thus obtaining the H-type ZSM-5 molecular sieve catalyst.

[0075] Preparation of 1,4-Butynediol Block Polyether 86g of molten 1,4-butynediol was added to a reaction vessel, followed by 0.43g of sodium hydroxide. After the addition was complete, the air inside the vessel was purged twice with nitrogen. Stirring was then started to ensure thorough mixing of the materials. The temperature was raised to 70°C, and 352g of ethylene oxide was slowly added dropwise. After the addition was complete, the reaction continued until the pressure no longer changed, yielding a 1,4-butynediol polyethoxylate intermediate. The amount of alkaline catalyst used was 1‰ of the total mass of the 1,4-butynediol and ethylene oxide. The amount of ethylene oxide used was 4.09 times the mass of 1,4-butynediol.

[0076] Add 7.8g of H-type ZSM-5 molecular sieve catalyst to the intermediate, heat to 90℃, and then add 348g of propylene oxide dropwise. After the addition is complete, continue the aging reaction until the pressure no longer changes, to obtain crude 1,4-butynediol block polyether. The amount of the H-type ZSM-5 molecular sieve catalyst is 10‰ of the total mass of the 1,4-butynediol, the ethylene oxide, and the propylene oxide. The amount of propylene oxide is 4.05 times the mass of the 1,4-butynediol.

[0077] The crude polyether was cooled to 60°C, and 78g of deionized water was added. The mixture was stirred for 60 minutes. The molecular sieve catalyst was first filtered out (collected and reused), and then the water in the crude product was removed to obtain the 1,4-butynediol block polyether product. The amount of deionized water used was 10% of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide.

[0078] The finished product of Example 10 was tested, and the results were: hydroxyl value 388.6 mg KOH / g, and potassium and sodium ion content 11.2 ppm.

[0079] Comparing Examples 9 and 10, it can be seen that increasing the volume (mL) of the acidic aqueous solution, the mass (g) of the sodium-type ZSM-5 molecular sieve, and the mass fraction of the acid are all detrimental to reducing the potassium and sodium ion content and bringing the hydroxyl value closer to the theoretical hydroxyl value.

[0080] Example 11 Preparation of H-type ZSM-5 molecular sieve catalysts First, 8g of sodium-type ZSM-5 molecular sieve was acid-washed with a 7.5% (nitric acid) aqueous solution at a temperature of 80℃ for 2 hours. The volume of the acidic aqueous solution was 80mL, meaning the ratio of the volume (mL) of the acidic aqueous solution to the mass (g) of the sodium-type ZSM-5 molecular sieve was 10:1. After acid washing, the sieve was repeatedly washed with deionized water until neutral. After washing, the sieve was dried at 120℃ for 4 hours to remove moisture and obtain the H-type ZSM-5 molecular sieve catalyst.

[0081] Preparation of 1,4-Butynediol Block Polyether 86g of molten 1,4-butynediol was added to a reaction vessel, followed by 0.42g of sodium hydroxide. After the addition was complete, the air inside the vessel was purged twice with nitrogen. Stirring was then started to ensure thorough mixing of the materials. The temperature was raised to 70°C, and 440g of ethylene oxide was slowly added dropwise. After the addition was complete, the reaction continued until the pressure no longer changed, yielding a 1,4-butynediol polyethoxylate intermediate. The amount of alkaline catalyst used was 0.8‰ of the total mass of the 1,4-butynediol and ethylene oxide. The amount of ethylene oxide used was 5.12 times the mass of the 1,4-butynediol.

[0082] Add 7.4g of H-type ZSM-5 molecular sieve catalyst to the intermediate, heat to 100℃, and then add 464g of propylene oxide dropwise. After the addition is complete, continue the ripening reaction until the pressure no longer changes, to obtain crude 1,4-butynediol block polyether. The amount of the H-type ZSM-5 molecular sieve catalyst is 7‰ of the total mass of the 1,4-butynediol, the ethylene oxide, and the propylene oxide. The amount of propylene oxide is 5.40 times the mass of the 1,4-butynediol.

[0083] The crude polyether was cooled to 60°C, and 60g of deionized water was added. The mixture was stirred for 60 minutes. The molecular sieve catalyst was first filtered out (and collected for reuse), and then the water in the crude product was removed to obtain the 1,4-butynediol block polyether product. The amount of deionized water used was 6.1% of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide.

[0084] The finished product of Example 11 was tested, and the results were: hydroxyl value 386.5 mg KOH / g, potassium and sodium ion content 7.6 ppm.

[0085] Example 12 Preparation of H-type ZSM-5 molecular sieve catalysts First, 6g of sodium-type ZSM-5 molecular sieve was acid-washed with an 8% sulfuric acid aqueous solution at a temperature of 80℃ for 2 hours. The volume of the sulfuric acid aqueous solution was 90mL, meaning the ratio of the volume (mL) of the acidic aqueous solution to the mass (g) of the sodium-type ZSM-5 molecular sieve was 15:1. After acid washing, the solution was repeatedly washed with deionized water until neutral. After washing, the solution was dried at 120℃ for 4 hours to remove moisture and obtain the H-type ZSM-5 molecular sieve catalyst.

[0086] Preparation of 1,4-Butynediol Block Polyether 86g of molten 1,4-butynediol was added to a reaction vessel, followed by 0.25g of potassium hydroxide. After the addition was complete, the air inside the vessel was purged twice with nitrogen. Stirring was then started to ensure thorough mixing of the materials. The temperature was raised to 70°C, and 264g of ethylene oxide was slowly added dropwise. After the addition was complete, the reaction was continued until the pressure no longer changed, yielding a 1,4-butynediol polyethoxylate intermediate. The amount of alkaline catalyst used was 0.7‰ of the total mass of the 1,4-butynediol and ethylene oxide. The amount of ethylene oxide used was 3.07 times the mass of the 1,4-butynediol.

