Preparation method of copper foil brightener additive

Abstract

The invention discloses a preparation method of a copper foil brightener additive, and belongs to the technical field of synthesis of sulfur-containing organic matters. The preparation method mainly comprises the following steps: by taking ethanolamine hydrochloride as a starting raw material, firstly generating sulfate amino alcohol hydrosalt, then synthesizing and generating an intermediate product by taking carbon disulfide as a sulfur source, carrying out simple spin-drying treatment on the intermediate product, and directly reacting with 1, 2, 3-trimethyl-1, 3-pentanedione to obtain the 1, 2, 3-pentanedione. The target product 3-(thiazoline-2-sulfydryl) sodium propanesulfonate can be obtained by reacting 1, 3-propane sultone at normal temperature for 4 hours. The additive prepared by the method disclosed by the invention has the advantages of cheap and easily available raw materials, mild reaction conditions, high yield and the like.

Description

Technical Field

[0001] This application relates to the technical field of synthesizing sulfur-containing organic compounds, and specifically to a preparation method of a copper foil brightener additive. Background Art

[0002] Common electrolytic copper foil additives can be classified into brighteners, leveling agents, and leveling agents according to their effects. Brighteners are generally compounds containing sulfur groups, which are used to regulate the brightness of the copper foil surface and at the same time serve the purpose of refining crystal grains. Common sulfur-containing compounds include thiourea additives, such as thiourea, N-allylthiourea, ethylenethiourea, tetramethylthiourea, etc. However, thiourea-based additives will cause the copper foil surface to become brittle. Another type of sulfur-containing additive is a compound containing a sulfonic acid group, represented by sodium polydithiopropanesulfonate (SPS), sodium 3-mercapto-1-propanesulfonate (MPS), and bis-(sulfonylethylsulfate)-disulfide (SES). This type of compound has good water solubility and forms an intermediate with sufficient concentration under certain conditions in combination with copper and chloride ions, significantly increasing the number of nucleation sites for copper deposition and effectively improving the brightness and physical properties of the obtained copper foil. The disadvantage is the precipitation of sulfides. The third type is to introduce a nitrogen-containing group into the sulfur-containing additive, which can give full play to the common advantages of S and N groups and reduce the problem of bringing in sulfur impurities. For example, modified thiourea prepared from thiourea and diethylenetriaminepentaacetic acid can effectively solve the problem of copper foil brittleness. 2-mercaptopyridine can make the prepared copper foil have both surface brightness and leveling effects at the same time. However, the solubility of the modified additive is not high, the yield is low, and the cost is high. In view of the defects of existing brighteners, it is necessary to develop an additive with good solubility, high yield, low cost, and capable of having both brightening and leveling effects at the same time.

[0003] Therefore, it is necessary to provide a preparation method of a copper foil brightener additive to solve the above problems.

[0004] It should be noted that the above information disclosed in this background art section is only used to understand the background art of the concept of this application, and therefore, it may include information that does not constitute prior art. Summary of the Invention

[0005] Based on the above problems existing in the prior art, the problem to be solved by this application is: to provide a preparation method of a copper foil brightener additive, which solves the problems of low solubility, low yield, and high cost of the modified material.

[0006] The technical solution adopted by this application to solve its technical problems is: a preparation method of a copper foil brightener additive, and the preparation method is as follows:

[0007] S1. Mix sulfuric acid (98%) with water in a 1:1 cold mixture, and slowly add the resulting cold mixture to water containing ethanolamine hydrochloride, with the acidity above 5 mol / L - 8 mol / L, ensuring the temperature during dropping is around 0°C - 5°C. After dropping, heat the mixture to 60°C - 150°C, and the reaction time is 1 - 4 hours to obtain a crude product of solid amino alcohol hydrogen sulfate;

[0008] S2. Dissolve chlorosulfonic acid in a beaker containing 100 mL of anhydrous diethyl ether for standby. Add ethanolamine hydrochloride to a flask containing diethyl ether to dissolve it, and then slowly drop the chlorosulfonic acid solution into the flask. After dropping, stir at -20°C - 0°C for 1 - 4 hours. The product is filtered and the precipitate is washed to obtain a crude product of solid amino alcohol hydrogen sulfate;

