A preparation process of sodium polydisulfide dipropane sulfonate

Abstract

The invention discloses a preparation process of sodium polydipropane disulfide sulfonate. In the preparation process, compound 1 and a disulfide reaction reagent react to obtain compound 2; compound 2 undergoes at least one of a hydrolysis reaction, a sulfonation reagent, and an acid-base reaction to obtain sodium polydipropane disulfide sulfonate. The preparation process obtains a high-purity product by optimizing starting raw materials, preparation and purification processes, and the obtained sodium polydipropane disulfide sulfonate meets the requirements of the field of PCB electroplating materials for its purity, impurity content, cost, etc.; and the preparation process is relatively simple to operate, raw materials are easy to obtain, the reaction production cycle is short, the yield is high, and it is conducive to reducing product costs, and large-scale production can be achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of PCB electroplating materials, and in particular relates to a preparation process of sodium polydipropane disulfide sulfonate. Background Art

[0002] Bis-(sodium sulfopropyl)-disulfide, CAS No. 27206-35-5. Bis-(sodium sulfopropyl)-disulfide is used as an acid copper plating brightener to obtain decorative and functional coatings. Bis-(sodium sulfopropyl)-disulfide can be used in combination with typical copper plating formulas such as non-ionic surfactants, polyamines and other hydrogen sulfide compounds, and can also be used with dyes. When used in combination with DPS and EXP2887, the coating effect will be better.

[0003] Chinese patent CN202011065367.3 discloses a synthesis process of high-purity sodium polydisulfide dipropane sulfonate: sodium sulfide and sulfur powder react with 1,3-propane sultone in the presence of alkali, then add an oxidant for oxidation, and then post-treat to obtain sodium polydisulfide dipropane sulfonate. In the above scheme, the side reaction products of sodium sulfide and sulfur powder undergo a disproportionation reaction with the alkali to reduce the by-products, and the oxidant is added to react the sodium thiosulfate generated synchronously in the disproportionation reaction with 1,3-propane sultone to generate the target product sodium polydisulfide dipropane sulfonate.

[0004] In general, the number of patents, especially in the field of sodium polydisulfide propane sulfonate, is relatively small. Among the existing patents, there are still many problems in the preparation process, such as: the raw materials of the product are not easy to obtain, the manufacturing cost is high, the yield is low, there are many wastes, and the preparation method is complicated. If the above problems are not solved, their large-scale application will be hindered, especially hindering them from becoming materials in the field of PCB electroplating materials. Summary of the invention

[0005] In order to overcome the shortcomings of the prior art, the purpose of the present invention is to provide a preparation process of sodium polydipropane disulfide sulfonate, which has relatively simple operation, easy raw materials, short reaction production cycle, high yield, and is conducive to reducing product cost; the product meets the requirements of the field of PCB electroplating materials for the purity, impurity content, cost, etc. of sodium polydipropane disulfide sulfonate, and can achieve large-scale production and application.

[0006] The purpose of the present invention can be achieved by adopting the following technical solutions:

[0007] A preparation process of sodium polydipropane disulfide sulfonate comprises the following preparation steps:

[0008] Preparation step S1: Compound 1 reacts with a disulfide reaction reagent to obtain compound 2;

[0009] Preparation step S2: Compound 2 undergoes at least one of a hydrolysis reaction, a sulfonation reagent, and an acid-base reaction to prepare sodium polydipropane disulfide sulfonate;

[0010] Wherein, the structural formula of compound 1 is the general structure shown in Formula I:

[0011]

[0012] The structural formula of compound 2 is the general structure shown in formula II:

[0013]

[0014] The reaction equation of preparation step S1 is shown in the following formula (1):

[0015]

[0016] The reaction equation of preparation step S2 is shown in the following formula (2):

[0017]

[0018] Wherein, Y1 and Y2 are independently at least one of halogen, OH, OCOR, and OSO2R; R is a metal, H, a saturated or unsaturated, straight-chain or branched, heteroatom-containing or heteroatom-free C1-C 30 Hydrocarbon or C1-C 30 A type of aromatic hydrocarbon.

[0019] Furthermore, in the preparation step S1, the disulfidation reaction reagent is at least one of sulfide, elemental sulfur, and thiosulfate.

[0020] Furthermore, the sulfide is an acid salt of sulfur, a normal salt of sulfur and a polysulfide.

[0021] Furthermore, in the preparation step S2, the sulfonating reagent is at least one of a reaction mixture of SO2 and an oxide or hydroxide of a Group IA metal or a Group IIA metal, sulfite, bisulfite, concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, and sulfur trioxide.

