Preparation Method and Application of Five-Membered Nitrogen Heterocyclic Monothiopropane Sulfonate

Abstract

The present invention discloses a preparation method and application of five-membered nitrogen heterocyclic monothiopropane sulfonate, and its structural general formula is as follows: , where X is any one of N, O, and S, and Y is any one of Na, K, and Cs. The beneficial effects of the present invention are that it can simply and quickly achieve the one-pot preparation of five-membered nitrogen heterocyclic monothiopropane sulfonate with high yield (>85%) and high purity (>95%), and the reaction conditions are conducive to industrial scale-up production; in the production of electrolytic copper foil, it can significantly improve the tensile properties of copper foil materials when combined with other additives, and can produce 6μm ultra-thin electrolytic copper foil materials with low defects, fine grains, and high tensile strength (>60kgf / mm 2 )

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and particularly to a preparation method and application of five-membered nitrogen heterocyclic compounds. Background Art

[0002] Copper foil materials are key materials in the manufacturing of printed circuit boards (PCBs). As the basic connection components of electronic devices, electrolytic copper foils provide the conductive layers for PCBs. For example, in devices such as smartphones and computer motherboards, it can ensure the stable transmission of circuit signals. The quality of copper foils in multi-layer PCB structures directly affects the integrity of signal transmission. At the same time, copper foil materials are also important components of lithium batteries. In terms of the negative electrode current collectors of lithium batteries, electrolytic copper foils carry the processes of lithium ion insertion and extraction. With the development of new energy vehicles and portable electronic devices, the performance requirements for lithium batteries have increased, and the quality of electrolytic copper foils has become even more important.

[0003] High resistance additives can affect the growth direction and microstructure of copper crystals during the growth process of electrolytic copper foils. They can refine copper crystals and reduce grain boundary defects, thereby improving the tensile resistance, fatigue resistance, etc. of copper foils. For example, certain organic additives can adsorb on the surface of copper crystal nuclei, change their growth kinetics, and make copper crystals grow in a direction more conducive to improving the overall performance. In some special environments, such as in electronic devices under high temperature and high humidity conditions, electrolytic copper foils need to have good antioxidant and corrosion resistance properties. High resistance additives can form a protective film with the copper foil surface or change the surface energy of the copper foil, thereby improving its corrosion and oxidation resistance and extending the service life of electrolytic copper foils.

[0004] For example, Chinese Patent Publication No. CN101153405A discloses a plating composition, which reacts a five-membered nitrogen-containing heterocyclic compound with 1-halo-2,3-epoxypropane to form a brightener, and its function is to improve the surface gloss and stability of the plating layer.

[0005] There are many synthesis methods for five-membered nitrogen heterocyclic compounds. The following are some common synthesis methods:

[0006] Catalytic cyclization method: By introducing a catalyst to promote the cyclization reaction, common catalysts include acids, bases, metal catalysts, etc. Oxidative nucleophilic substitution method: Using a nucleophile and an oxidant to generate a corresponding intermediate, and then carrying out a cyclization reaction through the intermediate to obtain the target compound. Metal catalysis method: Using a metal catalyst to promote the reaction, which has the characteristics of mild reaction conditions and high reaction selectivity. During the synthesis process, it is necessary to select appropriate synthesis methods and reaction conditions according to specific reaction substrates and target products, and optimize and improve them to improve the reaction efficiency and selectivity. However, the specific synthesis method of five-membered nitrogen heterocyclic monothiopropanesulfonate has not been reported.

[0007] Chinese Invention Patent Publication No. CN106279032B discloses a method for synthesizing five-membered nitrogen heterocyclic compounds by gold catalysis. Under argon protection, triazine, diazo, gold catalyst and solvent are sequentially added into a reaction tube, and then the temperature is raised to 60 °C and reacted for 12 hours to obtain five-membered nitrogen heterocycles. The reaction time of this synthesis method is relatively long. Summary of the Invention

[0008] There is no clear research conclusion or widely recognized view on whether five-membered nitrogen heterocyclic monothiopropanesulfonate can refine copper crystals. However, the inventors found that five-membered nitrogen heterocyclic monothiopropanesulfonate can refine copper crystals, reduce grain boundary defects, thereby improving the tensile resistance, fatigue resistance, etc. of copper foils. Its synthesis process is convenient, fast, safe, and has high yield and purity, and is expected to become a new additive in the copper foil industry.

