A method for preparing anhydrous Na2S and derivatives thereof

Abstract

The application discloses a preparation method of anhydrous Na2S and derivatives thereof, and belongs to the technical field of substance synthesis. The method comprises the following steps: under the atmosphere of inert gas or nitrogen, phosphine sulfur compound R3PS is fully reacted with sodium under the condition of non-polar hydrocarbon solvent or without solvent to generate phosphine base compound R3P and Na2S; after the reaction is completed, the solid Na2S is separated from the reaction system by using the property that Na2S is insoluble in organic solvents, then the solid Na2S is cleaned by using an organic solvent and vacuum dried to obtain the anhydrous Na2S; the chemical formula of the phosphine sulfur compound is R3PS, R3PS is R 1 R 2 R 3 P and Na2S, after the reaction is completed, the solid Na2S is separated from the reaction system by using the property that Na2S is insoluble in organic solvents, then the solid Na2S is cleaned by using an organic solvent and vacuum dried to obtain the anhydrous Na2S; the chemical formula of the phosphine sulfur compound is R3PS, R3PS is R 1 R 2 R 3 PS; the chemical formula of the phosphine base compound is R3P, R3P is R 1 R 2 R 3 P; R 1 , R 2 and R 3 are independently selected from aromatic or aliphatic substituents, wherein at least one R is an aromatic substituent. The method is safe, simple to operate, easy to control, environment-friendly and easy to be industrialized and scaled up.

Description

Technical Field

[0001] The present invention relates to the technical field of material synthesis, and more particularly to a method for preparing anhydrous Na2S. Background Art

[0002] Sodium sulfide (Na2S) is widely used in the dyeing, leather, papermaking, textile, and cotton fabric dyeing industries, and is also widely used in the pharmaceutical industry. Industrially, sodium sulfide can be produced by high-temperature calcination and reduction of Glauber's salt and coal powder, by absorbing H2S in a sodium hydroxide solution, or by precipitating barium sulfate through a double decomposition reaction between sodium sulfate and barium sulfide. However, these methods only produce aqueous sodium sulfide, making it difficult to produce anhydrous sodium sulfide. Aqueous sodium sulfide cannot be used in fields such as polymer material manufacturing, which often require anhydrous sodium sulfide.

[0003] In principle, anhydrous sodium sulfide can be obtained through the reaction of H2S and metallic sodium, or the reaction of metallic sodium and sulfur; the former requires the use of very toxic H2S, and the latter, the reaction is difficult to control and prone to explosion.

[0004] The present invention is dedicated to finding a preparation method of anhydrous sodium sulfide which is safe, environmentally friendly and easy to industrially scale up. Summary of the Invention

[0005] 1. Technical problems to be solved

[0006] In view of the problems existing in the prior art, the object of the present invention is to provide a method for preparing anhydrous Na2S, which provides a method for preparing anhydrous sodium sulfide that is safe, simple to operate, easy to control, environmentally friendly, and easy to industrially scale up.

[0007] 2. Technical solution

[0008] To solve the above problems, the present invention adopts the following technical solutions.

[0009] A method for preparing anhydrous Na2S, comprising the following steps: reacting a phosphine-sulfur compound R3PS with metallic sodium in a non-polar hydrocarbon solvent or without solvent under an inert gas or nitrogen atmosphere to generate a phosphine-based compound R 1 R 2 R 3 P and Na2S, after the reaction is completed, solid Na2S is separated from the reaction system by taking advantage of the fact that Na2S is insoluble in organic solvents, and then the solid Na2S is washed with an organic solvent and vacuum dried to obtain anhydrous Na2S;

[0010]

[0011] The chemical formula of phosphine-sulfur compounds is R3PS, where R3PS is R 1 R 2 R 3 PS; the chemical formula of phosphine compounds is R3P, R3P is R 1 R 2 R 3 P; R 1 、R 2 and R 3 are independently selected from aromatic or aliphatic substituents, R 1 、R 2 and R 3 At least one of them is an aromatic substituent, R 1 、R 2 and R 3 Can be the same or different.

[0012] The present invention will be further described below:

[0013] Phosphine-sulfur compounds R 1 R 2 R 3 PS reacts with the metal reducing agent sodium in the absence of solvent or non-polar hydrocarbon solvent under inert gas or nitrogen atmosphere to generate organic phosphine R 1 R 2 R 3 P and Na2S.

