A kind of preparation method of propargyl alcohol

Abstract

The present application relates to the field of organic synthesis technology, and specifically discloses a method for preparing propargyl alcohol. A method for preparing propargyl alcohol, comprising the following steps: 1,3-dichloropropylene and sodium carbonate aqueous solution are mixed and heated to 70-80 DEG C of reflux reaction for 4-6h, first put into dimethyl sulfoxide and mix evenly, then put into sodium hydroxide, react under the conditions of 100-150 DEG C, remove sodium chloride after the reaction ends, obtain propargyl alcohol crude product, distillation, obtain propargyl alcohol. The yield and purity of propargyl alcohol using the preparation method of propargyl alcohol of the present application can reach 73.8% and 99.9% respectively, improve the yield and purity of propargyl alcohol, and the preparation method is simple, production safety is high, sodium hydroxide is directly put into the reactor during the reaction, the time of preliminary reaction stratification is reduced, production steps are saved, heat loss and material loss are reduced when reflux and upper organic phase are taken, and production efficiency is improved.

Description

Technical Field

[0001] The present application relates to the technical field of organic synthesis, and more specifically, to a method for preparing propargyl alcohol. Background Art

[0002] Propargyl alcohol is a key intermediate widely used in the pharmaceutical, pesticide, electroplating and resin industries. It is mainly used in the preparation of pharmaceutical sulfadiazine, fosfomycin drugs, pesticide propargite and electroplating nickel brightener, etc.

[0003] In the related art, the methods for preparing propargyl alcohol are mainly divided into the following two types: one is to first add trioxymethylene, solvent and catalyst into a reactor and introduce acetylene, heat the reactor to a certain temperature and then activate the catalyst, adjust the pH value by alkali solution during the activation process, stop introducing acetylene after the activation is completed, then add 1,4-butynediol and organic solvent into the reactor, continue to heat the reactor to the BYD decomposition temperature, 1,4-butynediol is decomposed into propargyl alcohol and formaldehyde under the action of the catalyst, propargyl alcohol is separated from the reaction solution in the form of gas to obtain propargyl alcohol, but the acetylene in this method has the risk of explosion, and the production is relatively unsafe; the other is to add 1,3 -Dichloropropylene and saturated alkali metal carbonate solution are added to the reactor and heated to reflux. After the reflux is completed, the stratification is allowed to stand, and the upper organic phase is taken to obtain crude 3-chloropropylene alcohol. Inhibitor, 3-chloropropylene alcohol and alkali metal hydroxide are added to the polar solvent dimethyl sulfoxide, heated to 70-100°C, and the reaction is kept warm for 1-3 hours. After the reaction is completed, the temperature is lowered until a precipitate is precipitated, and concentrated hydrochloric acid is added to neutralize to neutrality. After the precipitate is completely precipitated, it is filtered, and the filter cake is washed with dimethyl sulfoxide until it is light yellow. The obtained filtrate is distilled to obtain crude propargyl alcohol, and propargyl alcohol is obtained after refining. This method is safe for production, but the reaction steps are complicated in the production process and the production efficiency is low. Summary of the invention

[0004] In order to improve the safety problem of producing propargyl alcohol and increase the yield of propargyl alcohol, the present application provides a method for preparing propargyl alcohol.

[0005] In a first aspect, the present application provides a method for preparing propargyl alcohol, which adopts the following technical scheme:

[0006] A method for preparing propargyl alcohol comprises the following steps:

[0007] Mix 1,3-dichloropropylene and sodium carbonate aqueous solution, heat to 70-80°C, reflux for reaction for 4-6h, first add dimethyl sulfoxide in a molar ratio (1.0-1.2) to 1,3-dichloropropylene and mix evenly, then add sodium hydroxide, react at 100-150°C, remove sodium chloride after the reaction, obtain crude propargyl alcohol, and distill to obtain propargyl alcohol.

