Preparation method and application of ammonium thiocarbonate sulfonate inner salt
By preparing the thiocarbonate ammonium sulfonate internal salt as a new high antigen, the problem of unstable copper foil production caused by the easy decomposition of the existing SH110 is solved, and the tensile performance of the copper foil is significantly improved and the process is simple and safe.
Patent Information
- Application Number
- CN202411688807.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-25
- Publication Date
- 2025-03-28
- Estimated Expiration
- 2044-11-25
AI Technical Summary
The high antigen SH110 used in the production of existing electrolytic copper foils is easy to decompose, resulting in unstable copper foil production process and difficult to find alternatives.
By preparing the inner salt of thiocarbonate ammonium sulfonate as a new high antigen, it can significantly improve the tensile strength and stability of the copper foil. The preparation method of the thiocarbonate ammonium sulfonate internal salt includes reacting raw material A and B in a solvent, adding a catalyst to undergo a timing reaction, and finally obtaining a high yield and high purity product by cooling and crystallization.
It realizes the efficient preparation of thiocarbonate ammonium sulfonate internal salt, improves the tensile and fatigue resistance of copper foil, and is simple and safe in the process, suitable for industrial production.
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Figure CN119176769B_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic synthesis, in particular to a preparation method and application of ammonium thiocarbonate sulfonate inner salt. Background Art
[0002] As an excellent electronic current collector material, copper foil is widely used in different fields such as integrated circuits and lithium batteries. In particular, with the rise of China's new energy vehicle industry, the demand for lithium-ion power batteries is increasing day by day. When copper foil is applied to lithium-ion cathode materials, copper foil materials with low tensile strength are prone to breakage during the coating process. Therefore, tensile strength is an important indicator for evaluating the performance of copper foil materials.
[0003] As an additive in the production of electrolytic copper foil, high-resistance agent can greatly improve the tensile strength of copper foil at low concentrations. In the existing electrolytic copper foil production process, SH110 (sodium thiazolyl disulfide propane sulfonate) is widely used as a high-resistance agent. However, SH110 itself is easy to decompose, and its composition is constantly changing due to long storage time. In the actual production process, it will lead to unstable copper foil production process and easily cause various defects in copper foil (such as torn edges, nail marks, seersucker, etc.). Therefore, it is very meaningful to seek a high-resistance agent to replace SH110.
[0004] Ammonium thiocarbonate sulfonate inner salt can be synthesized by the following method:
[0005] Method 1:
[0006] As starting material, a compound having at least one epoxy group is used.
[0007] The above compound is reacted with phosgene or an alkyl chloroformate to obtain an adduct.
[0008] The above adduct is reacted with a compound containing anionic sulfur to obtain a compound having at least one five-membered cyclic monothiocarbonate group.
[0009] Method 2:
[0010] The invention adopts an epoxy compound and carbon oxysulfide as reactants, a nitrogen-bridged triaryloxyaluminum coordination compound as a catalyst, and in the presence of a co-catalyst, a five-membered ring monothiocarbonate is prepared through an addition reaction.
[0011] Ammonium carbonate is added to the five-membered ring monothiocarbonate to obtain ammonium thiocarbonate sulfonate inner salt after reaction.
[0012] The above synthesis methods of ammonium thiocarbonate sulfonate inner salts have a long reaction time and a complicated process. Summary of the invention
[0013] There is no clear research conclusion or widely accepted view on whether ammonium sulfonate thiocarbonate inner salt can refine copper crystals. However, the inventors found that ammonium sulfonate thiocarbonate inner salt can refine copper crystals and reduce grain boundary defects, thereby improving the tensile strength and fatigue resistance of copper foil. Its synthesis process is convenient, fast and safe, and its yield and purity are high. It is expected to become a new additive in the copper foil industry.
[0014] Based on the above technical background, the inventors found that low concentration of ammonium thiocarbonate sulfonate can significantly improve the tensile strength of copper foil, and its chemical properties are stable, the synthesis process is cheap, easy to operate, safe, and the yield and purity are high, and it is expected to become a new excellent high-resistance agent.
[0015] The problems to be solved by the present invention are at least one of the following: first, the synthesis time of ammonium thiocarbonate sulfonate inner salt is long and the process is cumbersome; second, the possibility of ammonium thiocarbonate sulfonate inner salt as a new high resistance agent for electrolytic copper foil is sought, and for this purpose, a preparation method and application of ammonium thiocarbonate sulfonate inner salt are provided.
