Preparation method and application of five-membered azacyclo-monothiopropane sulfonate

Abstract

The invention discloses a preparation method and application of five-membered azacyclo-monothiopropane sulfonate, the structural general formula of the five-membered azacyclo-monothiopropane sulfonate is # imgabs0 #, X is any one of N, O and S, and Y is any one of Na, K and Cs. The method has the beneficial effects that the five-membered azacyclo-monothiopropane sulfonate with high yield (gt, 85%) and high purity (gt, 95%) can be simply and quickly prepared by a one-pot method, and the reaction conditions are beneficial to industrial amplification production; the tensile property of the copper foil material can be remarkably improved by matching with other additives in the production of the electrolytic copper foil, and the 6-micron ultrathin electrolytic copper foil material with low defects, fine grains and high tensile strength (gt; 60kgf / mm < 2 >) can be produced.

Description

Technical Field

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

[0002] Copper foil material is a key material in the manufacture of printed circuit boards (PCBs). PCB is the basic connecting component of electronic devices, and electrolytic copper foil provides it with a conductive layer. For example, in devices such as smartphones and computer motherboards, it can ensure the stable transmission of circuit signals. The quality of copper foil in the multi-layer PCB structure directly affects the integrity of signal transmission. At the same time, copper foil material is also an important component of lithium batteries. In the negative electrode current collector of lithium batteries, electrolytic copper foil carries the embedding and extraction process of lithium ions. With the development of new energy vehicles and portable electronic devices, the performance requirements of lithium batteries have increased, and the quality of electrolytic copper foil has become increasingly important.

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

[0004] For example, Chinese invention patent publication number CN101153405A discloses a composition for electroplating, in which a five-membered nitrogen-containing heterocyclic compound is reacted with 1-halogenated-2,3-propylene oxide to generate a brightener, which functions to improve the surface gloss and stability of the coating.

[0005] There are many methods for synthesizing five-membered nitrogen heterocyclic compounds. The following are some common synthesis methods: Catalytic cyclization method: The cyclization reaction is promoted by introducing a catalyst. Commonly used catalysts include acids, bases, metal catalysts, etc. Oxidative nucleophilic substitution method: The corresponding intermediate is generated by the reaction of a nucleophilic reagent with an oxidant, and then the intermediate is subjected to a cyclization reaction to obtain the target compound. Metal catalysis method: Metal catalysts are used 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 the specific reaction substrates and target products, and optimize and improve them to improve the efficiency and selectivity of the reaction. However, the specific synthesis method of five-membered nitrogen heterocyclic monothiopropane sulfonate has not been reported.

[0006] Chinese invention patent publication number CN106279032B discloses a method for synthesizing a five-membered nitrogen heterocyclic compound using gold catalysis, wherein triazine, diazo, gold catalyst and solvent are sequentially added to a reaction tube under argon protection, and then the temperature is raised to 60 degrees Celsius for 12 hours to obtain a five-membered nitrogen heterocyclic compound. The reaction time of this synthesis method is relatively long. Summary of the invention

[0007] There is no clear research conclusion or widely accepted view on whether five-membered nitrogen heterocyclic monothiopropane sulfonate can refine copper crystals. However, the inventors found that five-membered nitrogen heterocyclic monothiopropane sulfonate 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.

[0008] The problems to be solved by the present invention are at least one of the following: first, the synthesis time of five-membered nitrogen heterocyclic monothiopropane sulfonate is long and the process is cumbersome; second, the possibility of five-membered nitrogen heterocyclic monothiopropane sulfonate as a new high-resistance agent for electrolytic copper foil is sought, and for this purpose, a preparation method and application of five-membered nitrogen heterocyclic monothiopropane sulfonate are provided.

[0009] The technical solution of the present invention is: a method for preparing a five-membered nitrogen heterocyclic monothiopropane sulfonate, and the general structural formula of the five-membered nitrogen heterocyclic monothiopropane sulfonate is as follows: , wherein X is any one of N, O, and S, and Y is any one of Na, K, and Cs. The preparation method comprises the following steps: Denoted as A, the raw material Denoted as B, raw material A is poured into a solvent, and an alkali catalyst is added to dissolve until the system is clear. Raw material B is dissolved in the solvent, and then the solution containing B is added dropwise into the alkaline solution containing A. The reaction produces a large amount of white precipitate product, which is separated and dried to obtain the five-membered nitrogen heterocyclic monothiopropane sulfonate.

[0010] The solvent in the above scheme is one or more of water, methanol, ethanol, n-propanol, isopropanol and n-butanol.

[0011] The molar ratio of raw materials A to B in the above scheme is 1:1.0-1.5.

[0012] The base catalyst in the above scheme is one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate and cesium carbonate.

[0013] The reaction temperature in the above scheme is 20°C-50°C.

[0014] The reaction time of A and B in the above scheme is 10min-3h.