[0009] S3. Dissolve amino alcohol hydrogen sulfate or amino alcohol hydrogen sulfate ester in carbon disulfide, add 650 mL of 5 mol / L - 6 mol / L KOH aqueous solution, react at 20°C - 130°C for 3 - 12 hours. After cooling to room temperature, extract the reaction mixture with dichloromethane. The combined organic layers are dried with Na2SO4, and the solvent is completely removed under reduced pressure to obtain the intermediate product tetrahydrothiazole - 2 - thione;

[0010] S4. Dissolve 1,3 - propanesultone in 100 mL of methanol for standby. Dissolve the obtained tetrahydrothiazole - 2 - thione in an organic solvent, add an equal amount of base, and then gradually drop the methanol containing 1,3 - propanesultone into the tetrahydrothiazole - 2 - thione solution while reacting. Finish dropping within half an hour, and then react for 2 - 4 hours. Filter to obtain a precipitate, wash it with ethanol and diethyl ether to obtain a crude product, and recrystallize with ethanol to obtain the product sodium 3 - (dihydrothiazole - 2 - mercapto) propane sulfonate, with the highest yield up to 90%.

[0011] Further, the reaction solvent in S4 is a mixed solvent of water and carbon disulfide.

[0012] Further, the sodium 3 - (dihydrothiazole -

[0013] 2 - mercapto) propane sulfonate formed by the reaction of tetrahydrothiazole - 2 - thione and 1,3 - propanesultone has the molecular structure of

[0014] Further, the acid used in S1 and S2 is one of concentrated sulfuric acid or chlorosulfonic acid. When the acid is concentrated sulfuric acid, the reaction temperature is 60°C - 150°C, and when the acid is chlorosulfonic acid, the reaction temperature is -20°C - 0°C.

[0016] Further, the bases used in the reactions of S3 and S4 are Na2CO3, K2CO3, Cs2CO3,

[0017] One of K3PO3, K2HPO3, NaOH, KOH, KOBu t and KOCH3.

[0018] Furthermore, the organic solvent used in the reaction in S4 is one of methanol, ethanol, propanol, petroleum

[0019] ether, ethyl ether, acetonitrile, toluene, ethyl ether, acetone, xylene.

[0020] The beneficial effects of this application are as follows: The raw material uses relatively inexpensive ethanolamine, which has good solubility, and the highest yield can reach 90%. The cost is low. Although there are three steps in the reaction, the intermediate products are all purified and directly used in the next step, which can be regarded as a one-step reaction.

[0021] In addition to the purposes, features, and advantages described above, this application also has other purposes, features, and advantages. The following will refer to the drawings to further elaborate on this application in detail. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The specification drawings forming a part of this application are used to provide a further understanding of this application. The schematic embodiments and descriptions thereof of this application are used to explain this application and do not constitute an improper limitation to this application.

[0023] In the drawings:

[0024] Figure 1 is the synthesis route diagram of sodium 3-(dihydrothiazole-2-mercapto)propane sulfonate of this application;

[0025] Figure 2 is the 1H NMR spectrum diagram of sodium 3-(dihydrothiazole-2-mercapto)propane sulfonate of this application;

[0026] Figure 3 is the 13C NMR spectrum diagram of sodium 3-(dihydrothiazole-2-mercapto)propane sulfonate of this application;

[0027] Figure 4 is the infrared spectrum diagram of sodium 3-(dihydrothiazole-2-mercapto)propane sulfonate of this application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0028] It should be noted that, without conflict, the embodiments in this application and the features in the embodiments can be combined with each other. The following will refer to the drawings and combine with the embodiments to elaborate on this application in detail.

[0029] To enable those skilled in the art to better understand the solution of this application, the technical solutions in the embodiments of this application will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of this application. Obviously, the described embodiments are only a part of the embodiments of this application, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in this application without creative efforts shall fall within the scope of protection of this application.