[0016] The technical solution of the present invention is: a method for preparing ammonium thiocarbonate sulfonate inner salt, and the general structural formula of ammonium thiocarbonate sulfonate inner salt is as follows: , wherein X is any one of C, N, O, S, and n is 3 or 4, and the preparation method thereof comprises the following steps: Denoted as A, the raw material Denoted as B, raw material A is poured into a solvent, heated under reflux until dissolved and until the system is clear, raw material B is dissolved in the solvent, and then the solution containing B is added dropwise into the solution containing A while hot, react for a period of time, and then a catalyst is added, and the reaction is continued for 10min-40min, and then the system is cooled to room temperature and crystallized to obtain ammonium thiocarbonate sulfonate.
[0017] The solvent in the above scheme is one or more of water, methanol, ethanol, n-propanol, isopropanol and n-butanol.
[0018] The heating temperature in the above scheme is 40°C-90°C.
[0019] The reaction temperature before the catalyst is added in the above scheme is 40°C-90°C.
[0020] The catalyst in the above scheme is one or more of 1 wt% hydrochloric acid, 1 wt% glacial acetic acid, 1 wt% scandium trifluoromethanesulfonate, and 1 wt% p-toluenesulfonic acid.
[0021] The molar ratio of A to B in the above scheme is 1:1.0-2.0.
[0022] The reaction time of A and B in the above scheme is 1h-3h.
[0023] Application of ammonium sulfonate thiocarbonate inner salt: the ammonium sulfonate thiocarbonate inner salt prepared by any of the above-mentioned preparation methods of ammonium sulfonate thiocarbonate inner salt is used as a high resistance agent for electrolytic copper foil.
[0024] The application of ammonium thiocarbonate sulfonate inner salt comprises the following steps: taking an electrolyte containing copper sulfate and sulfuric acid, ammonium thiocarbonate sulfonate inner salt and other additives and mixing them evenly to obtain a mixed solution; using a cathode roller or a titanium plate as a cathode and a coated iridium tantalum oxide as an anode, and electrodepositing in the mixed solution to continuously produce electrolytic copper foil, or using a titanium plate to produce electrolytic copper foil on a small trial basis.
[0025] The beneficial effect of the present invention is that A and B are used as raw materials and organic acid is used as a catalyst to simply and efficiently prepare high-yield (>89%) and high-purity (>98%) thiocarbonate sulfonate ammonium inner salt by a one-pot method, which is very conducive to large-scale production; the thiocarbonate sulfonate ammonium inner salt can be used in combination with other additives in the production of copper foil to significantly improve the tensile properties of the copper foil material, and can produce low-defect, low-roughness, high-tensile strength (>70 kgf / mm 2 ) of 6 μm ultra-thin electrolytic copper foil material. DETAILED DESCRIPTION
[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described examples are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field belong to the scope of protection of the present invention.
[0027] The synthetic reaction formula of ammonium thiocarbonate sulfonate inner salt is as follows:
[0028]
[0029] Embodiment 1: A method for preparing ammonium thiocarbonate sulfonate inner salt, comprising the following steps:
[0030] Add 200 mL of n-butanol and 238 g (2.0 mol) of tetrahydrothiazolethione to a 1000 mL four-necked flask and stir evenly. Heat to 90 °C until the solution is clear, slowly drop 244 g (2.0 mol dissolved in 100 mL of n-butanol) of 1,3-propane sultone, control the drop rate with a peristaltic pump, and control the drop temperature at 85 °C-90 °C. After the drop addition of 1,3-propane sultone is completed, control the temperature to 90 °C and keep warm for 3 hours; then add 20 mL of 1 wt% hydrochloric acid to end the reaction, and maintain 90 °C for 40 min; after the solution is cooled to room temperature, a large amount of white flaky crystals precipitate, transfer the reaction solution to a Bush suction funnel, wash the filter cake with n-butanol and dry it to obtain 453.6 g (yield 94.5%, purity 99.3%) of white powder product.