[0014] By utilizing the property that Na2S is insoluble in organic solvents, solid Na2S is separated from the reaction system.

[0015] Phosphine sulfur compounds R 1 R 2 R 3 P.S. and R. 1 R 2 R 3 P is soluble in organic solvents.

[0016] If the phosphine-sulfur compound R 1 R 2 R 3 PS reacts with the metal reducing agent sodium in the absence of solvent. After the reaction is completed, an organic solvent can be added to the reaction system to make the organic phosphine R 1 R 2 R 3 P and unreacted phosphine sulfide compound R 1 R 2 R 3 PS is dissolved in an organic solvent, and solid Na2S and an organic phase are obtained by filtration. The solid Na2S is then washed with an organic solvent and vacuum dried to obtain anhydrous Na2S.

[0017] In addition to the oil solvent, the organic phase contains organic phosphine R 1 R 2 R 3 P and possible unreacted phosphine-sulfur compounds R 1 R 2 R 3 PS; finally, the organic phosphine R is purified by organic synthesis methods, such as silica gel column, recrystallization, or distillation. 1 R 2 R 3 P and any unreacted phosphine-sulfur compound R 1 R 2 R 3 PS can be effectively separated to obtain pure organic phosphine R 1 R 2 R 3 P.

[0018] If the phosphine-sulfur compound R 1 R 2 R 3 PS reacts with metal reducing agent sodium in a non-polar hydrocarbon solvent. After the reaction is completed, solid Na2S and an organic phase can be obtained by filtration. The solid Na2S is then washed with an organic solvent and vacuum dried to obtain anhydrous Na2S. In addition to the oil solvent, the organic phase contains organic phosphine R 1 R 2 R 3 P and possible unreacted phosphine-sulfur compounds R 1 R 2 R 3 PS; finally, the organic phosphine R is purified by organic synthesis methods, such as silica gel column, recrystallization, or distillation. 1 R 2 R 3 P and any unreacted phosphine-sulfur compound R 1 R 2 R 3 PS can be effectively separated to obtain pure organic phosphine R 1 R 2 R 3 P.

[0019] The organic solvent can be the non-polar hydrocarbon solvent described in the present invention or a phosphine-sulfur compound R 1 R 2 R 3 PS and organic phosphine R 1 R 2 R 3 Other organic solvents in which P is soluble.

[0020] Furthermore, in the phosphine-sulfur compound R 1 R 2 R 3 Before PS reacts with sodium, it also includes step 1: first use R 1 R 2 R 3 P and sulfur react completely to form phosphine-sulfur compound R 1 R 2 R 3 PS, the R 1 R 2 R 3 The molar ratio of P to sulfur is 1:1.

[0021] Furthermore, the phosphine-sulfur compound R 1 R 2 R 3 PS reacts with metallic sodium in a non-polar hydrocarbon solvent or without solvent to generate Na2S and phosphine-based compound R 1 R 2 R 3 P is step 2, the metallic sodium in step 2 and R in step 1 1 R 2 R 3 The molar ratio of P is 2:1;

[0022] The process further comprises step 3: adding sulfur to the reaction system in step 2, and sequentially performing steps 1, 2, and 3 to form the following cyclic reaction system:

[0023]

[0024] Further, sodium and phosphine sulfur compound R 1 R 2 R 3 The molar ratio of PS is 0.1-5:1.

[0025] Further, sodium and phosphine sulfur compound R 1 R 2 R 3 The molar ratio of PS is 1-2:1.

[0026] Furthermore, the sodium metal used in the method can be in the form of micron powder, liquid or bulk metal.

[0027] Furthermore, the non-polar hydrocarbon solvent and the phosphine-sulfur compound R 1 R 2 R 3 The weight ratio of PS is 0.5-20:1.

[0028] Furthermore, the non-polar hydrocarbon solvent and the phosphine-sulfur compound R1 R 2 R 3 The weight ratio of PS is 2-5:1.

[0029] Furthermore, the reaction temperature of the phosphine-sulfur compound and metallic sodium is 0-300°C.

[0030] Furthermore, the reaction temperature of the phosphine-sulfur compound and metallic sodium is 60-200°C.

[0031] Furthermore, the non-polar hydrocarbon solvent is selected from alkanes or aromatic hydrocarbons.

[0032] Furthermore, the non-polar hydrocarbon solvent can be selected from one or a mixture of any multiple of n-hexane, n-heptane, polyethylene, polypropylene, benzene, toluene, ethylbenzene, o-xylene, p-xylene and trimethylbenzene.