[0022] Furthermore, the reaction temperature in the preparation step S1 is -50-200°C, the reaction pressure is -0.05-1MPa, and the reaction time is 0.1-72 hours;

[0023] The reaction temperature in the preparation step S2 is -50-200°C, the reaction pressure is -0.05-1MPa, and the reaction time is 0.1-72 hours.

[0024] Furthermore, in the preparation step S1, the molar ratio of compound 1 to the disulfide reaction reagent is 1:0.1-10;

[0025] The molar ratio of compound 2 to the sulfonation reagent in the preparation step S2 is 1:0.1-10.

[0026] Furthermore, the preparation step S1 is reacted in a reaction solvent A, wherein the reaction solvent A is one or a combination of two or more of water, methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl carbonate, ether, acetonitrile, dioxane, N,N-dimethylformamide, and dimethyl sulfoxide;

[0027] Preparation step S2 is reacted in a reaction solvent B, wherein the reaction solvent B is one or a combination of two or more of water, methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl carbonate, ether, acetonitrile, dioxane, N,N-dimethylformamide, and dimethyl sulfoxide.

[0028] Furthermore, the method further comprises the following preparation steps:

[0029] The obtained sodium polydipropane disulfide sulfonate is recrystallized with a purified solvent to obtain purified sodium polydipropane disulfide sulfonate.

[0030] Furthermore, the purification solvent is one or a combination of two or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl carbonate, ether, acetonitrile, dioxane, N,N-dimethylformamide, and dimethyl sulfoxide.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] 1. A preparation process of sodium polydipropane disulfide sulfonate of the present invention obtains a high-purity product by optimizing starting raw materials, preparation and purification processes. The obtained sodium polydipropane disulfide sulfonate meets the requirements of the purity, impurity content, cost, etc. of sodium polydipropane disulfide sulfonate in the field of PCB electroplating materials; and the preparation process is relatively simple to operate, the raw materials are easy to obtain, the reaction production cycle is short, the yield is high, it is conducive to reducing product costs, and large-scale production and application can be achieved.

[0033] 2. The by-products and impurities generated during the preparation and purification process provided by the present invention are easy to purify and separate, and the impurities in the product can reach the high-purity practical application standard without going through a complicated purification process, thereby simplifying the product preparation process, making the product yield high and the product purity high, and being able to meet the production and quality requirements of large-scale applications. DETAILED DESCRIPTION

[0034] Below, the present invention is further described in conjunction with the specific implementation method. It should be noted that this specific implementation method is a part of the non-limiting specific implementation method, which is used to explain the present invention in more detail. However, the present invention is not limited to the following embodiments. The embodiments and the description only illustrate the principle of the present invention; that is, the following description is only a part of the preferred implementation examples of the present invention, and the scope of the rights of the present invention cannot be limited by this. For ordinary technicians in this technical field, without departing from the spirit, principle and scope of the present invention, the present invention can also make various changes, improvements and modifications. The additional features of these improvements can exist alone or in any combination. These changes, improvements and modifications should also be regarded as within the scope of the invention claimed for protection of the present invention. In addition, the raw materials used in the present invention are generally common commercial products, so there is no need to specifically limit their sources.

[0035] The nuclear magnetic resonance analysis test was performed using an AVANCE 400 MHz nuclear magnetic resonance spectrometer from Bruker.

[0036] The purity was tested by high performance liquid chromatography (HPLC).

[0037] The pressure values ​​mentioned in this patent application, unless otherwise specified, refer to gauge pressure, which refers to the amount by which the total absolute pressure exceeds the surrounding atmospheric pressure or the pressure at a certain point in the liquid that is higher than the atmospheric pressure.

[0038] Reaction temperature, unless otherwise specified, generally refers to the reaction oil bath temperature.

[0039] The yield is expressed as the percentage ratio of the actual product mass to the theoretical product mass. The theoretical product mass is calculated based on the amount of raw materials not in excess in the reaction equation.

[0040] Example 1

[0041] A preparation process of sodium polydipropane disulfide sulfonate comprises the following preparation steps:

[0042] (1) Preparation step 1:

[0043]

[0044] In a reactor, 1 mole of compound 1 is reacted with a disulfide reaction reagent; the molar ratio of compound 1 to the disulfide reaction reagent is 1:1, the disulfide reaction reagent is a mixed reagent of S and Na2S with a molar ratio of 1:1, the solvent is a mixed solvent of water and THF, the reaction temperature is 35°C, the reaction pressure is normal pressure, the reaction time is 3 hours, and after the reaction is completed, the organic phase is collected and spin-dried to obtain compound 2.