[0015] The application of the five-membered nitrogen heterocyclic monothiopropane sulfonate is to use the five-membered nitrogen heterocyclic monothiopropane sulfonate prepared by the preparation method of the five-membered nitrogen heterocyclic monothiopropane sulfonate as described above as a high resistance agent for electrolytic copper foil.

[0016] The above application includes the following steps: taking an electrolyte containing copper sulfate and sulfuric acid, a five-membered nitrogen heterocyclic monothiopropane sulfonate 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 scale.

[0017] The beneficial effects of the present invention are that A and B are used as raw materials, and an inorganic base or an inorganic carbonate is used as a catalyst, and a high-yield (>85%) and high-purity (>95%) five-membered nitrogen heterocyclic monothiopropane sulfonate is prepared simply and quickly by a one-pot method, and the reaction conditions are conducive to industrial scale-up production; in the production of electrolytic copper foil, other additives can be used to significantly improve the tensile properties of the copper foil material, and low-defect, fine-grained, high-tensile strength (>60kgf / mm 2 ) of 6 μm ultra-thin electrolytic copper foil material. DETAILED DESCRIPTION

[0018] 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.

[0019] The synthesis reaction formula of five-membered nitrogen heterocyclic monothiopropane sulfonate is as follows:

[0020] Example 1: A method for preparing a five-membered nitrogen heterocyclic monothiopropane sulfonate compound, comprising the following steps: Add 200 mL of n-butanol and 238 g (2.0 mol) of tetrahydrothiazolidinethione to a 1000 mL beaker and stir evenly with a mechanical stirrer. Most of the solids are not dissolved. Then add 112.2 g of potassium hydroxide (2.0 mol) and stir until the solution is clear. Slowly add 244 g (2.0 mol dissolved in 100 mL of n-butanol) of 1,3-propane sultone. Use a peristaltic pump to control the dripping rate. The dripping temperature is 40°C-45°C. After the addition of 1,3-propane sultone is completed, the temperature is controlled at 45°C and kept warm for 10 minutes. A large amount of white solid is precipitated 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 Bush suction funnel. Wash the filter cake with n-butanol and dry it to obtain a white fluffy powdery solid.

[0021] Example 2: A method for preparing a five-membered nitrogen heterocyclic monothiopropane sulfonate compound, comprising the following steps: Add 200 mL of isopropanol and 204 g (2.0 mol) of ethylene thiourea to a 1000 mL beaker and stir evenly with a mechanical stirrer. Most of the solids are not dissolved. Then add 80 g of sodium hydroxide (2.0 mol) and stir until the solution is clear. Slowly add 244 g (2.0 mol dissolved in 100 mL of isopropanol) of 1,3-propane sultone. Use a peristaltic pump to control the dripping rate. The dripping temperature is 45°C-50°C. After the addition of 1,3-propane sultone is completed, the temperature is controlled at 50°C and kept warm for 1 hour. A large amount of white solid is precipitated 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 Bush suction funnel. Wash the filter cake with isopropanol and dry it to obtain a white fluffy powdery solid.

[0022] Example 3: A method for preparing a five-membered nitrogen heterocyclic monothiopropane sulfonate compound, comprising the following steps: Add 200 mL of n-propanol and 206 g (2.0 mol) of tetrahydrooxazole-2-thione to a 1000 mL beaker and stir evenly with a mechanical stirrer. Most of the solids are not dissolved. Then add 80 g of sodium hydroxide (2.0 mol) and stir until the solution is clear. Slowly add 244 g (2.0 mol dissolved in 100 mL of n-propanol) of 1,3-propane sultone. Use a peristaltic pump to control the dripping rate. The dripping temperature is 15°C-20°C. After the addition of 1,3-propane sultone is completed, the temperature is controlled at 20°C and kept warm for 3 hours. A large amount of white solid is precipitated 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 Bush suction funnel. Wash the filter cake with isopropanol and dry it to obtain a white fluffy powdery solid.

[0023] Example 4: A method for preparing a five-membered nitrogen heterocyclic monothiopropane sulfonate compound. Different from Example 1, the solvent n-butanol is replaced by isopropanol.

[0024] Example 5: A method for preparing a five-membered nitrogen heterocyclic monothiopropane sulfonate compound. Different from Example 1, potassium hydroxide is replaced by potassium carbonate.

[0025] Example 6: A method for preparing a five-membered nitrogen heterocyclic monothiopropane sulfonate compound. Different from Example 1, the reaction temperature is maintained at room temperature.

[0026] 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 above-mentioned combination of ethylene thiourea, tetrahydropyrrole-2-thione, tetrahydrothiazolidinethione and 1,3-propane sultone and alkaline catalyst, and should include all general structural combinations of raw materials A and B.

[0027] The purity and yield test results of the five-membered nitrogen heterocyclic monothiopropane sulfonates prepared in Examples 1-6 are summarized as follows:

[0028] It can be seen from the test 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 the present application optimizes the preparation steps of the five-membered nitrogen heterocyclic monothiopropane sulfonate, which is conducive to industrial scale-up synthesis.