[0033] Furthermore, the non-polar hydrocarbon solvent can be selected from one or a mixture of any two or more of toluene, ethylbenzene, o-xylene, p-xylene and mesitylene.

[0034] Furthermore, the organic phosphine R 1 R 2 R 3 P does not react with metallic sodium in the absence of solvent or in the presence of non-polar hydrocarbon solvents.

[0035] Furthermore, the organic phosphine R 1 R 2 R 3 P does not react with non-polar hydrocarbon solvents under non-polar hydrocarbon solvent conditions.

[0036] Furthermore, the phosphine-sulfur compound R 1 R 2 R 3 PS is one or more of triphenylphosphine sulfide, tri(o-methylphenyl)phosphine sulfide, phenyldimethylphosphine sulfide, tri(p-methylphenyl)phosphine sulfide or diphenylmethylphosphine sulfide.

[0037] Furthermore, the phosphine-sulfur compound R 1 R 2 R 3 PS is triphenylphosphine sulfide.

[0038] Furthermore, the non-polar hydrocarbon solvent is selected from one or a mixture of toluene, p-xylene and o-xylene.

[0039] Since the organic phosphine R 1 R 2 R 3 P does not react with metallic sodium in the absence of solvent or in non-polar hydrocarbon solvents. 1 R 2 R3 P also does not react with non-polar hydrocarbon solvents, so the phosphine sulfide compound R 1 R 2 R 3 When PS reacts with sodium metal, the only product obtained is organic phosphine R 1 R 2 R 3 P and Na2S, the reaction does not produce by-products, and finally, the phosphine sulfur compound R 1 R 2 R 3 PS can react with the metal reducing agent sodium to prepare organic phosphine R with high selectivity. 1 R 2 R 3 P and Na2S.

[0040] Furthermore, the phosphine-sulfur compound R 1 R 2 R 3 PS is triphenylphosphine sulfide.

[0041] Furthermore, R 1 、R 2 and R 3 Can be independently selected from C1-C 20 Straight or branched chain alkyl or alkenyl, C3-C 20 Cycloalkyl, C7-C 20 Aralkyl, C6-C 20 Aryl and C2-C 20 of a heterocyclic group.

[0042] Furthermore, R 1 、R 2 and R 3 Independently selected from phenyl with C1-C6 long chain or branched alkyl, heterocyclic aromatic hydrocarbon containing N, O, S atoms and C1-C 20 Long chain or branched chain alkyl groups.

[0043] A method for preparing a Na2S derivative comprises the following steps: reacting Na2S prepared by a method for preparing anhydrous Na2S with sulfur in a molten state to obtain a sodium polysulfide compound Nax1Sy1, where x1 and y1 are both positive integers.

[0044] A method for preparing a Na2S derivative can also be carried out using the following steps: dissolving Na2S obtained by a method for preparing anhydrous Na2S in an aqueous solution, boiling and refluxing the Na2S aqueous solution, and adding sulfur to react to obtain a sodium polysulfide compound Nax1Sy1, where x1 and y1 are both positive integers.

[0045] A method for preparing dialkyl sulfide comprises the following steps: reacting Na2S prepared by a method for preparing anhydrous Na2S with an alkyl halide RX to prepare dialkyl sulfide R2S.

[0046] 3. Beneficial effects

[0047] Compared with the prior art, the advantages of the present invention are:

[0048] (1) The phosphine-sulfur compound of the present invention and metallic sodium are reacted in a non-polar hydrocarbon solvent or without solvent, and the phosphine-sulfur compound R 1 R 2 R 3 PS can react with high selectivity to generate Na2S and R 1 R 2 R 3 P, the preparation process R 1 R 2 R 3 P will not react with metallic sodium, and the reaction can prepare anhydrous Na2S. The preparation method is safe, simple to operate, easy to control, environmentally friendly, and easy to industrially scale up the production of anhydrous sodium sulfide.