[0008] By adopting the above technical scheme, 1,3-dichloropropylene reacts with sodium carbonate solution to generate 3-chloropropylene alcohol, sodium carbonate and sodium chloride, dimethyl sulfoxide is added to evenly mix 1,3-dichloropropylene and sodium carbonate aqueous solution, and then sodium hydroxide is added to make part of sodium hydroxide react with sodium bicarbonate to generate sodium carbonate, which can provide sodium carbonate for the reaction system, and another part of sodium hydroxide reacts with 3-chloropropylene alcohol to generate propargyl alcohol and sodium chloride, and the sodium chloride is removed to obtain propargyl alcohol.

[0009] Preferably, the reaction conditions of the 1,3-dichloropropylene and sodium carbonate solution are heating to 75° C. and reflux for 5 hours.

[0010] By adopting the above technical solution, the reaction conditions of 1,3-dichloropropylene and sodium carbonate solution are heating to 75° C. and reflux for 5 hours, which is more conducive to the full reaction of 1,3-dichloropropylene and sodium carbonate solution.

[0011] Preferably, the mass concentration of the sodium carbonate aqueous solution is 5-10%.

[0012] By adopting the above technical solution, the mass concentration of the sodium carbonate aqueous solution is adjusted to allow 1,3-dichloropropylene and sodium carbonate to fully react.

[0013] Preferably, the molar ratio of the 1,3-dichloropropylene to the sodium carbonate solution is 1:(1.1-1.2).

[0014] By adopting the above technical scheme, the molar ratio of 1,3-dichloropropylene and sodium carbonate solution is adjusted, which is conducive to the full reaction of 1,3-dichloropropylene and sodium carbonate to generate sodium bicarbonate and 3-chloropropylene alcohol, thereby improving the yield of propynyl alcohol.

[0015] Preferably, the molar ratio of 1,3-dichloropropylene to sodium hydroxide is 1:(2.0-2.1).

[0016] By adopting the above technical scheme, the molar ratio of sodium hydroxide to 1,3-dichloropropylene is adjusted, which is more conducive to the full reaction of sodium hydroxide with sodium bicarbonate and 3-chloropropylene alcohol, thereby improving the yield of propynyl alcohol.

[0017] Preferably, the method for removing sodium chloride comprises the following steps: after the reaction is completed, cooling to 20-25°C to precipitate part of the sodium chloride solid, filtering to remove the sodium chloride solid, heating the remaining liquid to 60-80°C, filtering, and collecting the filtrate. By adopting the above technical scheme, after sodium hydroxide and sodium bicarbonate react with 3-chloropropenol, cooling to precipitate sodium chloride, filtering, and then heating to 60-80°C to make the sodium chloride solid, filtering, and collecting the filtrate to obtain a crude propynol product with sodium chloride removed.

[0018] Preferably, the distillation comprises the following steps: firstly removing dimethyl sulfoxide from the crude propargyl alcohol, then adding isopropyl ether, azeotropic dehydration, fractionation, collecting the fraction at 114-115° C., and obtaining propargyl alcohol.

[0019] By adopting the technical scheme, under the conditions of a normal pressure tower bottom temperature of 150-160° C. and a tower top temperature of 130-140° C., dimethyl sulfoxide is removed, the tower top is a mixture of propargyl alcohol and water, the tower bottom is dimethyl sulfoxide, isopropyl ether is added to the crude propargyl alcohol at the tower top, azeotropic dehydration is performed, water and isopropyl ether are removed, and a fraction at 114-115° C. is collected to obtain propargyl alcohol.

[0020] Preferably, the mass ratio of the isopropyl ether to the crude propargyl alcohol is 1:(1.7-1.9).

[0021] By adopting the above technical scheme and adjusting the mass ratio of isopropyl ether to crude propargyl alcohol, the yield and purity of propargyl alcohol can be improved.

[0022] In summary, the present application includes at least one of the following beneficial technical effects:

[0023] (1) The present invention controls the reaction conditions of 1,3-dichloropropylene and sodium carbonate solution to heat to 75° C. and reflux for 5 h, so that the yield and purity of propargyl alcohol can reach 73.1% and 99.4% respectively, thereby improving the yield and purity of propargyl alcohol.