[0030] As Figures 1-4 shown, this application provides a preparation method of a copper foil brightener additive, including: Example 1

[0031] (I) Slowly add the product obtained by cold mixing 200 ml of sulfuric acid (98%) and water in a 1:1 ratio to 200 ml of water containing 1 mole of ethanolamine hydrochloride. After mixing evenly, heat the mixture to 150 °C, react for 1 hour, and distill off the water after cooling to obtain solid amino alcohol bisulfate;

[0032] Alternatively, first dissolve 140 g (1.2 moles) of chlorosulfonic acid in 100 ml of anhydrous diethyl ether for later use. Add 1.0 mole of ethanolamine hydrochloride to a 500 ml flask, dissolve it with 100 ml of anhydrous diethyl ether, place the flask in an ice-salt bath at -20 °C to 0 °C, and then slowly drop the chlorosulfonic acid solution into the flask while stirring. After dropping, continue to stir and react for 2 hours. Filter to obtain the precipitate, and wash it with ethanol and diethyl ether to obtain solid amino alcohol bisulfate;

[0033] (II) Dissolve the amino alcohol bisulfate or amino alcohol bisulfate ester in 500 ml of carbon disulfide, add 650 ml of 6 mol / L KOH aqueous solution, react at 130 °C for 12 hours, cool to room temperature, extract the reaction mixture with dichloromethane, combine the organic layers, dry the combined organic layers with Na2SO4, and completely remove the solvent under reduced pressure to obtain the intermediate product tetrahydrothiazolethione;

[0034] (III) Dissolve 1 mole of 1,3-propanesultone in 100 ml of methanol for later use. Dissolve the obtained intermediate product tetrahydrothiazolethione in a beaker containing 100 ml of organic solvent, add 1 mole of Na2CO3, and then slowly drop the methanol containing 1,3-sultone into the beaker. React for 4 hours, filter to obtain the precipitate, wash it with ethanol and diethyl ether to obtain the crude product, and recrystallize with ethanol to obtain the product sodium 3-(dihydrothiazole-2-ylthio)propane sulfonate, yield: 60%.

[0035] Example 2

[0036] (I) The product obtained by cooling and mixing 200 ml of sulfuric acid (98%) and water in a ratio of 1:1 is slowly added to 200 ml of water containing 1 mole of ethanolamine hydrochloride. After mixing evenly, the mixture is heated to 60 °C and reacted for 1 hour. After cooling, the water is distilled off to obtain solid amino alcohol hydrogen sulfate;

[0037] Or first dissolve 140 g (1.2 moles) of chlorosulfonic acid in 100 ml of anhydrous diethyl ether for standby. Add 1.0 mole of ethanolamine hydrochloride to a 500-ml flask and dissolve it with 100 ml of anhydrous diethyl ether. Place the flask in an ice-salt bath at -20 °C to 0 °C, and then slowly add the chlorosulfonic acid solution dropwise to the flask while stirring. After the addition is complete, continue to stir and react for 2 hours. Filter to obtain the precipitate, and wash it with ethanol and diethyl ether to obtain amino alcohol hydrogen sulfate;

[0038] (II) Dissolve amino alcohol hydrogen sulfate or amino alcohol hydrogen sulfate ester in 500 ml of carbon disulfide, add 650 ml of 5 mol / L KOH aqueous solution, and react at 20 °C for 3 hours. After cooling to room temperature, extract the reaction mixture with dichloromethane. Combine the organic layers, dry the combined organic layers with Na2SO4, and completely remove the solvent under reduced pressure to obtain the intermediate product tetrahydrothiazolethione;

[0039] (III) Dissolve 1 mole of 1,3-propanesultone in 100 ml of methanol for standby. Dissolve the obtained intermediate product tetrahydrothiazolethione in a beaker containing 100 ml of organic solvent, add 1 mole of Na2CO3, and then slowly add the methanol containing 1,3-sultone dropwise to the beaker. React for 2 hours, filter to obtain the precipitate, wash it with acetone, ethyl acetate or tetrahydrofuran to obtain the crude product, and recrystallize with ethanol to obtain the product sodium 3-(dihydrothiazol-2-ylthio)propanesulfonate, yield: 70%.