[0049] (2) The present invention is to use R 1 R 2 R 3 P and sulfur react completely, R 1 R 2 R 3 The molar ratio of P and sulfur is 1:1, and the reaction produces R 1 R 2 R 3 PS, then to R 1 R 2 R 3 Adding metallic sodium and R 1 R 2 R 3 PS reaction, metallic sodium and R 1 R 2 R 3 The molar ratio of P is 2:1, and the reaction produces Na2S and R 1 R 2 R 3 After P, continue to add R 1 R 2 R 3 P and an equal molar amount of sulfur react to form R 1 R 2 R 3 PS, continue to add metallic sodium to make the metallic sodium and R 1 R 2 R 3PS reacts to produce Na2S and R 1 R 2 R 3 P; continue to add sulfur to the reaction solution to make sulfur and R 1 R 2 R 3 P reacts to form R 1 R 2 R 3 PS, R 1 R 2 R 3 P is effectively utilized repeatedly to achieve the purpose of continuous preparation of anhydrous Na2S.

[0050] (3) The present invention can prepare a sodium polysulfide compound Nax1Sy1 by reacting the anhydrous Na2S prepared by the present invention with an appropriate amount of sulfur in a molten state. The sodium polysulfide compound Nax1Sy1 is anhydrous.

[0051] (4) The present invention prepares dialkyl sulfide R2S by reacting anhydrous Na2S prepared by the present invention with an alkyl halide RX. DETAILED DESCRIPTION

[0052] The present invention is further described below with reference to specific embodiments, but the protection scope of the present invention is not limited thereto:

[0053] Examples 1-14 and Comparative Example 1 are about phosphine-sulfur compound R 1 R 2 R 3 PS reacts with metallic sodium in the absence of solvent or in a non-polar hydrocarbon solvent under an inert gas or nitrogen atmosphere to generate an organic phosphine R 1 R 2 R 3 P and anhydrous Na2S; no by-products are generated in this preparation process.

[0054] Example 1

[0055] 0.5 mmol of triphenylphosphine sulfide, 1.0 mmol of sodium metal, and 1.5 mL of toluene were placed in a glass tube, heated to 110°C under nitrogen protection, kept warm for 3 hours, cooled to room temperature, and filtered to obtain an organic phase and a solid. The solid was washed with an organic solvent and vacuum dried to obtain 0.49 mmol of anhydrous Na2S. The organic phase was decompressed to remove the organic solvent and purified to obtain 0.49 mmol of triphenylphosphine in a yield of 98%.

[0056] Comparative Example 1

[0057] The other conditions are the same as in Example 1, and the difference between Comparative Example 1 and Example 1 is that the polar solvent tetrahydrofuran is used as the solvent, and the temperature is 70°C, and 0.28 mmol of Ph3P is obtained in a yield of 56%, containing 42% of Ph2PH.

[0058] Example 2

[0059] A glass tube is charged with 0.5 mmol of tri(p-methylphenyl)phosphine sulfide, 1.0 mmol of metallic sodium, and 1.5 mL of toluene, and heated to 110°C under nitrogen protection for 3 h. After cooling to room temperature, the organic phase and solid are obtained by filtration. The solid is washed with an organic solvent and dried under vacuum to obtain 0.48 mmol of anhydrous Na2S. The organic solvent is removed from the organic phase under reduced pressure, and purification is performed to obtain 0.48 mmol of tri(p-methylphenyl)phosphine in a yield of 96%.

[0060] Example 3

[0061] A glass tube is charged with 0.5 mmol of tri(p-methylphenyl)phosphine sulfide, 1.0 mmol of metallic sodium, and 1.5 mL of toluene, and heated to 110°C under nitrogen protection for 3 h. After cooling to room temperature, the organic phase and solid are obtained by filtration. The solid is washed with an organic solvent and dried under vacuum to obtain 0.48 mmol of anhydrous Na2S. The organic solvent is removed from the organic phase under reduced pressure, and purification is performed to obtain 0.48 mmol of tri(p-methylphenyl)phosphine in a yield of 96%.

[0062] Example 4

[0063] A glass tube is charged with 0.5 mmol of tri(p-methylphenyl)phosphine sulfide, 1.0 mmol of metallic sodium, and 1.5 mL of toluene, and heated to 110°C under nitrogen protection for 3 h. After cooling to room temperature, the organic phase and solid are obtained by filtration. The solid is washed with an organic solvent and dried under vacuum to obtain 0.48 mmol of anhydrous Na2S. The organic solvent is removed from the organic phase under reduced pressure, and purification is performed to obtain 0.48 mmol of tri(p-methylphenyl)phosphine in a yield of 96%.