[0087] Add 5.6g of H-type ZSM-5 molecular sieve catalyst to the intermediate, heat to 75℃, and then add 580g of propylene oxide dropwise. After the addition is complete, continue the ripening reaction until the pressure no longer changes, to obtain crude 1,4-butynediol block polyether. The amount of the H-type ZSM-5 molecular sieve catalyst is 6‰ of the total mass of the 1,4-butynediol, the ethylene oxide, and the propylene oxide. The amount of propylene oxide is 6.74 times the mass of the 1,4-butynediol.

[0088] The crude polyether was cooled to 60°C, and 83g of deionized water was added. The mixture was stirred for 60 minutes. The molecular sieve catalyst was first filtered out (collected and reused), and then the water in the crude product was removed to obtain the 1,4-butynediol block polyether product. The amount of deionized water used was 9% of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide.

[0089] The finished product of Example 12 was tested, and the results were: hydroxyl value 384.2 mg KOH / g, potassium and sodium ion content 4.8 ppm.

[0090] Comparative Example 1 86g of molten 1,4-butynediol was added to a reactor, followed by 1.6g of potassium hydroxide. After the addition was complete, the air inside the reactor was replaced twice with nitrogen. The stirring was then started to ensure thorough mixing of the materials. The temperature was raised to 70°C, and 88g of ethylene oxide was slowly added dropwise. After the addition was complete, the reaction was continued until the pressure no longer changed. Then, 120g of propylene oxide was added dropwise, and the reaction was continued until the pressure no longer changed. Crude 1,4-butynediol block polyether was obtained. The crude product was then subjected to water washing and adsorption dehydration steps to obtain the finished 1,4-butynediol block polyether.

[0091] The finished product of Comparative Example 1 was tested, and the result was: hydroxyl value 516.2 mgKOH / g.

[0092] In this application, the hydroxyl value was determined according to the phthalic anhydride method specified in GB / T 7383-2007. The potassium and sodium ion contents were determined using a PerkinElmer_NexlON 350S inductively coupled plasma mass spectrometer.

[0093] The materials used in this application are conventional materials that are readily available for purchase.

[0094] The above embodiments are merely preferred embodiments of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention shall fall within the scope of protection claimed by the present invention.

Claims

1. A method for preparing 1,4-butynediol block polyether, characterized in that, Includes the following steps: Under alkaline catalyst, 1,4-butynediol and ethylene oxide were mixed and heated to 70°C for ring-opening polymerization. The mixture was then kept at this temperature and allowed to mature until the pressure no longer decreased, thus obtaining an intermediate. H-type ZSM-5 molecular sieve catalyst was added to the intermediate, and after heating to 70-100℃, propylene oxide was added dropwise. After the addition was completed, the mixture was kept at the temperature and allowed to mature until the pressure no longer decreased, thus obtaining crude 1,4-butynediol block polyether.

2. The preparation method according to claim 1, characterized in that, The amount of alkaline catalyst used is 0.5‰-1‰ of the total mass of 1,4-butynediol and ethylene oxide. The alkaline catalyst is selected from potassium hydroxide or sodium hydroxide, and the amount of ethylene oxide used is 1.02-5.2 times the mass of 1,4-butynediol.

3. The preparation method according to claim 1, characterized in that, The amount of the H-type ZSM-5 molecular sieve catalyst used is 5‰-10‰ of the total mass of the 1,4-butynediol, the ethylene oxide, and the propylene oxide.

4. The preparation method according to claim 1 or 3, characterized in that, The amount of propylene oxide used is 1.35-6.8 times the mass of 1,4-butynediol.

5. The preparation method according to any one of claims 1 to 4, characterized in that, The preparation of the H-type ZSM-5 molecular sieve catalyst includes the following steps: Sodium-type ZSM-5 molecular sieves were acid-washed with an acidic aqueous solution at a temperature of 80°C for 2 hours. The mass fraction of acid in the acidic aqueous solution was 2.5%-15%, and the ratio of the volume (mL) of the acidic aqueous solution to the mass (g) of the sodium-type ZSM-5 molecular sieve was 5-20:

1. After pickling, wash repeatedly with deionized water until neutral; After washing, the catalyst was dried at 120°C for 4 hours to obtain the H-type ZSM-5 molecular sieve catalyst.

6. The preparation method according to claim 5, characterized in that, The acid in the acidic aqueous solution has a mass fraction of 5%-10%.

7. The preparation method according to claim 5 or 6, characterized in that, The acid in the acidic aqueous solution is selected from at least one of phosphoric acid, nitric acid, and sulfuric acid.

8. The preparation method according to claim 7, characterized in that, The acid in the acidic aqueous solution has a mass fraction of 5%-7.5%, and the acid in the acidic aqueous solution is phosphoric acid.

9. The preparation method according to claim 8, characterized in that, The volume (mL) of the acidic aqueous solution is 5-15 times the mass (g) of the sodium-type ZSM-5 molecular sieve.

10. The preparation method according to claim 1, characterized in that, It also includes the following steps: After cooling the obtained crude 1,4-butynediol block polyether to 60°C, deionized water was added and the mixture was stirred for at least 60 minutes. The amount of deionized water used was 5%-10% of the total mass of the 1,4-butynediol, ethylene oxide, and propylene oxide. The molecular sieve catalyst was filtered out, and the moisture in the crude product was removed to obtain the 1,4-butynediol block polyether product.