[0040] Example 3

[0041] (I) The product obtained by cooling and mixing 200 ml of sulfuric acid (98%) and water in a ratio of 1:1 is slowly added to 200 ml of water containing 1 mole of ethanolamine hydrochloride. After mixing evenly, the mixture is heated to 130 °C and reacted for 2 hours. After cooling, the water is distilled off to obtain solid amino alcohol hydrogen sulfate;

[0042] Or first dissolve 140 g (1.2 moles) of chlorosulfonic acid in 100 ml of anhydrous diethyl ether for standby. Add 1.0 mole of ethanolamine hydrochloride to a 500-ml flask and dissolve it with 100 ml of anhydrous diethyl ether. Place the flask in an ice-salt bath at -20 °C to 0 °C, and then slowly add the chlorosulfonic acid solution dropwise to the flask while stirring. After the addition is complete, continue to stir and react for 1 hour. Filter to obtain the precipitate, and wash it with ethanol and diethyl ether to obtain solid amino alcohol hydrogen sulfate;

[0043] (II) Dissolve the amino alcohol hydrogensulfate or amino alcohol sulfate ester in 500 mL of carbon disulfide, add 650 mL of 6 mol / L KOH aqueous solution, react at 80 °C for 4 hours. After cooling to room temperature, extract the reaction mixture with dichloromethane. Combine the organic layers, dry the combined organic layers with Na2SO4, and completely remove the solvent under reduced pressure to obtain the intermediate product tetrahydrothiazolethione.

[0044] (III) Dissolve 1 mole of 1,3 - propanesultone in 100 mL of methanol for standby. Dissolve the obtained intermediate product tetrahydrothiazolethione in a beaker containing 100 mL of organic solvent, add 1 mole of base, and then gradually add the methanol containing 1,3 - sultone dropwise to the beaker. React for 3 hours, filter to obtain the precipitate, wash with ethanol and diethyl ether to obtain the crude product, and recrystallize with ethanol to obtain the product sodium 3 - (dihydrothiazole - 2 - mercapto) propane sulfonate, yield: 89%.

[0045] According to the comparison of multiple examples: The optimal temperature for preparing amino alcohol sulfate ester during the preparation process is 130 °C, the optimal reaction time is 2 hours. The optimal stirring time of amino alcohol hydrogensulfate during the preparation process is 1 hour. The optimal concentration of KOH aqueous solution during the preparation of tetrahydrothiazolethione is 6 mol / L, the optimal reaction temperature is 80 °C, the optimal reaction time is 4 hours. The optimal reaction time during the preparation of the final product is 2 - 3 hours, and the optimal reaction temperature is 20 °C.

[0046] Examples of preparing copper foil with additives:

[0047] a. Use an ordinary spray - type copper - dissolving system, a cathode roll with a width of 1000 mm and a roll diameter of 2 m, and a copper foil machine with a total electrolyte volume of about 30 m³ in the system for testing. Control the electrolyte temperature at 40 - 60 °C, the copper ion content at 70 - 90 g / L, the sulfuric acid content at 100 - 150 g / L, the chloride ion content at 30 - 40 ppm, and the additive flow rate at 1.5 L / h. By adjusting the concentrations of brighteners, leveling agents, surfactants, and high - resistance agents in the additive and the copper foil thickness, and using a relatively high current density as much as possible to produce electrolytic copper foils with different tensile strengths, to meet the requirements of each level of general resistance, medium resistance, high resistance, and ultra - high resistance. The copper foil samples are tested after baking at room temperature and 100 °C for 20 min.

[0048] b. Additives for 6-μm ultra-high copper foil resistance and the properties of the copper foil produced thereby. The brightener uses sodium polydithiopropane sulfonate and sodium N,N-dimethyl dithiocarbamoyl propane sulfonate, and their mass ratio is 8:1. The leveller uses collagen with a molecular weight of 2000M. The surfactant uses polyethylene glycol and hydroxyethyl cellulose, and their mass ratio is 5:1. The high-resistance agent is high-resistance agent WG. The brightener, leveller, surfactant, and high-resistance agent are configured into aqueous solutions with concentrations of 20 g / L, 40 g / L, 5 g / L, and 30 g / L respectively. The additive is added to the electrolyte by a peristaltic pump at a rate of 1.5 L / h. According to the copper foil thickness specification of 6 μm and the current density of 0.5 A / cm 2 , set the raw foil current and line speed. After stable production, take the full-width sample to test the mechanical properties of the sample at room temperature and after baking at 200 °C for 20 min, and test the surface roughness Rz, matte surface roughness Ra, and Rz of the baked sample. The test results show that the tensile strength at room temperature is 500 MPa, the elongation is 6%, the tensile strength after baking is 300 MPa, the elongation is 7.5%, the Rz of the smooth surface is 2.56 μm, the Rz of the matte surface is 2.72 μm, and the Ra of the matte surface is 0.5 μm.