[0024] (2) In the present application, by adding sodium hydroxide and reacting at 55° C., the yield and purity of propargyl alcohol can reach 73.2% and 99.6% respectively, further improving the yield and purity of propargyl alcohol.

[0025] (3) The yield and purity of propargyl alcohol can reach 73.3-73.4% and 99.6-99.8% respectively by controlling the mass concentration of the sodium carbonate aqueous solution, thereby further improving the yield and purity of propargyl alcohol.

[0026] (4) The present invention controls the molar ratio of 1,3-dichloropropylene to sodium carbonate so that the yield and purity of propargyl alcohol can reach 73.3-73.4% and 99.9%, respectively, further improving the yield and purity of propargyl alcohol.

[0027] (5) The present invention controls the molar ratio of sodium hydroxide to 1,3-dichloropropylene so that the yield of propargyl alcohol can reach 73.5-73.6%, thereby further improving the yield of propargyl alcohol.

[0028] (6) The present invention controls the heating temperature of the remaining liquid in the method of removing sodium chloride so that the yield of propargyl alcohol can reach 73.7-73.8%, further improving the yield of propargyl alcohol.

[0029] (7) The present invention controls the mass ratio of isopropyl ether to crude propargyl alcohol so that the yield of propargyl alcohol can reach 73.9-74.0%, thereby improving the yield of propargyl alcohol. DETAILED DESCRIPTION

[0030] The present application is further described in detail below in conjunction with specific embodiments.

[0031] The following raw materials in this application are all commercially available products, and are intended to fully disclose the raw materials in this application, and should not be construed as limiting the sources of the raw materials. Specifically: 1,3-dichloropropylene, cis-1,3-dichloropropylene, with an effective substance content of 99%; isopropyl ether, with an effective substance content of 99.8%.

[0032] Example 1

[0033] The preparation method of propargyl alcohol in Example 1 is prepared by the following steps:

[0034] Mix 1,3-dichloropropylene and a sodium carbonate aqueous solution with a mass concentration of 4%, heat to 70°C, reflux for reaction for 5 hours, add dimethyl sulfoxide first, mix evenly, then add sodium hydroxide, react at 50°C, remove sodium chloride after the reaction, obtain crude propargyl alcohol, and distill to obtain propargyl alcohol;

[0035] Among them, the molar ratio of 1,3-dichloropropylene to sodium carbonate is 1:1.0; the molar ratio of 1,3-dichloropropylene to dimethyl sulfoxide is 1:1.1; and the molar ratio of 1,3-dichloropropylene to sodium hydroxide is 1:1.9.

[0036] The specific method for removing sodium chloride is as follows: after the reaction is completed, the temperature is lowered to 23° C. to precipitate part of the sodium chloride solid, the sodium chloride solid is removed by filtration, the remaining liquid is heated to 55° C., filtered, and the filtrate is collected.

[0037] The specific method of distillation is: under the conditions of a bottom temperature of 150-160°C and a top temperature of 130-140°C, dimethyl sulfoxide is removed from the bottom of the tower, and a mixture of propargyl alcohol and water is obtained at the top of the tower. 160g of isopropyl ether is added to 100mL of crude propargyl alcohol at the top of the tower, azeotropic dehydration is performed, fractionation is performed, and the fraction at 115°C is collected to obtain propargyl alcohol.

[0038] Example 2

[0039] The preparation method of propargyl alcohol in Example 2 is different from that in Example 1 in that 1,3-dichloropropylene and a sodium carbonate aqueous solution with a mass concentration of 4% are mixed, heated to 75° C. and refluxed for reaction for 5 hours, and the remaining operations are the same as in Example 1.

[0040] Example 3

[0041] The preparation method of propargyl alcohol in Example 3 is different from that in Example 1 in that 1,3-dichloropropylene and a sodium carbonate aqueous solution with a mass concentration of 4% are mixed, heated to 80° C. and refluxed for reaction for 5 hours, and the remaining operations are the same as in Example 1.

[0042] Example 4

[0043] The difference between the preparation method of propargyl alcohol in Example 4 and that in Example 2 is that sodium hydroxide is added and the reaction is carried out at 55° C. The remaining operations are the same as those in Example 2.