[0031] Embodiment 2: A method for preparing ammonium thiocarbonate sulfonate inner salt, comprising the following steps:
[0032] Add 200 mL of methanol and 238 g (2.0 mol) of tetrahydrothiazolethione to a 1000 mL four-necked flask and stir evenly. Heat to 40 °C until the solution is clear, slowly drop 244 g (2.0 mol dissolved in 100 mL of methanol) of 1,3-propane sultone, control the dripping rate with a peristaltic pump, and control the dripping temperature at 40 °C-45 °C. After the addition of 1,3-propane sultone is completed, control the temperature to 40 °C and keep warm for 3 hours; then add 20 mL of 1 wt% hydrochloric acid to end the reaction, and maintain 40 °C for 40 min; after the solution is cooled to room temperature, a large amount of white flaky crystals precipitate, transfer the reaction solution to a Bush suction funnel, wash the filter cake with methanol and dry it to obtain 430.6 g (yield 89.7%, purity 99.1%) of white powder product.
[0033] Embodiment 3: A method for preparing ammonium thiocarbonate sulfonate inner salt, comprising the following steps:
[0034] Add 200 mL of isopropanol and 238 g (2.0 mol) of tetrahydrothiazolethione to a 1000 mL four-necked flask and stir evenly. Heat to 80 ° C until the solution is clear, slowly drop 244 g (2.0 mol dissolved in 100 mL of isopropanol) of 1,3-propane sultone, control the dripping rate with a peristaltic pump, and control the dripping temperature at 75 ° C-80 ° C. After the addition of 1,3-propane sultone is completed, control the temperature to 80 ° C and keep warm for 3 hours; then add 20 mL of 1 wt% hydrochloric acid to end the reaction, and maintain 80 ° C for 40 min; after the solution is cooled to room temperature, a large amount of white flaky crystals precipitate, and the reaction solution is transferred to a Bush suction funnel. The filter cake is washed with isopropanol and dried to obtain 470.5 g (yield 98.0%, purity 99.2%) of white powder product.
[0035] Embodiment 4: A method for preparing ammonium thiocarbonate sulfonate inner salt, comprising the following steps:
[0036] Add 200 mL of n-butanol and 238 g (2.0 mol) of tetrahydrothiazolethione to a 1000 mL four-necked flask and stir evenly. Heat to 90 ° C until the solution is clear, slowly drop 244 g (2.0 mol dissolved in 100 mL of n-butanol) of 1,3-propane sultone, control the dripping rate with a peristaltic pump, and control the dripping temperature at 85 ° C-90 ° C. After the addition of 1,3-propane sultone is completed, control the temperature to 90 ° C and keep warm for 3 hours; then add 0.1 g of p-toluenesulfonic acid to end the reaction, and maintain 90 ° C for 40 min; after the solution is cooled to room temperature, a large amount of white flaky crystals precipitate, and the reaction solution is transferred to a Bush suction funnel. The filter cake is washed with n-butanol and dried to obtain 450.5 g (yield 93.8%, purity 98.1%) of white powder product.
[0037] Example 5: A method for preparing ammonium thiocarbonate sulfonate inner salt, comprising the following steps:
[0038] Add 200 mL of isopropanol and 204 g (2.0 mol) of ethylene thiourea to a 1000 mL four-necked flask and stir evenly. Heat to 80 °C until the solution is clear, slowly drop 244 g (2.0 mol dissolved in 100 mL of isopropanol) of 1,3-propane sultone, control the dripping rate with a peristaltic pump, and control the dripping temperature at 75 °C-80 °C. After the addition of 1,3-propane sultone is completed, control the temperature to 80 °C and keep warm for 1 h; then add 20 mL of 1 wt% hydrochloric acid to end the reaction, and maintain 80 °C for 10 min; after the solution is cooled to room temperature, a large amount of white flaky crystals precipitate, transfer the reaction solution to a Bush suction funnel, wash the filter cake with isopropanol and dry it to obtain 405.1 g (yield 90.4%, purity 98.3%) of white powder product.
[0039] Example 6: A method for preparing ammonium thiocarbonate sulfonate inner salt. Different from Example 1, 1,3-propane sultone is replaced by 1,4-butane sultone.
[0040] Example 7: A method for preparing ammonium thiocarbonate sulfonate inner salt. Different from Example 5, ethylenethiourea is replaced by tetrahydrooxathione.
[0041] Example 8: A method for preparing ammonium thiocarbonate sulfonate inner salt. Different from Example 5, ethylenethiourea is replaced by tetrahydropyrrole-2-thione.
