Quaternary ammonium salt compound with tripyridyl benzene as skeleton and preparation method

Abstract

The invention discloses a quaternary ammonium salt compound with tripyridyl benzene as a skeleton and a preparation method, and belongs to the technical field of quaternary ammonium salt compounds. Tripyridylbenzene is used as a reaction substrate, the tripyridylbenzene and a halogen-substituted alkyl compound or alkoxy compound are subjected to nucleophilic substitution to generate a quaternary ammonium salt compound, and the obtained quaternary ammonium salt compound has excellent surface activity and can be used as a brightening agent for cyanide-free gold electroplating. Wide application prospects are realized in the fields of surfactants and electroplating additives.

Description

Technical Field

[0001] The invention belongs to the technical field of quaternary ammonium salt compounds, and relates to a quaternary ammonium salt compound with tripyridylbenzene as a skeleton and a preparation method thereof, as well as use of the quaternary ammonium salt compound as a surfactant and an electroplating solution additive. Background Art

[0002] Surfactants are substances that can significantly reduce the surface tension of liquids and are widely used in detergents, emulsifiers, dispersants, wetting agents, foaming agents, etc. Quaternary ammonium surfactants are widely used in personal care products, household cleaning products, textile printing and dyeing, oilfield chemicals, etc. due to their excellent surface activity, good biodegradability and low toxicity.

[0003] Most of the existing quaternary ammonium salt surfactants are traditional alkyl quaternary ammonium salts, which have simple structures and relatively single application fields. In recent years, in order to meet the market demand for functional surfactants, researchers have continuously developed quaternary ammonium salts with new structures, such as introducing polyether segments, aromatic ring groups, etc., in order to obtain better performance, such as stronger emulsification ability, higher antistatic performance, etc. However, the existing new quaternary ammonium salts still have shortcomings in some aspects, such as high synthesis cost, complex production process, limited performance improvement, etc. Small molecule quaternary ammonium salts are usually composed of a clear chemical structure and have a single molecular composition and structure. This makes them easier to identify and determine during chemical analysis and characterization. Due to the clear structure, the physicochemical properties of small molecule quaternary ammonium salts (such as molecular weight, melting point, boiling point, solubility, etc.) are usually known and predictable. This makes it easier to control and adjust their performance when designing and optimizing products.

[0004] Electroplating is a technology that uses the principle of electrolysis to deposit a layer of metal or alloy film on the surface of metal or other materials. It is widely used to improve the surface hardness, wear resistance, corrosion resistance, conductivity, etc. of materials. Electroplating additives are an important component of the electroplating solution, which can improve the dispersibility of the electroplating solution and improve the quality and performance of the electroplated layer.

[0005] Common electroplating additives include leveling agents, brighteners, wetting agents, etc. Among them, the leveling agent can adjust the electrochemical properties of the electroplating solution, affect the current density and potential distribution during the electroplating process, and thus optimize the growth process of the electroplated layer. It helps to form a more uniform, dense and strongly bonded coating. Brighteners can significantly improve the brightness and smoothness of the coating, giving the coating a mirror-like luster. This is essential for decorative gold plating applications and can enhance the aesthetics and market competitiveness of the product. In the gold electroplating process, brighteners help to achieve uniform deposition of gold atoms during the electroplating process, ensuring that the coating forms a uniform crystalline structure at the microscopic level. This helps to reduce defects in the coating, such as pitting, pinholes and pits. Brighteners can improve the bonding between the coating and the substrate, making the coating more firmly attached to the surface of the substrate. This is essential to ensure the durability and functionality of the coating.

[0006] Quaternary ammonium salt compounds are often used as brighteners for electroplating gold because they carry positive charges in the plating solution and can be adsorbed on the cathode surface to increase polarization. Brighteners for electroplating gold are usually divided into inorganic brighteners and organic brighteners. Inorganic brighteners usually include some metal elements or semi-metal elements, such as copper, nickel, cobalt, arsenic, thallium and antimony, and their dosage is generally between 0.1-1 mg / L. These inorganic brighteners can significantly improve the grain size and brightness of the coating, and have an important influence on the color, pinhole rate, hardness, stress and wear resistance of the coating. However, the addition of inorganic brighteners usually increases the stress of the gold coating and deteriorates its ductility. In addition, some inorganic brighteners such as arsenic and thallium have greater toxicity and may cause harm to human health during use. Organic brighteners are usually small molecule compounds containing sulfur or nitrogen, and their dosage is generally between 0.1-10 g / L. For example, U.S. Patent No. 6565732B1 points out that heterocyclic compounds, such as bipyridine, phenanthroline, thiophene carboxylic acid and pyridine, are effective brighteners for gold plating liquids, and their dosage is in the range of 0.1-10 g / L. German Patent DE 2355581 also mentions that pyridine-3-sulfonic acid is a typical organic brightener, which can move or expand the current density range of depositing bright gold layer toward high current density, and its dosage is 1-10 g / L. However, excessive addition of organic brighteners can lead to additive plating, which increases the brittleness of the coating. Therefore, it is necessary to develop new organic brighteners to avoid the use of certain highly toxic inorganic additives, and at the same time, it is not easy to cause additive plating. Summary of the invention