[0044] Example 5

[0045] The difference between the preparation method of propargyl alcohol in Example 5 and that in Example 2 is that sodium hydroxide is added and the reaction is carried out at 60° C. The remaining operations are the same as those in Example 2.

[0046] Example 6

[0047] The difference between the preparation method of propargyl alcohol in Example 6 and Example 4 is that 1,3-dichloropropylene and a 5% sodium carbonate aqueous solution are mixed, heated to 75° C. and refluxed for reaction for 5 hours. The remaining operations are the same as in Example 4.

[0048] Example 7

[0049] The preparation method of propargyl alcohol in Example 7 is different from that in Example 4 in that 1,3-dichloropropylene and an aqueous sodium carbonate solution with a mass concentration of 8% are mixed, heated to 75° C. and refluxed for reaction for 5 hours, and the remaining operations are the same as those in Example 4.

[0050] Example 8

[0051] The difference between the preparation method of propargyl alcohol in Example 8 and Example 4 is that 1,3-dichloropropylene and a sodium carbonate aqueous solution with a mass concentration of 10% are mixed, heated to 75° C. and refluxed for reaction for 5 hours, and the remaining operations are the same as in Example 4.

[0052] Example 9

[0053] The difference between the preparation method of propargyl alcohol in Example 9 and Example 4 is that 1,3-dichloropropylene and a sodium carbonate aqueous solution with a mass concentration of 12% are mixed, heated to 75° C. and refluxed for reaction for 5 hours. The remaining operations are the same as in Example 4.

[0054] Example 10

[0055] The preparation method of propargyl alcohol in Example 10 is different from that in Example 7 in that the molar ratio of 1,3-dichloropropylene to sodium carbonate is 1:1.1, and the remaining operations are the same as those in Example 7.

[0056] Embodiment 11

[0057] The difference between the preparation method of propargyl alcohol in Example 11 and that in Example 7 is that the molar ratio of 1,3-dichloropropylene to sodium carbonate is 1:1.2, and the remaining operations are the same as those in Example 7.

[0058] Example 12

[0059] The preparation method of propargyl alcohol in Example 12 is different from that in Example 7 in that the molar ratio of 1,3-dichloropropylene to sodium carbonate is 1:1.3, and the remaining operations are the same as those in Example 7.

[0060] Example 13

[0061] The difference between the preparation method of propargyl alcohol in Example 13 and Example 10 is that the molar ratio of sodium hydroxide to 1,3-dichloropropylene is 1:2.0, and the remaining operations are the same as those in Example 7.

[0062] Embodiment 14

[0063] The difference between the preparation method of propargyl alcohol in Example 14 and Example 10 is that the molar ratio of sodium hydroxide to 1,3-dichloropropylene is 1:2.1, and the remaining operations are the same as those in Example 7.

[0064] Embodiment 15

[0065] The preparation method of propargyl alcohol in Example 14 is different from that in Example 10 in that the molar ratio of sodium hydroxide to 1,3-dichloropropylene is 1:2.2, and the remaining operations are the same as those in Example 7.

[0066] Example 16

[0067] The difference between the preparation method of propargyl alcohol in Example 16 and Example 14 is that the specific method for removing sodium chloride is: after the reaction is completed, the temperature is lowered to 23°C to precipitate part of the sodium chloride solid, the sodium chloride solid is filtered out, the remaining liquid is heated to 60°C, filtered, and the filtrate is collected. The remaining operations are the same as in Example 14.

[0068] Embodiment 17

[0069] The difference between the preparation method of propargyl alcohol in Example 17 and Example 14 is that the specific method for removing sodium chloride is: after the reaction is completed, the temperature is lowered to 23°C to precipitate part of the sodium chloride solid, the sodium chloride solid is filtered out, the remaining liquid is heated to 70°C, filtered, and the filtrate is collected. The remaining operations are the same as in Example 14.