[0045] (2) Preparation step 2:

[0046]

[0047] In a reactor, 1 mol of compound 2 in the above formula is reacted with sodium sulfite; the molar ratio of compound 2 to sodium sulfite is 1:2; the solvent is DMF, the reaction temperature is 110° C., the reaction pressure is normal pressure, the reaction time is 1 hour, and after the reaction is completed, the solvent is dried to obtain sodium polydisulfide dipropane sulfonate, with a crude yield of 65%.

[0048] (3) Purification step 3:

[0049] In a reactor, 1 mol of sodium polydisulfide propane sulfonate was dissolved in water, and purified solvent ethanol was added for recrystallization. The insoluble matter was filtered out and dried to obtain fine sodium polydisulfide propane sulfonate. The purification yield was 90% and the product purity was 99.2%.

[0050] The NMR characterization data are as follows: 1 H NMR (400MHz, D2O): δ3.0ppm, 2.9ppm, 2.2ppm.

[0051] Example 2

[0052] A preparation process of sodium polydipropane disulfide sulfonate comprises the following preparation steps:

[0053] (1) Preparation step 1:

[0054]

[0055] In a reactor, 1 mole of compound 1 is reacted with a disulfide reaction reagent; the molar ratio of compound 1 to the disulfide reaction reagent is 1:2, the disulfide reaction reagent is sodium thiosulfate, the solvent is a mixed solvent of water and dioxane, the reaction temperature is 65°C, the reaction pressure is normal pressure, the reaction time is 30 minutes, and after the reaction is completed, the organic phase is collected and spin-dried to obtain compound 2.

[0056] (2) Preparation step 2:

[0057]

[0058] In a reactor, 1 mol of compound 2 in the above formula is reacted with a mixture of sulfur trioxide and chlorosulfonic acid; the molar ratio of compound 2 to sulfur trioxide and chlorosulfonic acid is 1:2:1; the solvent is a mixed solvent of dioxane and water, the reaction temperature is 80°C, the reaction pressure is normal pressure, the reaction time is 4 hours, and after the reaction is completed, an excess of sodium hydroxide aqueous solution is added to continue the reaction for 1 hour, the aqueous phase is collected, and the water is vortexed to obtain sodium polydisulfide dipropane sulfonate, with a crude yield of 57%.

[0059] (3) Purification step 3:

[0060] In a reactor, 1 mol of sodium polydisulfide propane sulfonate was dissolved in water, and purified solvent acetone was added for recrystallization. The insoluble matter was filtered out and dried to obtain fine sodium polydisulfide propane sulfonate. The purification yield was 88% and the product purity was 99.1%.

[0061] The NMR characterization data are as follows: 1 H NMR (400MHz, D2O): δ3.0ppm, 2.9ppm, 2.2ppm.

[0062] Example 3

[0063] A preparation process of sodium polydipropane disulfide sulfonate comprises the following preparation steps:

[0064] (1) Preparation step 1:

[0065]

[0066] In a reactor, 1 mole of compound 1 is reacted with a disulfide reaction reagent; the molar ratio of compound 1 to the disulfide reaction reagent is 1:5, the disulfide reaction reagent is sodium sulfide, the solvent is a mixed solvent of water and ethyl acetate, the reaction temperature is 80°C, the reaction pressure is normal pressure, the reaction time is 1.5 hours, and after the reaction is completed, the organic phase is collected and spin-dried to obtain compound 2.

[0067] (2) Preparation step 2:

[0068]

[0069] In a reactor, 1 mol of compound 2 in the above formula is reacted with sodium bisulfite; the molar ratio of compound 2 to sodium bisulfite is 1:5; the solvent is a mixed solvent of methanol and water, the reaction temperature is 80° C., the reaction pressure is normal pressure, the reaction time is 12 hours, and after the reaction is completed, the solvent is removed by rotation to obtain sodium polydisulfide dipropane sulfonate, with a crude product yield of 58%.

[0070] (3) Purification step 3:

[0071] In a reactor, 1 mol of sodium polydisulfide propane sulfonate was dissolved in water, and purified solvent ethyl acetate was added for recrystallization. The insoluble matter was filtered off and dried to obtain fine sodium polydisulfide propane sulfonate. The purification yield was 86% and the product purity was 99.2%.