[0064] Example 5

[0065] A glass tube is charged with 0.5 mmol of tri(p-methylphenyl)phosphine sulfide, 1.0 mmol of metallic sodium, and 1.5 mL of toluene, and heated to 110°C under nitrogen protection for 3 h. After cooling to room temperature, the organic phase and solid are obtained by filtration. The solid is washed with an organic solvent and dried under vacuum to obtain 0.48 mmol of anhydrous Na2S. The organic solvent is removed from the organic phase under reduced pressure, and purification is performed to obtain 0.48 mmol of tri(p-methylphenyl)phosphine in a yield of 96%.

[0066] It can be found from Examples 1-5 that different phosphine sulfide compounds R 1 R 2R 3 PS reacts with metal reducing agent sodium in the absence of solvent or in non-polar hydrocarbon solvent to obtain the corresponding organic phosphine R 1 R 2 R 3 P and anhydrous Na2S, and the yield is high.

[0067] Example 6

[0068] Other conditions were the same as those in Example 1. The difference between Example 6 and Example 1 was that 0.5 mmol of metallic sodium was used for the reaction to obtain 0.25 mmol of triphenylphosphine, with a sodium-based yield of 100%.

[0069] It can be found from Examples 1 and 6 that metallic sodium and phosphine-sulfur compound R 1 R 2 R 3 When the molar ratio of PS is 1-2:1, sodium can react with the reactants more fully and the utilization rate of metallic sodium is higher.

[0070] Example 7

[0071] Other conditions were the same as those in Example 1. The difference between Example 7 and Example 1 was that the reaction was carried out at 80° C. for 10 hours to obtain 0.5 mmol of triphenylphosphine and 0.5 mmol of anhydrous Na 2 S in a yield of 100%.

[0072] Example 8

[0073] Other conditions were the same as those in Example 1. The difference between Example 8 and Example 1 was that the reaction was carried out at 150° C. for 2 hours to obtain 0.48 mmol of triphenylphosphine and 0.48 mmol of anhydrous Na 2 S, with a yield of 96%.

[0074] It can be found from Examples 1 and 7-8 that the phosphine-sulfur compound R provided by the present invention 1 R 2 R 3 When PS reacts with metallic sodium in the absence of solvent or in a non-polar hydrocarbon solvent, the organic phosphine R can be prepared at a temperature below 170°C. 1 R 2 R 3 P.

[0075] Example 9

[0076] Other conditions were the same as those in Example 1. Example 9 differed from Example 1 in that 85% pure Ph3PS was used (other main components of the raw materials: 3% HOCH2CH2OH, 5% EtOH, 5% MeOCH2CH2OMe) to obtain 0.30 mmol of triphenylphosphine and 0.30 mmol of anhydrous Na2S in a yield of 60%.

[0077] It can be found from Example 9 that the phosphine sulfur compound R 1 R 2 R 3 The purity of PS can be less than 100%.

[0078] Example 10

[0079] Put 0.5 mmol of triphenylphosphine sulfide, 1.0 mmol of sodium metal, and 1.5 mL of ethylbenzene into a glass tube, and heat to 136°C under nitrogen protection, and keep the temperature for 3 h, and then cool to room temperature, and filter to obtain an organic phase and a solid, and clean the solid with an organic solvent, and vacuum dry to obtain 0.45 mmol of anhydrous Na2S, and remove the organic solvent from the organic phase under reduced pressure, and purify to obtain 0.45 mmol of triphenylphosphine, with a yield of 90%.

[0080] Example 11

[0081] The other conditions are the same as in Example 1, except that p-xylene is used as the solvent in Example 11, and 0.45 mmol of triphenylphosphine, 0.45 mmol of anhydrous Na2S, and a yield of 90% are obtained.

[0082] Example 12

[0083] The other conditions are the same as in Example 1, except that o-xylene is used as the solvent in Example 12, and 0.46 mmol of triphenylphosphine, 0.46 mmol of anhydrous Na2S, and a yield of 92% are obtained.

[0084] Example 13

[0085] The other conditions are the same as in Example 1, except that m-xylene is used as the solvent in Example 13, and 0.45 mmol of triphenylphosphine, 0.45 mmol of anhydrous Na2S, and a yield of 90% are obtained.