[0009] The problems to be solved by the present invention are at least one of the following: one is that the synthesis time of five-membered nitrogen heterocyclic monothiopropanesulfonate is relatively long and the process is cumbersome; the other is to seek the possibility of using five-membered nitrogen heterocyclic monothiopropanesulfonate as a new high-resistant agent for electrolytic copper foils. Therefore, a preparation method and application of five-membered nitrogen heterocyclic monothiopropanesulfonate are provided.

[0010] The technical solution of the present invention is: a preparation method of five-membered nitrogen heterocyclic monothiopropanesulfonate, and the general structural formula of five-membered nitrogen heterocyclic monothiopropanesulfonate is as follows: , where X is any one of N, O, and S, and Y is any one of Na, K, and Cs. The preparation method includes the following steps: Denote the raw material as A, and denote the raw material as B. Pour raw material A into a solvent, add an alkali catalyst and dissolve until the system is clear. Dissolve raw material B in the solvent, and then drop the solution containing B into the alkaline solution containing A. A large amount of white precipitate products are generated by the reaction. After separation and drying, the five-membered nitrogen heterocyclic monothiopropanesulfonate is obtained.

[0011] In the above solution, the solvent is one or more of water, methanol, ethanol, n-propanol, isopropanol, and n-butanol.

[0012] In the above solution, the molar ratio of raw materials A to B is 1:1.0 - 1.5.

[0013] In the above solution, the alkali catalyst is one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate.

[0014] In the above solution, the reaction temperature is 20 °C - 50 °C.

[0015] In the above solution, the reaction time of A and B is 10 min - 3 h.

[0016] Application of pentacyclic nitrogen heterocyclic monothiopropanesulfonate, using the pentacyclic nitrogen heterocyclic monothiopropanesulfonate prepared by the preparation method of pentacyclic nitrogen heterocyclic monothiopropanesulfonate as described above as a high resistance agent for electrolytic copper foil.

[0017] The above application includes the following steps: taking an electrolyte containing copper sulfate and sulfuric acid, pentacyclic nitrogen heterocyclic monothiopropanesulfonate and other additives and mixing them evenly to obtain a mixed solution; using a cathode roller or a titanium plate as the cathode and a coated iridium tantalum oxide as the anode to electro-deposit continuously to produce electrolytic copper foil in the mixed solution, or using a titanium plate for small-scale production of electrolytic copper foil.

[0018] The beneficial effect of the present invention is to use A and B as raw materials and an inorganic base or an inorganic carbonate as a catalyst to simply and quickly achieve the one-pot preparation of pentacyclic nitrogen heterocyclic monothiopropanesulfonate with a high yield (>85%) and high purity (>95%); the reaction conditions are conducive to industrial scale-up production; in the production of electrolytic copper foil, cooperating with other additives can significantly improve the tensile properties of the copper foil material, and can produce a 6 μm ultra-thin electrolytic copper foil material with low defects, fine grains and high tensile strength (> 60 kgf / mm 2 ) Specific embodiments

[0019] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described examples are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art belong to the scope of protection of the present invention.

[0020] The synthesis reaction formula of pentacyclic nitrogen heterocyclic monothiopropanesulfonate is as follows:

[0021]

[0022] Example 1: A preparation method of a pentacyclic nitrogen heterocyclic monothiopropanesulfonate compound, including the following steps:

[0023] Add 200 mL of n-butanol and 238 g (2.0 mol) of thiazolidine-2-thione to a 1000 mL beaker. Use mechanical stirring to mix evenly. Most of the solid does not dissolve. Then add 112.2 g of potassium hydroxide (2.0 mol). Stir until the solution is clear. Slowly add dropwise 244 g (2.0 mol dissolved in 100 mL of n-butanol) of 1,3-propanesultone. Control the dropping rate with a peristaltic pump. The dropping temperature is 40°C - 45°C. After the addition of 1,3-propanesultone is complete, control the temperature at 45°C and keep it warm for 10 min. A large amount of white solid precipitates out, and the solution system is viscous. Continue to add 50 mL of n-butanol until the solution can be stirred normally. Cool to room temperature and transfer the reaction solution to a Buchner funnel. Wash the filter cake with n-butanol and then dry it to obtain a white, fluffy, powdery solid.