[0070] Embodiment 18

[0071] The difference between the preparation method of propargyl alcohol in Example 18 and Example 14 is that the specific method for removing sodium chloride is: after the reaction is completed, the temperature is lowered to 23°C to precipitate part of the sodium chloride solid, the sodium chloride solid is removed by filtration, the remaining liquid is heated to 80°C, filtered, and the filtrate is collected. The remaining operations are the same as in Example 14.

[0072] Embodiment 19

[0073] The difference between the preparation method of propargyl alcohol in Example 19 and Example 14 is that the specific method for removing sodium chloride is: after the reaction is completed, the temperature is lowered to 23°C to precipitate part of the sodium chloride solid, the sodium chloride solid is filtered out, the remaining liquid is heated to 90°C, filtered, and the filtrate is collected. The remaining operations are the same as in Example 14.

[0074] Embodiment 20

[0075] The difference between the preparation method of propargyl alcohol in Example 20 and Example 17 is that the specific method of distillation is: adding 170g of isopropyl ether to 100g of crude propargyl alcohol, azeotropic dehydration, fractionation, collecting the fraction at 115°C, and the remaining operations are the same as Example 17.

[0076] Embodiment 21

[0077] The difference between the preparation method of propargyl alcohol in Example 21 and Example 17 is that the specific method of distillation is: adding 180g of isopropyl ether to 100g of crude propargyl alcohol, azeotropic dehydration, fractionation, collecting the fraction at 115°C, and the remaining operations are the same as Example 17.

[0078] Embodiment 22

[0079] The difference between the preparation method of propargyl alcohol in Example 22 and Example 17 is that the specific method of distillation is: adding 190g of isopropyl ether to 100g of crude propargyl alcohol, azeotropic dehydration, fractionation, collecting the fraction at 115°C, and the remaining operations are the same as Example 17.

[0080] Embodiment 23

[0081] The difference between the preparation method of propargyl alcohol in Example 23 and Example 17 is that the specific method of distillation is: adding 200g of isopropyl ether to 100g of crude propargyl alcohol, azeotropic dehydration, fractionation, collecting the fraction at 115°C, and the remaining operations are the same as Example 17.

[0082] Comparative Example 1

[0083] The preparation method of propargyl alcohol in Comparative Example 1 is prepared by the following steps:

[0084] S1. In a 2000ml reaction bottle, add 900ml water and 3.3mol sodium carbonate, stir and mix evenly, then add 3mol cis-1,3-dichloropropylene, heat to 105°C, stir and reflux vigorously for 8 hours, and the reflux is completed when the residual amount of cis-1,3-dichloropropylene detected by gas chromatography is less than 0.5%. After the reflux is completed, stand and separate, and suck the upper organic phase into a receiving bottle to obtain 248g 3-chloropropylene alcohol. Add the lower aqueous phase obtained in step 1 to a crystallization bottle, cool to 5°C, and precipitate sodium bicarbonate. After the precipitation is completely precipitated, extract the mother liquor and concentrate it to obtain 600ml water. Filter the remaining concentrated solution while hot to obtain 170g sodium chloride crystals and filtrate. Add the concentrated water and filtrate to the crystallization bottle, stir and add 100g water and 120g caustic soda to obtain a saturated soda ash solution for recycling.

[0085] S2, in a 2000ml reaction bottle, add 496g of dimethyl sulfoxide, 1g of hydroquinone and 3-chloropropenol obtained in step S1, heat to 70°C, and add 102g of caustic soda flakes in 20 portions, the caustic soda flakes are added for about 1 hour, and the mixture is stirred for 2 hours after the addition is complete. After the reaction is completed, the mixture is cooled to 40°C, 37wt% concentrated hydrochloric acid is added to neutralize the mixture to a pH value of 7, and the mixture is further cooled to 30°C, and a precipitate begins to precipitate. After the precipitation is complete, the mixture is filtered, and the filter cake is washed with dimethyl sulfoxide until the filtrate is light yellow. The filtrate is fractionated under normal pressure, and the fraction at 95-115°C is collected to obtain 170g of crude propargyl alcohol;

[0086] S3. Add 50 g of isopropyl ether to the crude propargyl alcohol obtained in step S2, and perform azeotropic dehydration using a fractionating column with a theoretical plate number of 4 until the obtained condensate is not layered (at this time, water is basically removed), and fractionate the remaining liquid after azeotropic dehydration using a fractionating column with a theoretical plate number of 10, control the reflux ratio to 2:1, collect the fraction at 114-115 ° C, and obtain 104 g of colorless liquid, i.e., propargyl alcohol.

