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CN-121974836-A - Preparation method of polydithio-dipropyl sulfonate and copper plating solution

CN121974836ACN 121974836 ACN121974836 ACN 121974836ACN-121974836-A

Abstract

The application relates to the technical field of electroplating, in particular to a preparation method of polydithio-dipropyl sulfonate and copper plating solution. The preparation method of the polydithio-dipropyl sulfonate comprises the following steps of preparing alkaline alcohol liquid, adding carbon disulfide into the alkaline alcohol liquid to generate dithiocarbonate to obtain reaction liquid, adding 1, 3-propane sultone into the reaction liquid to generate and separate out dithiocarbonate sulfonate, carrying out hydrolysis reaction on the dithiocarbonate sulfonate to generate 3-mercaptopropane sulfonate, and carrying out oxidation reaction on the 3-mercaptopropane sulfonate to generate the polydithio-dipropyl sulfonate. The present application provides a novel synthesis of polydithio-dipropyl sulfonate.

Inventors

  • WU HAOZHONG
  • LIU BINYUN
  • TAN CHAOLI
  • LI JINGYA
  • ZOU HAOBIN
  • XIAO DINGJUN

Assignees

  • 广东光华科技股份有限公司
  • 光华科学技术研究院(广东)有限公司
  • 广东东硕科技有限公司

Dates

Publication Date
20260505
Application Date
20260120

Claims (10)

  1. 1. A process for the preparation of polydithio-dipropyl sulfonate, comprising the steps of: preparing an alkaline alcohol solution, wherein the alkaline alcohol solution comprises an alcohol compound, and the structure of the alcohol compound is that Wherein R is selected from C 1-6 alkyl; Adding carbon disulfide into the alkaline alcohol solution, and carrying out nucleophilic addition reaction on a certain content of the alcohol compound and the carbon disulfide to generate dithiocarbonate, wherein the dithiocarbonate is dissolved in the residual content of the alcohol compound to obtain a reaction solution, and the dithiocarbonate comprises the following groups: ; Adding 1, 3-propane sultone into the reaction liquid, wherein the dithiocarbonate and the 1, 3-propane sultone undergo nucleophilic substitution reaction to generate and separate out dithiocarbonate sulfonate, and the dithiocarbonate sulfonate comprises the following groups: ; hydrolyzing the dithiocarbonate sulfonate to generate 3-mercaptopropane sulfonate; Oxidizing the 3-mercaptopropane sulfonate to form polydithio-dipropyl sulfonate, the polydithio-dipropyl sulfonate comprising the following groups: 。
  2. 2. The method for producing polydithio-dipropyl sulfonate according to claim 1, wherein the alcohol compound is a primary alcohol compound.
  3. 3. The method for producing polydithio-dipropyl sulfonate according to claim 1, wherein the basic alcohol solution includes a first basic substance which is dissolved in the alcohol compound or dispersed in the alcohol compound.
  4. 4. A process for the preparation of polydithio-dipropyl sulfonate according to claim 3, characterized by comprising at least one of the following features: (1) The first alkaline substance is at least one of inorganic alkali and organic alkali, the inorganic alkali is at least one of sodium hydroxide and potassium hydroxide, and the organic alkali is at least one of sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide and potassium tert-butoxide; (2) The ratio of the volume of the alcohol compound to the mole number of the first alkaline substance is (0.2-10) mL 1mmol; (3) The molar ratio of the first alkaline substance to the carbon disulfide to the 1, 3-propane sultone is 1 (1.00-1.05): 1.00-1.20.
  5. 5. The method for producing a polydithio-dipropyl sulfonate according to claim 1 wherein the step of subjecting the dithiocarbonate sulfonate to hydrolysis reaction comprises the step of mixing the dithiocarbonate sulfonate, a second basic substance and water to hydrolysis reaction.
  6. 6. The method of preparing polydithio-dipropyl sulfonate of claim 5 including at least one of the following features: (1) The molar ratio of the dithiocarbonate sulfonate to the second alkaline substance is 1 (1.0-2.0); (2) The second alkaline substance is selected from at least one of sodium hydroxide and potassium hydroxide.
  7. 7. The method for producing polydithio-dipropyl sulfonate of claim 1 wherein the step of oxidizing the 3-mercapto-propane sulfonate includes the step of mixing the 3-mercapto-propane sulfonate with an oxidizing agent, the oxidizing agent including at least one of hydrogen peroxide and oxygen.
  8. 8. The method for producing polydithio-dipropyl sulfonate according to any one of claims 1 to 7, characterized by comprising at least one of the following features: (1) Adding the carbon disulfide into the alkaline alcohol solution for 30-120 min; (2) The reaction temperature for nucleophilic addition reaction is 5-20 ℃; (3) The nucleophilic addition reaction takes place for 60-90 min; (4) The time for adding the 1, 3-propane sultone into the reaction liquid is 60-120 min; (5) The reaction temperature for nucleophilic substitution reaction is 15-35 ℃; (6) The nucleophilic substitution reaction takes place for 120-180 min; (7) The temperature for hydrolysis reaction is 40-100 ℃; (8) The hydrolysis reaction takes place for 1-4 hours; (9) The temperature for oxidation reaction is 15-35 ℃; (10) The time for the oxidation reaction is 2-4 hours.
  9. 9. The method for producing a polydithio-dipropyl sulfonate according to any one of claims 1 to 7, further comprising the steps of, after the polydithio-dipropyl sulfonate is produced: collecting the polydithio-dipropyl sulfonate to obtain a crude product; The crude product is recrystallized using an organic solvent.
  10. 10. Copper plating solution, characterized by comprising polydithio-dipropyl sulfonate, which is prepared by the preparation method according to any one of claims 1 to 9.