[0042] It should be noted that the raw materials A and B in the examples of the present application include but are not limited to the combination of the above-mentioned ethylene thiourea, tetrahydropyrrole-2-thione, tetrahydrothiazolidinethione and 1,3-propane sultone, 1,4-butane sultone, but include a combination of all general structures of raw materials A and B.
[0043] The purity and yield tests of the ammonium thiocarbonate sulfonate inner salts prepared in Examples 1-8 were summarized as follows:
[0044]
[0045] It can be seen from the test data in the above table that the ammonium thiocarbonate sulfonate inner salt produced by the preparation process of the present invention has a high yield and purity. The technical solution of the present application optimizes the preparation steps of the ammonium thiocarbonate sulfonate inner salt, which is conducive to industrial scale-up synthesis.
[0046] The prepared ammonium thiocarbonate sulfonate inner salt has the function of improving the tensile properties of electrolytic copper foil and can effectively improve the performance of copper foil.
[0047] The application of ammonium thiocarbonate sulfonate inner salt comprises the following steps: taking 500 mL of raw foil liquid, wherein the contents of the components in the solution are 2ppm-40ppm of ammonium thiocarbonate sulfonate inner salt, 205g / L of CuS04:5H20 solution, 90g / L of sulfuric acid, 40ppm of chloride ion solution, 1ppm of polyethylene glycol (6000), 45ppm of sodium polydisulfide dipropane sulfonate and 10ppm of collagen; a titanium plate is used as a cathode, and a coated iridium tantalum oxide is used as an anode, wherein the size of the iridium tantalum oxide anode plate is 15cm x 6cm x 0.5cm, the size of the titanium plate is 15cm x 6cm x 0.5cm, the distance between the anode and cathode plates is 3cm, the size of the Haring trough is 105mm x 150mm x 85mm, and the temperature is 50℃ and 50A / dm 3 Electrolytic copper foil of 6 μm was obtained by electroplating at a current density of 40 s.
[0048]
[0049] Combined with Table 2, the electrolyte was used. The ammonium thiocarbonate sulfonate inner salt used in Implementation Groups 1 to 11 was the product of Example 1. A total of 12 parallel experiments were conducted. As the concentration of the ammonium thiocarbonate sulfonate inner salt increased, the tensile strength soared from 32.75 kgf / mm of the blank control to 2 When adding high resistance agent concentration of 2ppm, 5ppm, and 7ppm, the tensile strength gradually increases to 37.20kgf / mm 2 、42.79kgf / mm 2 、46.51kgf / mm2 At 20ppm, the tensile strength has reached 65.36 kgf / mm 2 ; When the additive concentration gradually increases (2ppm to 40ppm), from 37.20kgf / mm 2 Increased to 70.20kgf / mm 2 When adding 0ppm-17ppm, the surface glossiness of the copper foil decreases with the increase of concentration, and the glossiness increases at 20ppm, and then continues to decrease when the concentration increases. Compared with the lithium battery copper foil without adding thiocarbonate sulfonate ammonium inner salt, the tensile properties of the lithium battery copper foil prepared by the present invention are significantly improved.
Claims
1. The application of ammonium thiocarbonate sulfonate inner salt is characterized by: The general structural formula of ammonium thiocarbonate sulfonate inner salt is as follows: , wherein X is any one of C, N, O, S, and n is 3 or 4. The preparation method comprises the following steps: Denoted as A, the raw material Denoted as B, raw material A is poured into a solvent, heated under reflux until dissolved and until the system is clear, raw material B is dissolved in the solvent, and then the solution containing B is dropped into the solution containing A while hot, react for a period of time, and then a catalyst is added, and the reaction is continued for 10min-40min, and then the system is cooled to room temperature and crystallized to obtain ammonium thiocarbonate sulfonate inner salt, and the prepared ammonium thiocarbonate sulfonate inner salt is used as a high resistance agent for electrolytic copper foil.
2. The use of the ammonium thiocarbonate sulfonate inner salt as claimed in claim 1, characterized in that: The following steps are involved: An electrolyte containing copper sulfate and sulfuric acid, ammonium thiocarbonate sulfonate and other additives are mixed evenly to obtain a mixed solution; a cathode roller or a titanium plate is used as a cathode, and a coated iridium tantalum oxide is used as an anode, and electrolytic copper foil is continuously produced by electrodeposition in the mixed solution, or a titanium plate is used to produce electrolytic copper foil on a small scale.