[0087] Comparative Example 2

[0088] The preparation method of propargyl alcohol in Comparative Example 2 is prepared by the following steps:

[0089] First, an unsupported basic copper carbonate catalyst, trioxymethylene and ethylene glycol are added to a reactor, acetylene is introduced, and the reactor is heated to 140°C for activation. The pH value is adjusted by sodium hydroxide during the activation process. After the catalyst activation is completed, the introduction of acetylene gas is stopped, and 1,4-butynediol and an organic solvent are added to the reactor. The reactor is continuously heated to decomposition. Under the action of the unsupported basic copper carbonate catalyst, 1,4-butynediol is decomposed to generate propynyl alcohol and formaldehyde, and the propynyl alcohol is separated from the reaction solution in the form of gas.

[0090] Comparative Example 3

[0091] The preparation method of propargyl alcohol in Comparative Example 3 is different from that in Example 1 in that 1,3-dichloropropylene and sodium carbonate aqueous solution are mixed, heated to 65° C. and refluxed for reaction for 5 hours.

[0092] Comparative Example 4

[0093] The preparation method of propargyl alcohol in Comparative Example 4 is different from that in Example 1 in that 1,3-dichloropropylene and sodium carbonate aqueous solution are mixed, heated to 85° C. and refluxed for reaction for 5 hours.

[0094] Comparative Example 5

[0095] The preparation method of propargyl alcohol in Comparative Example 5 is different from that in Example 1 in that sodium hydroxide is added and the reaction is carried out at 45°C.

[0096] Comparative Example 6

[0097] The preparation method of propargyl alcohol in Comparative Example 6 is different from that in Example 1 in that sodium hydroxide is added and the reaction is carried out at 65°C.

[0098] Performance Testing The propargyl alcohol obtained in Examples 1-23 and Comparative Examples 1-6 was tested using the following method. The specific test results are shown in Table 1.

[0099] Yield: Based on 1,3-dichloropropylene, calculated through the calculation of propynyl alcohol product and reaction equilibrium.

[0100] Purity: The purity of propargyl alcohol was determined by gas chromatography.

[0101] Table 1 Propynol test results

[0102]

[0103]

[0104] The test results in Table 1 show that, by adopting the preparation method of propargyl alcohol of the present application, the yield and purity of propargyl alcohol can reach up to 73.8% and 99.9% respectively, which improves the yield and purity of propargyl alcohol. The preparation method is simple and has high production safety. In the reaction process, sodium hydroxide is directly added to the reactor, which reduces the time of initial reaction stratification, saves production steps, reduces heat loss and material loss during reflux and taking the upper organic phase, and improves production efficiency.

[0105] In Examples 1-3, the preparation method of propargyl alcohol in Example 2 was adopted, and the yield and purity of propargyl alcohol could reach 73.1% and 99.4%, respectively, which were higher than those in Example 1 and Example 3, thereby improving the yield and purity of propargyl alcohol. The reaction conditions of 1,3-dichloropropylene and sodium carbonate solution were heating to 75° C. and reflux for 5 h, which was more conducive to improving the yield and purity of propargyl alcohol.

[0106] In combination with Example 2 and Example 4-5, the preparation method of propargyl alcohol in Example 4 is adopted, and the yield and purity of propargyl alcohol can reach 73.2% and 99.6%, respectively, which are higher than those in Example 2 and Example 5, thereby improving the yield and purity of propargyl alcohol. It may be that adding sodium hydroxide and reacting at 55° C. is more conducive to improving the yield and purity of propargyl alcohol.

[0107] In combination with Example 4 and Examples 6-9, the preparation method of propargyl alcohol in Example 6-8 is adopted, and the yield and purity of propargyl alcohol can reach 73.3-73.4% and 99.6-99.8%, respectively, which are higher than those in Example 2 and Example 9, thereby improving the yield and purity of propargyl alcohol, which may be more conducive to improving the yield and purity of propargyl alcohol when the mass concentration of the sodium carbonate aqueous solution is 5-10%.