[0086] It can be found from Examples 1, Comparative Example 1, and Examples 10-13 that ethylbenzene, toluene, m-xylene, o-xylene, and p-xylene are all nonpolar hydrocarbon solvents, while tetrahydrofuran is a polar solvent; the phosphine sulfur compound R 1 R 2 R 3 The phosphine sulfur compound R 1 R 2 R 3 The phosphine sulfur compound PS can selectively react to generate the organic phosphine R 1 R 2 R 3P and divalent metal sulfide, no by-products are generated; while phosphine sulfide compounds R 1 R 2 R 3 PS reacts with metallic sodium in a polar solvent to generate by-products, phosphine-sulfur compounds R 1 R 2 R 3 PS cannot react to form organophosphine R with high selectivity. 1 R 2 R 3 P.

[0087] Examples 14, 16-19 are to use R 1 R 2 R 3 P and R 1 R 2 R 3 P and an equal molar amount of sulfur react fully and completely to form phosphine-sulfur compound R 1 R 2 R 3 PS, then the phosphine-sulfur compound R 1 R 2 R 3 Example of preparing anhydrous Na2S by reacting PS with metallic sodium in a non-polar hydrocarbon solvent.

[0088] Example 14

[0089] 0.5 mmol of triphenylphosphine and 0.5 mmol of sulfur were heated in 1.5 mL of toluene at 110°C for 1 h to quantitatively obtain Ph3PS. Then, under nitrogen, 1.0 mmol of sodium metal was added and the reaction continued for 3 h. The solid was filtered under nitrogen, rinsed with toluene, and dried under vacuum to obtain 0.5 mmol of anhydrous Na2S in a 100% yield.

[0090] Example 15 is to repeatedly recycle R 1 R 2 R 3 P Example of preparing anhydrous Na2S.

[0091] Example 15

[0092] Step 1: 0.5 mmol of triphenylphosphine and 0.5 mmol of sulfur were heated in 1.5 mL of toluene at 110°C for 1 h to allow for complete reaction to obtain Ph3PS. Step 2: 1.0 mmol of metallic sodium was then added under nitrogen and the reaction continued for 3 h. Step 3: After the reaction in step 2 was completed, 0.5 mmol of sulfur was added and steps 1, 2, and 3 were repeated four times. The solid was then filtered under nitrogen to obtain a solid, which was rinsed with toluene and dried in vacuo to obtain 2.5 mmol of anhydrous Na2S. The sulfur base yield was 100%.

[0093] Example 16

[0094] Other conditions were the same as those in Example 14. The difference between Example 16 and Example 14 was that diphenylmethylphosphine was used to obtain anhydrous Na2S, 0.45 mmol, with a yield of 90%.

[0095] Example 17

[0096] Other conditions were the same as those in Example 14. The difference between Example 17 and Example 14 was that dimethylphenylphosphine was used to obtain anhydrous Na2S, 0.48 mmol, with a yield of 96%.

[0097] Example 18

[0098] Other conditions were the same as those in Example 14. The difference between Example 18 and Example 14 was that 1.5 mL of ethylbenzene was used to obtain anhydrous Na2S, 0.47 mmol, with a yield of 94%.

[0099] Example 19

[0100] Other conditions were the same as those in Example 14. The difference between Example 19 and Example 14 was that 1.5 mL of p-xylene was used to obtain anhydrous Na2S, 0.48 mmol, with a yield of 96%.

[0101] It can be found from Examples 14, 16 and 15 that different R 1 R 2 R 3 P first reacts with sulfur, and then the obtained phosphine-sulfur compound R is used 1 R 2 R 3 PS can then react with metallic sodium in a non-polar hydrocarbon solvent to prepare anhydrous Na2S, and a good yield can be obtained.

[0102] It can be found from Examples 14, 18 and 19 that the use of R 1 R 2 R 3 P first reacts with sulfur, and then the obtained phosphine-sulfur compound R is used1 R 2 R 3 PS then reacts with metallic sodium in a non-polar hydrocarbon solvent to prepare anhydrous Na2S. Using different non-polar hydrocarbon solvents, such as ethylbenzene, p-xylene, and toluene, a good yield can be obtained.

[0103] Examples 20-21 are examples of using anhydrous Na2S prepared by the method for preparing anhydrous Na2S provided by the present invention to prepare the sodium polysulfide compound Nax1Sy1.

[0104] Example 20

[0105] 1 mmol of anhydrous Na2S obtained in the above example, 1 mmol of sulfur, and 0.5 mL of deionized water were mixed, heated under reflux at 110°C for 20 h, evaporated to dryness, and vacuum-dried at 200°C to obtain 0.92 mmol of anhydrous Na2S2 as a light yellow solid in a yield of 92%.