[0024] Example 2: A method for preparing a five-membered nitrogen heterocyclic monothiopropanesulfonate compound, comprising the following steps:

[0025] Add 200 mL of isopropanol and 204 g (2.0 mol) of ethylene thiourea to a 1000 mL beaker. Use mechanical stirring to mix evenly. Most of the solid does not dissolve. Then add 80 g of sodium hydroxide (2.0 mol). Stir until the solution is clear. Slowly add dropwise 244 g (2.0 mol dissolved in 100 mL of isopropanol) of 1,3-propanesultone. Control the dropping rate with a peristaltic pump. The dropping temperature is 45°C - 50°C. After the addition of 1,3-propanesultone is complete, control the temperature at 50°C and keep it warm for 1 h. A large amount of white solid precipitates out, and the solution system is viscous. Continue to add 50 mL of isopropanol until the solution can be stirred normally. Cool to room temperature and transfer the reaction solution to a Buchner funnel. Wash the filter cake with isopropanol and then dry it to obtain a white, fluffy, powdery solid.

[0026] Example 3: A method for preparing a five-membered nitrogen heterocyclic monothiopropanesulfonate compound, comprising the following steps:

[0027] Add 200 mL of n-propanol and 206 g (2.0 mol) of oxazolidine-2-thione to a 1000 mL beaker. Use mechanical stirring to mix evenly. Most of the solid does not dissolve. Then add 80 g of sodium hydroxide (2.0 mol). Stir until the solution is clear. Slowly add dropwise 244 g (2.0 mol dissolved in 100 mL of n-propanol) of 1,3-propanesultone. Control the dropping rate with a peristaltic pump. The dropping temperature is 15°C - 20°C. After the addition of 1,3-propanesultone is complete, control the temperature at 20°C and keep it warm for 3 h. A large amount of white solid precipitates out, and the solution system is viscous. Continue to add 50 mL of n-propanol until the solution can be stirred normally. Cool to room temperature and transfer the reaction solution to a Buchner funnel. Wash the filter cake with isopropanol and then dry it to obtain a white, fluffy, powdery solid.

[0028] Example 4: A preparation method of a five-membered nitrogen heterocyclic monothiopropane sulfonate compound, which is different from Example 1, uses isopropanol instead of n-butanol as the solvent.

[0029] Example 5: A preparation method of a five-membered nitrogen heterocyclic monothiopropane sulfonate compound, which is different from Example 1, uses potassium carbonate instead of potassium hydroxide.

[0030] Example 6: A preparation method of a five-membered nitrogen heterocyclic monothiopropane sulfonate compound, which is different from Example 1, maintains the reaction temperature at room temperature.

[0031] It should be noted that in the examples of this application, raw materials A and B include, but are not limited to, the above-mentioned ethylene thiourea, pyrrolidine-2-thione, thiazolidine-2-thione, 1,3-propane sultone, and the combination of alkaline catalysis. All combinations of general formula structures of raw materials A and B should be included.

[0032] The summary results of the purity and yield tests of the five-membered nitrogen heterocyclic monothiopropane sulfonates prepared in Examples 1-6 are as follows:

[0033]

[0034] It can be seen from the detection data in the above table that the five-membered nitrogen heterocyclic monothiopropane sulfonate produced by the preparation process of the present invention has a high yield and purity. The technical solution of this application optimizes the preparation steps of the five-membered nitrogen heterocyclic monothiopropane sulfonate, which is conducive to industrial scale-up synthesis.

[0035] The above-prepared five-membered nitrogen heterocyclic monothiopropane sulfonate has the effect of improving the tensile properties of electrolytic copper foil and can effectively improve the performance of copper foil.