[0072] The NMR characterization data are as follows: 1 H NMR (400MHz, D2O): δ3.0ppm, 2.9ppm, 2.2ppm.

[0073] Example 4

[0074] A preparation process of sodium polydipropane disulfide sulfonate comprises the following preparation steps:

[0075] (1) Preparation step 1:

[0076]

[0077] In a reactor, 1 mole of compound 1 is reacted with a disulfide reaction reagent; the molar ratio of compound 1 to the disulfide reaction reagent is 1:2, the disulfide reaction reagent is sodium thiosulfate, the solvent is a mixed solvent of water and acetone, the reaction temperature is 50° C., the reaction pressure is normal pressure, the reaction time is 8 hours, and after the reaction is completed, the organic phase is collected and spin-dried to obtain compound 2.

[0078] (2) Preparation step 2:

[0079]

[0080] In a reactor, 1 mol of compound 2 in the above formula is reacted with concentrated sulfuric acid; the molar ratio of compound 2 to concentrated sulfuric acid is 1:2; the solvent is a mixed solvent of ethanol and water, the reaction temperature is 40°C, the reaction pressure is normal pressure, the reaction time is 2 hours, and after the reaction is completed, an excess of sodium hydroxide aqueous solution is added to continue the reaction for 1 hour, and the solvent is vortexed to obtain poly (sodium disulfide dipropane sulfonate), with a crude product yield of 61%.

[0081] (3) Purification step 3:

[0082] In a reactor, 1 mol of sodium polydisulfide propane sulfonate was dissolved in water, and purified solvent ethanol was added for recrystallization. The insoluble matter was filtered out and dried to obtain fine sodium polydisulfide propane sulfonate. The purification yield was 89% and the product purity was 99.1%.

[0083] The NMR characterization data are as follows: 1 H NMR (400MHz, D2O): δ3.0ppm, 2.9ppm, 2.2ppm.

[0084] Example 5

[0085] A preparation process of sodium polydipropane disulfide sulfonate comprises the following preparation steps:

[0086] (1) Preparation step 1:

[0087]

[0088] In a reactor, 1 mole of compound 1 is reacted with a disulfide reaction reagent; the molar ratio of compound 1 to the disulfide reaction reagent is 1:2.5, the disulfide reaction reagent is sodium sulfide, the solvent is a mixed solvent of water and THF, the reaction temperature is 30°C, the reaction pressure is normal pressure, the reaction time is 24 hours, and after the reaction is completed, the organic phase is collected and spin-dried to obtain compound 2.

[0089] (2) Preparation step 2:

[0090]

[0091] In a reactor, 1 mol of compound 2 in the above formula is reacted with sodium hydroxide; the molar ratio of compound 2 to sodium hydroxide is 1:2; the solvent is a mixed solvent of ethanol and water, the reaction temperature is 60° C., the reaction pressure is normal pressure, the reaction time is 5 hours, and after the reaction is completed, the solvent is removed by rotation to obtain sodium polydisulfide dipropane sulfonate, with a crude product yield of 62%.

[0092] (3) Purification step 3:

[0093] In a reactor, 1 mol of sodium polydisulfide propane sulfonate was dissolved in water, and a purification solvent THF was added for recrystallization. The insoluble matter was filtered out and dried to obtain the fine sodium polydisulfide propane sulfonate. The purification yield was 85% and the product purity was 99.3%.

[0094] The NMR characterization data are as follows: 1 H NMR (400MHz, D2O): δ3.0ppm, 2.9ppm, 2.2ppm.

[0095] Example 6

[0096] A preparation process of sodium polydipropane disulfide sulfonate comprises the following preparation steps:

[0097] (1) Preparation step 1:

[0098]

[0099] In a reactor, 1 mole of compound 1 is reacted with a disulfide reaction reagent; the molar ratio of compound 1 to the disulfide reaction reagent is 1:1, the disulfide reaction reagent is a mixed reagent of S and Na2S in a molar ratio of 1:1, the solvent is a mixed solvent of water and DMF, the reaction temperature is 120°C, the reaction pressure is normal pressure, the reaction time is 12 hours, and after the reaction is completed, the organic phase is collected and spin-dried to obtain compound 2.

[0100] (2) Preparation step 2:

[0101]

[0102] In a reactor, 1 mol of compound 2 in the above formula is reacted with fuming sulfuric acid; the molar ratio of compound 2 to fuming sulfuric acid is 1:2; the solvent is a mixed solvent of THF and water, the reaction temperature is 60°C, the reaction pressure is normal pressure, the reaction time is 1 hour, and after the reaction is completed, an excess of sodium hydroxide aqueous solution is added to continue the reaction for 1 hour, and the solvent is vortexed to obtain poly (sodium disulfide dipropane sulfonate) with a crude yield of 58%.