Description

Preparation method of polydithio-dipropyl sulfonate and copper plating solution Technical Field The application relates to the technical field of electroplating, in particular to a preparation method of polydithio-dipropyl sulfonate and copper plating solution. Background The acidic copper sulfate system is widely applied to the fields of printed circuit boards and integrated circuits because of uniform plating layer, bright plating surface, fine crystallization, high current efficiency, good deep plating capability and simple wastewater treatment. In addition to the necessary inorganic components of water, copper sulfate, sulfuric acid and chloride ions, some small amount of organic compounds are added into the acidic copper sulfate electroplating solution to adjust the current distribution in the electroplating process and change the plating capacity of the electroplating solution. In the acid copper plating process, the brightening agent can inhibit abnormal growth of crystal grains, refine crystallization of a plating layer, improve the glossiness and uniformity of the surface of the plating layer, and play a vital role in improving the performance and quality of a copper plating layer. The most used brighteners are polydithio-dipropyl sulfonates and are mainly used in the sodium salt form (SPS). The synthesis method of SPS has two strategies, ① is firstly oxidized and then substituted, for example, sodium sulfide and sulfur powder are used for generating sodium persulfate, then propane sultone is added for reaction to prepare SPS (patent CN 202011065367.3), ② is firstly substituted and then oxidized, for example, sodium hydrosulfide method (patent CN 200910061390.2), sodium thiosulfate method (patent CN201611255544.8 and patent CN 201710092055.3), thiourea method (patent CN 202211370844.6) and thioacetamide method (CN 202410230782.1). Among the above methods, sodium hydrosulfide method needs to involve highly toxic hydrogen sulfide gas, has high operational crisis, sodium thiosulfate method by-product sodium sulfate is not easy to remove, product quality is reduced, thiourea method synthesis and purification steps are complicated, a large amount of waste water is generated in the ion exchange process, and the like, and thioacetamide method uses copper oxide as an oxidant, and the reduced substance is insoluble in a soaking solvent and remains in the product. Thus, there is a need to provide new synthetic routes to polydithio-dipropyl sulfonate. Disclosure of Invention Based on the above, the first aspect of the application provides a preparation method of polydithio-dipropyl sulfonate, which adopts the following technical scheme: A method for preparing polydithio-dipropyl sulfonate, comprising the following steps: preparing an alkaline alcohol solution, wherein the alkaline alcohol solution comprises an alcohol compound, and the structure of the alcohol compound is that Wherein R is selected from C 1-6 alkyl; Adding carbon disulfide into the alkaline alcohol solution, and carrying out nucleophilic addition reaction on a certain content of the alcohol compound and the carbon disulfide to generate dithiocarbonate, wherein the dithiocarbonate is dissolved in the residual content of the alcohol compound to obtain a reaction solution, and the dithiocarbonate comprises the following groups: ; Adding 1, 3-propane sultone into the reaction liquid, wherein the dithiocarbonate and the 1, 3-propane sultone undergo nucleophilic substitution reaction to generate and separate out dithiocarbonate sulfonate, and the dithiocarbonate sulfonate comprises the following groups: ; hydrolyzing the dithiocarbonate sulfonate to generate 3-mercaptopropane sulfonate; Oxidizing the 3-mercaptopropane sulfonate to form polydithio-dipropyl sulfonate, the polydithio-dipropyl sulfonate comprising the following groups: 。 In a second aspect, the present application provides a copper plating solution comprising polydithio-dipropyl sulfonate, which is prepared by the preparation method as described above. Compared with the traditional scheme, the application has the following beneficial effects: The application provides a method for synthesizing polydithio-dipropyl sulfonate, which comprises the steps of firstly generating dithiocarbonate sulfonate, wherein when the dithiocarbonate sulfonate is prepared, a certain content of alcohol compounds and carbon disulfide generate corresponding dithiocarbonate, the salt can be dissolved in unreacted alcohol compounds, and reaction liquid containing the dithiocarbonate is obtained after the reaction, and the step of separating the dithiocarbonate is omitted. Then adding 1, 3-propane sultone into the reaction liquid, carrying out nucleophilic substitution reaction on the 1, 3-propane sultone and dithiocarbonate to generate and precipitate dithiocarbonate sulfonate which is indissoluble in alcohol compounds, and removing unreacted carbon disulfide and intermediate dithiocarbonate which are dissolved