[0036] The application of five-membered nitrogen heterocyclic monothiopropane sulfonate as a high anti-agent for electrolytic copper foil includes the following steps: Mix an electrolyte containing copper sulfate and sulfuric acid, five-membered nitrogen heterocyclic monothiopropane sulfonate, and other additives evenly to obtain a mixed solution; Use a cathode roll or a titanium plate as the cathode and a coated iridium tantalum oxide as the anode to continuously produce electrolytic copper foil by electrodeposition in the mixed solution, or use a titanium plate for small-scale production of electrolytic copper foil. The specific method for preparing electrolytic copper foil includes the following steps: Take 500 mL of raw foil solution, and the content of each component in the solution is 5 ppm - 40 ppm of five-membered nitrogen heterocyclic monothiopropane sulfonate, 210 g / L of CuS04:5H20 solution, 105 g / L of sulfuric acid, 45 ppm of chloride ion solution, 1.5 ppm of polyethylene glycol (6000), 40 ppm of sodium polydithiopropane sulfonate, and 8 ppm of collagen; Use a titanium plate as the cathode and a coated iridium tantalum oxide as the anode. The size of the iridium tantalum oxide anode plate is 15 cm x 6 cm x 0.5 cm, and the size of the titanium plate is 15 cm x 6 cm x 0.5 cm. The distance between the anode and cathode plates is 3 cm, and the size of the Hull cell is 105 mm x 150 mm x 85 mm. Electrodeposit for 40 s at a current density of 50℃, 50 A / dm 3 to obtain a 6 μm electrolytic copper foil.

[0037]

[0038] Combined with Table 2, take the electrolyte for use. The five-membered nitrogen heterocyclic monothiopropane sulfonate used in Experimental Groups 1 - 6 is the product of Example 1. A total of 7 groups of parallel experiments are carried out. As the concentration of the five-membered nitrogen heterocyclic monothiopropane sulfonate increases, the tensile strength soars. From the control group with zero addition of 34.91 kgf / mm 2 to the tensile strength when the addition concentrations are 5 ppm, 10 ppm, and 15 ppm also gradually increases to 43.91 kgf / mm 2 , 47.79 kgf / mm 2 , 50.07 kgf / mm 2 . At 20 ppm, the tensile strength has reached 55.36 kgf / mm 2 ; When the additive concentration gradually increases (from 5 ppm to 40 ppm), it rises from 43.91 kgf / mm 2 to 66.04 kgf / mm 2 . When the concentration is 0 ppm - 15 ppm, the surface gloss of the copper foil decreases as the concentration increases, and the gloss shows an upward trend at 30 ppm. It is proved that the five-membered nitrogen heterocyclic monothiopropane sulfonate has the effect of improving the tensile performance of electrolytic copper foil and can effectively improve the performance of copper foil.

Claims

1. Application of pentacyclic nitrogen heterocyclic monothiopropane sulfonate, characterized in that: Using a five-membered nitrogen heterocyclic monothiopropanesulfonate as a high resistance agent for electrolytic copper foil, the structural general formula of the five-membered nitrogen heterocyclic monothiopropanesulfonate is as follows: , where X is any one of N, O, and S, and Y is any one of Na, K, and Cs. Its preparation method includes the following steps: taking the raw material denoted as A, taking the raw material denoted as B, pouring the raw material A into a solvent, adding an alkali catalyst to dissolve until the system becomes clear, dissolving the raw material B in the solvent, then dropping the solution containing B into the alkaline solution containing A, a large amount of white precipitate products are generated during the reaction, after separation and drying, the five-membered nitrogen heterocyclic monothiopropanesulfonate is obtained, and the alkali catalyst is an inorganic base or an inorganic carbonate.

2. The application of the five-membered nitrogen heterocyclic monothiopropane sulfonate according to claim 1, characterized in that: The steps include: Take an electrolyte containing copper sulfate and sulfuric acid, a pentacyclic nitrogen heterocyclic monothiopropane sulfonate and other additives, mix them evenly to obtain a mixed solution; use a cathode roller or a titanium plate as the cathode, and a coated iridium tantalum oxide as the anode to continuously produce electrolytic copper foil by electrodeposition in the mixed solution, or use a titanium plate for small-scale production of electrolytic copper foil.

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