[0106] Example 21

[0107] 1 mmol of anhydrous Na2S obtained in the above example, 3 mmol of sulfur, and 0.5 mL of deionized water were mixed, heated under reflux at 110°C for 20 h, evaporated to dryness, and then vacuum-dried at 200°C to obtain 0.96 mmol of anhydrous Na2S4 as a dark yellow solid in a yield of 96%.

[0108] Examples 22-23 are examples of preparing dialkyl sulfide R2S by reacting anhydrous Na2S prepared using the method for preparing anhydrous Na2S provided by the present invention with an alkyl halide RX.

[0109] Example 22

[0110] The anhydrous Na2S 1mmol, EtOH 2mL, n - C6H 13 Cl 2mmol, phase transfer catalyst tetrabutylammonium chloride 0.1mmol, temperature 70 degrees, after heating for 15h, (n - C6H 13 )2S 0.88mmol,88%.

[0111] Example 23

[0112] The anhydrous Na2S 1mmol, EtOH 2mL, n - C6H 13 Br 2mmol, phase transfer catalyst tetrabutylammonium chloride 0.1mmol, temperature 70 degrees, after heating for 15h, (n - C6H13 )2S 0.93mmol,93%.

[0113] Example 24 is an example of preparing dialkyl sulfide R2S using a sodium polysulfide compound prepared by the method for preparing a Na2S derivative provided by the present invention.

[0114] Example 24

[0115] The anhydrous Na2S4 obtained in the above embodiment (as described above, obtained from 1 mmol of Na2S and 3 mmol of S), 5 mL of dried and dehydrated THF, 2 mmol of (EtO)3SiCH2CH2CH2Cl, and the temperature were 70 degrees for 15 h to obtain a polysulfide compound {(EtO)3SiCH2CH2CH2)}2S4 mixture 0.82 mmol, with a yield of 82%.

[0116] In addition to the above embodiments, the present invention may also have other implementations. Any technical solution formed by equivalent replacement or equivalent transformation falls within the scope of protection required by the present invention.

Claims

1. A method for preparing anhydrous Na2S, characterized in that: The method comprises the following steps: Step 1: first use R 1 R 2 R 3 P and sulfur react completely to form phosphine-sulfur compound R 1 R 2 R 3 PS, the R 1 R 2 R 3 The molar ratio of P to sulfur is 1:1; Step 2: Under an inert gas or nitrogen atmosphere, the phosphine-sulfur compound R3PS is reacted with metallic sodium in a non-polar hydrocarbon solvent to generate a phosphine-based compound R 1 R 2 R 3 P and Na2S, after the reaction is completed, solid Na2S is separated from the reaction system by utilizing the property that Na2S is insoluble in organic solvents, and then the solid Na2S is washed with an organic solvent and vacuum dried to obtain anhydrous Na2S; the metallic sodium in step 2 and the R in step 1 1 R 2 R 3 The molar ratio of P is 2:1; the non-polar hydrocarbon solvent is selected from one of toluene, ethylbenzene, p-xylene and mesitylene and any combination thereof, and the non-polar hydrocarbon solvent and the phosphine-sulfur compound R 1 R 2 R 3 The weight ratio of PS is 2-5:1; the reaction temperature of the phosphine-sulfur compound and metallic sodium is 60-200°C; Step 3: adding sulfur to the reaction system in Step 2, and performing Step 1, Step 2 and Step 3 in sequence to form the following cyclic reaction system: ； The chemical formula of phosphine-sulfur compounds is R3PS, where R3PS is R 1 R 2 R 3 PS; the chemical formula of phosphine compounds is R3P, R3P is R 1 R 2 R 3 P; the phosphine-sulfur compound R 1 R 2 R 3 PS is one of triphenylphosphine sulfide, tri(o-methylphenyl)phosphine sulfide, phenyldimethylphosphine sulfide, tri(p-methylphenyl)phosphine sulfide or diphenylmethylphosphine sulfide, or a mixture of any multiple thereof.

2. The method for preparing anhydrous Na2S according to claim 1, wherein: Phosphine-sulfur compounds R 1 R 2 R 3 PS is triphenylphosphine sulfide.

3. The method for preparing anhydrous Na2S according to claim 1, wherein: R 1 、R 2 and R 3 Independently selected from phenyl with C1-C6 long chain or branched alkyl, heterocyclic aromatic hydrocarbon containing N, O, S atoms and C1-C 20 Long chain or branched chain alkyl groups.

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