[0103] (3) Purification step 3:

[0104] In a reactor, 1 mol of sodium polydisulfide propane sulfonate was dissolved in water, and dimethyl carbonate was added as a purification solvent for recrystallization. The insoluble matter was filtered out and dried to obtain the fine sodium polydisulfide propane sulfonate. The purification yield was 86% and the product purity was 99.3%.

[0105] The NMR characterization data are as follows: 1 H NMR (400MHz, D2O): δ3.0ppm, 2.9ppm, 2.2ppm.

[0106] The above experiments show that the sodium polydisulfide dipropane sulfonate prepared in the embodiment has high purity and low impurity content, which can meet the requirements of the application field. Moreover, the yield of the preparation method of the present invention can reach 65%, and the purity of the purified product is above 99%.

[0107] The above-mentioned embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and substitutions made by technicians in this field on the basis of the present invention shall fall within the scope of protection required by the present invention.

Claims

1. A preparation process of sodium polydipropane disulfide sulfonate, characterized in that: The method comprises the following preparation steps: Preparation step S1: Compound 1 reacts with a disulfide reaction reagent to obtain compound 2; Preparation step S2: Compound 2 undergoes sulfonation reaction and / or acid-base reaction to prepare sodium polydipropane disulfide sulfonate; Wherein, the structural formula of compound 1 is the general structure shown in Formula I: The structural formula of compound 2 is the general structure shown in formula II: Wherein, Y1 is halogen, Y2 is at least one selected from halogen, OH, OCOR, OSO2R, and Y1 and Y2 are different; R is a metal, H, a saturated or unsaturated, straight chain or branched, heteroatom-containing or heteroatom-free C1-C 30 Hydrocarbon or C1-C 30 A type of aromatic hydrocarbon group.

2. The preparation process of a sodium polydipropane disulfide sulfonate according to claim 1, characterized in that: In the preparation step S1, the disulfidation reaction reagent is at least one of sulfide, elemental sulfur, and thiosulfate.

3. The preparation process of a sodium polydisulfide dipropane sulfonate according to claim 2, characterized in that: The sulfide is an acid salt of sulfur, a normal salt of sulfur and a polysulfide.

4. The preparation process of a sodium polydisulfide dipropane sulfonate according to claim 1, characterized in that: In the preparation step S2, the sulfonating reagent is at least one of a reaction mixture of SO2 and an oxide or hydroxide of a Group IA metal or a Group IIA metal, sulfite, bisulfite, concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, and sulfur trioxide.

5. The preparation process of a sodium polydisulfide dipropane sulfonate according to claim 1, characterized in that: The reaction temperature in the preparation step S1 is -50-200°C, the reaction pressure is -0.05-1MPa, and the reaction time is 0.1-72 hours; The reaction temperature in the preparation step S2 is -50-200°C, the reaction pressure is -0.05-1MPa, and the reaction time is 0.1-72 hours.

6. The preparation process of a sodium polydisulfide dipropane sulfonate according to claim 1, characterized in that: In the preparation step S1, the molar ratio of compound 1 to the disulfide reaction reagent is 1:0.1-10; The molar ratio of compound 2 to the sulfonation reagent in the preparation step S2 is 1:0.1-10.

7. The preparation process of a sodium polydipropane disulfide sulfonate according to claim 1, characterized in that: Preparation step S1: reacting in a reaction solvent A, wherein the reaction solvent A is one or a combination of two or more of water, methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl carbonate, ether, acetonitrile, dioxane, N,N-dimethylformamide, and dimethyl sulfoxide; Preparation step S2 is reacted in a reaction solvent B, wherein the reaction solvent B is one or a combination of two or more of water, methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl carbonate, ether, acetonitrile, dioxane, N,N-dimethylformamide, and dimethyl sulfoxide.

8. The process for preparing sodium polydipropane disulfide sulfonate according to claim 1, characterized in that: The following preparation steps are also included: The obtained sodium polydipropane disulfide sulfonate is recrystallized with a purified solvent to obtain purified sodium polydipropane disulfide sulfonate.

9. The process for preparing sodium polydipropane disulfide sulfonate according to claim 8, characterized in that: The purification solvent is one or a combination of two or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl carbonate, ether, acetonitrile, dioxane, N,N-dimethylformamide, and dimethyl sulfoxide.

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