[0108] In combination with Example 7 and Examples 10-12, the preparation method of propargyl alcohol in Example 10-11 is adopted, and the yield and purity of propargyl alcohol can reach 73.3-73.4% and 99.9%, respectively, which are higher than those in Example 7 and Example 12, thereby improving the yield and purity of propargyl alcohol. The molar ratio of 1,3-dichloropropylene to sodium carbonate is 1:(1.1-1.2), which is more conducive to improving the yield and purity of propargyl alcohol.

[0109] In combination with Example 11 and Examples 13-15, the preparation method of propargyl alcohol in Examples 13-14 is adopted, and the yield of propargyl alcohol can reach 73.5-73.6%, which is higher than that in Example 11 and Example 15, and the yield of propargyl alcohol is improved, which may be related to the molar ratio of sodium hydroxide to 1,3-dichloropropylene being 1:(2.0-2.1), which is more conducive to improving the yield of propargyl alcohol.

[0110] In combination with Example 14 and Examples 16-19, the preparation method of propargyl alcohol in Examples 16-18 is adopted, and the yield of propargyl alcohol can reach 73.7-73.8%, which is higher than that in Example 14 and Example 19, and the yield of propargyl alcohol is improved. It may be that the remaining liquid is heated to 60-80°C in the method of removing sodium chloride, which is more conducive to improving the yield of propargyl alcohol.

[0111] In combination with Example 17 and Examples 20-23, the preparation method of propargyl alcohol in Examples 20-22 is adopted, and the yield of propargyl alcohol can reach 73.9-74.0%, which is higher than that in Example 17 and Example 23, thereby improving the yield of propargyl alcohol. This may be due to the mass ratio of isopropyl ether to crude propargyl alcohol being 1:(1.7-1.9), which is more conducive to improving the yield of propargyl alcohol.

[0112] In addition, in combination with the various index data of the detection method of Comparative Examples 1-6 and Example 1, it is found that compared with Examples 1-2, the yield and purity of propargyl alcohol in the present application are not low, the method is simple, and the production efficiency is high; moreover, in the present application, 1,3-dichloropropylene and sodium carbonate aqueous solution are mixed and heated to 70-80°C for reflux reaction for 4-6h, and then sodium hydroxide is added and reacted at 50-60°C, which can improve the yield and purity of propargyl alcohol to varying degrees.

[0113] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A method for preparing propargyl alcohol, characterized in that: It includes the following steps: Mix 1,3-dichloropropylene and sodium carbonate aqueous solution, heat to 70-80°C, reflux for 4-6h, add dimethyl sulfoxide at a molar ratio of (1.0-1.2) to 1,3-dichloropropylene and mix evenly, then add sodium hydroxide, react at 50-60°C, remove sodium chloride after the reaction, obtain crude propargyl alcohol, and distill to obtain propargyl alcohol; The reaction conditions of the 1,3-dichloropropylene and sodium carbonate solution were heated to 75 ° C and refluxed for 5h; The mass concentration of the sodium carbonate aqueous solution is 5-10%; The molar ratio of 1,3-dichloropropylene and sodium carbonate is 1: (1.1-1.2); The molar ratio of 1,3-dichloropropylene to sodium hydroxide is 1: (2.0-2.1); The method for removing sodium chloride comprises the following steps: after the reaction is completed, the temperature is cooled to 20-25 ℃ to precipitate part of the sodium chloride solid, the sodium chloride solid is removed by filtration, the remaining liquid is heated to 60-80 ℃, filtered, and the filtrate is collected; The distillation comprises the following steps: first removing dimethyl sulfoxide from the crude propargyl alcohol, then adding isopropyl ether, azeotropic dehydration, fractionation, collecting the fraction at 114-115 ℃ to obtain propargyl alcohol; The mass ratio of the isopropyl ether to the crude propargyl alcohol is 1:(1.7-1.9).

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