[0029] The five-membered nitrogen heterocyclic monothiopropane sulfonate prepared above has the function of improving the tensile properties of electrolytic copper foil and can effectively improve the performance of copper foil.

[0030] The application of five-membered nitrogen heterocyclic monothiopropane sulfonate as a high resistance agent for electrolytic copper foil includes the following steps: taking an electrolyte containing copper sulfate and sulfuric acid, five-membered nitrogen heterocyclic monothiopropane sulfonate 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 the mixed solution to continuously produce electrolytic copper foil, or using a titanium plate to produce electrolytic copper foil in a small trial. The specific method for preparing electrolytic copper foil includes the following steps: taking a raw foil liquid volume of 500mL, the content of each component in the solution is 5ppm-40ppm of five-membered nitrogen heterocyclic monothiopropane sulfonate, 210g / L of CuS0 4 :5H 2 0 solution, 105g / L sulfuric acid, 45ppm chloride ion solution, 1.5ppm polyethylene glycol (6000), 40ppm sodium polydisulfide dipropane sulfonate and 8ppm collagen; titanium plate as cathode, coated iridium tantalum oxide as anode, iridium tantalum oxide anode plate size 15cm x 6cm x 0.5cm, titanium plate size 15cm x 6cmx 0.5cm, cathode and anode plate spacing 3cm, Haring cell size 105mm x 150mm x 85mm, at 50℃, 50A / dm 3 Electrolytic copper foil of 6 μm was obtained by electroplating at a current density of 40 s.

[0031]

[0032] Combined with Table 2, the electrolyte was used. The five-membered nitrogen heterocyclic monothiopropane sulfonate used in Implementation Group 1-Implementation Group 6 was the product of Example 1. A total of 7 parallel experiments were conducted. As the concentration of the five-membered nitrogen heterocyclic monothiopropane sulfonate increased, the tensile strength soared, from 34.91 kgf / mm in the control group with zero addition. 2 The tensile strength also gradually increased to 43.91 kgf / mm when the addition concentration was 5ppm, 10ppm, and 15ppm. 2 、47.79 kgf / mm 2 、50.07 kgf / mm 2 At 20ppm, the tensile strength has reached 55.36 kgf / mm 2 ; When the additive concentration gradually increases (5ppm to 40ppm), from 43.91kgf / mm 2 Increased to 66.04kgf / mm 2 When adding 0ppm-15ppm, the surface glossiness of the copper foil decreases with the increase of concentration, and its glossiness tends to increase at 30ppm. It is proved that the 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.

Claims

1. A method for preparing a five-membered nitrogen heterocyclic monothiopropane sulfonate, characterized in that: The general structural formula of the five-membered nitrogen heterocyclic monothiopropane sulfonate is as follows: , wherein X is any one of N, O, and S, and Y is any one of Na, K, and Cs. The preparation method comprises the following steps: Denoted as A, the raw material Denoted as B, raw material A is poured into a solvent, and an alkali catalyst is added to dissolve until the system is clear. Raw material B is dissolved in the solvent, and then the solution containing B is added dropwise into the alkaline solution containing A. The reaction produces a large amount of white precipitate product, which is separated and dried to obtain the five-membered nitrogen heterocyclic monothiopropane sulfonate.

2. The method for preparing the five-membered nitrogen heterocyclic monothiopropane sulfonate according to claim 1, characterized in that: The solvent is one or more of water, methanol, ethanol, n-propanol, isopropanol and n-butanol.

3. The method for preparing the five-membered nitrogen heterocyclic monothiopropane sulfonate according to claim 1, characterized in that: The molar ratio of the raw materials A to B is 1:1.0-1.

5.

4. The method for preparing the five-membered nitrogen heterocyclic monothiopropane sulfonate according to claim 1, characterized in that: The alkaline catalyst is one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate and cesium carbonate.

5. The method for preparing the five-membered nitrogen heterocyclic monothiopropane sulfonate according to claim 1, characterized in that: The reaction temperature is 20°C-50°C.

6. The method for preparing the five-membered nitrogen heterocyclic monothiopropane sulfonate according to claim 1, characterized in that: The reaction time of A and B is 10min-3h.

7. Application of five-membered nitrogen heterocyclic monothiopropane sulfonate, characterized in that: The five-membered nitrogen heterocyclic monothiopropane sulfonate prepared by the preparation method of the five-membered nitrogen heterocyclic monothiopropane sulfonate as described in any one of claims 1 to 6 is used as a high resistance agent for electrolytic copper foil.

8. The use of the five-membered nitrogen heterocyclic monothiopropane sulfonate as claimed in claim 7, characterized in that: The following steps are involved: An electrolyte containing copper sulfate and sulfuric acid, five-membered nitrogen heterocyclic monothiopropane 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.

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