[0049] The above are only the preferred embodiments of the present application and are not used to limit the present application. For those skilled in the art, various changes and modifications can be made to the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included within the protection scope of the present application.

Claims

1. A preparation method of a copper foil brightener additive, characterized in that: The preparation method is as follows: S1. Sulfuric acid (98%) is cold-mixed with water at a ratio of 1:1, and the obtained cold mixture is slowly added to water containing ethanolamine hydrochloride, with the acidity above 5 mol / L - 8 mol / L. Ensure that the temperature during dropping is about 0°C - 5°C. After the dropping is completed, the mixture is heated to 60°C - 150°C, and the reaction time is 1 - 4 hours to obtain a crude product of solid amino alcohol hydrogen sulfate; S2. Chlorosulfonic acid is dissolved in a beaker containing 100 ml of anhydrous diethyl ether for standby. Ethanolamine hydrochloride is added to a flask containing diethyl ether and dissolved, and then the chlorosulfonic acid solution is slowly dropped into the flask and stirred for 1 - 4 hours. The product is filtered, and the precipitate is washed to obtain a crude product of solid amino alcohol hydrogen sulfate; S3. The amino alcohol hydrogen sulfate or amino alcohol hydrogen sulfate ester is dissolved in carbon disulfide, 650 ml of 5 mol / L - 6 mol / L KOH aqueous solution is added, and the reaction is carried out at a temperature of 20°C - 130°C for 3 - 12 hours. After cooling to room temperature, the reaction mixture is extracted with dichloromethane. The combined organic layers are dried with Na2SO4, and the solvent is completely removed under reduced pressure to obtain the intermediate product tetrahydrothiazolethione; S4. 1,3 - Propane sultone is dissolved in 100 ml of methanol for standby. The obtained tetrahydrothiazolethione is dissolved in an organic solvent, an equal amount of base is added, and then the methanol containing 1,3 - sultone is gradually dropped into the tetrahydrothiazolethione solution while reacting. The dropping is completed within half an hour, and then the reaction is continued for 2 - 4 hours. The precipitate is filtered, washed with ethanol and diethyl ether to obtain a crude product, and recrystallized with ethanol to obtain the product sodium 3-(dihydrothiazol - 2 - ylthio)propane sulfonate, with the highest yield up to 90%; 2. The preparation method of a copper foil brightener additive according to claim 1, characterized in that: The reaction solvent in S4 is a mixed solvent of water and carbon disulfide.

3. The preparation method of a copper foil brightener additive according to claim 1, characterized in that: The molecular structure of sodium 3-(dihydrothiazol-2-ylthio)propanesulfonate formed by the reaction of the tetrahydrothiazolthione with 1,3-propanesultone is 4. The preparation method of a copper foil brightener additive according to claim 1, characterized in that: The acid used in S1 and S2 is one of concentrated sulfuric acid or chlorosulfonic acid. When the acid is concentrated sulfuric acid, the reaction temperature is 60°C - 150°C; when the acid is chlorosulfonic acid, the reaction temperature is -20°C - 0°C.

5. The preparation method of a copper foil brightener additive according to claim 1, characterized in that: The bases used in the reactions in S3 and S4 are one of Na2CO3, K2CO3, Cs2CO3, K3PO3, K2HPO3, NaOH, KOH, KOBu t and KOCH3.

6. The preparation method of a copper foil brightening agent additive according to claim 1, wherein: The organic solvent used in the reaction in S4 is one of methanol, ethanol, propanol, petroleum ether, diethyl ether, acetonitrile, toluene, diethyl ether, acetone, xylene.

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