[0007] The purpose of the present invention is to provide a quaternary ammonium salt compound with tripyridylbenzene as a skeleton and a preparation method thereof, wherein tripyridylbenzene is used as a reaction substrate, and a halogen-substituted alkyl compound or alkoxy compound undergoes a nucleophilic substitution reaction to generate a quaternary ammonium salt compound, which is suitable for the fields of surfactants and electroplating additives. The purpose of the present invention is achieved by the following specific technical scheme.

[0008] The primary aspect of the present invention is to provide a quaternary ammonium salt compound with tripyridylbenzene as a skeleton, the structure of which is shown in the following formula: , In the formula, A is an alkylene group with 1-6 carbon atoms, such as methylene, ethylene, propylene, butylene, pentylene, hexylene; or a cycloalkylene group with 3-6 carbon atoms, such as cyclopropane 1,2-diyl, cyclobutane 1,3-diyl, cyclopentane 1,4-diyl, cyclohexane 1,5-diyl, benzylene; or a group in which the hydrogen atoms in the aforementioned alkylene and cycloalkylene groups are replaced, such as hydroxymethylene, 2-hydroxyethylene, 1-methylcyclopropane-2,3-diyl; or a repeating unit of the structure -OCH2-CH2-, wherein the number of repeating units is 1-4. Preferably, A is methylene, ethylene, benzylene or -OCH2-CH2-; X is Cl, Br or I, preferably, X is Cl or Br, and most preferably Cl.

[0009] Preferably, the structure of the compound is one of the following formulae: , , , , , .

[0010] Another aspect of the present invention is to provide a method for preparing the aforementioned compound, comprising the following steps: S1. dissolving 1,3,5-tri(4-pyridyl)benzene in an organic solvent to obtain a 1,3,5-tri(4-pyridyl)benzene solution; S2: adding a compound containing both halogen and hydroxyl to a 1,3,5-tri(4-pyridyl)benzene solution and heating for reaction; After the reaction is completed, the solution is cooled and purified by column chromatography to obtain the compound product.

[0011] Furthermore, the organic solvent in step S1 is one or more of ethylene glycol, propylene glycol, glycerol, and ethylene glycol monomethyl ether.

[0012] Furthermore, the compound containing both halogen and hydroxyl in step S2 is 3-chloro-1-propanol, 2-chloroethoxyethanol, 3-chloro-1,2-propylene glycol, 3-chloro-1-phenyl-1-propanol or triethylene glycol monochlorohydrin.

[0013] Furthermore, in step S2, the reaction temperature is 160-180° C., and the reaction time is 0.5-2 h.

[0014] Furthermore, in step S2, the molar ratio of the compound containing both halogen and hydroxyl to 1,3,5-tri(4-pyridyl)benzene is (2.9-3.1):1.

[0015] Another aspect of the present invention is to provide use of the aforementioned compound as a surfactant.

[0016] Another aspect of the present invention is to provide use of the aforementioned compound as an additive for an electroplating solution.

[0017] Furthermore, the electroplating solution is composed of: 20-50 g / L of sulfite, 10-15 g / L of sodium gold sulfite in terms of gold element, 10-20 g / L of sulfate, 10-20 g / L of phosphate, 10-30 g / L of pyrophosphate, 10-30 g / L of tartrate, and 0.1-1.0 mg / L of the above compounds as electroplating gold brightener.

[0018] Compared with the prior art, the present invention has the following advantages and beneficial effects: the compound of the present invention is used as a brightener for electroplating gold, the electroplating light emission speed is fast, the coating is bright and uniform, the addition amount is between 0.1-1 mg / L, the use of certain highly toxic inorganic additives can be avoided, and it is not easy to cause additive inclusion plating. DETAILED DESCRIPTION

[0019] The technical solution of the present invention is described clearly and completely below. Obviously, the described implementation is only a part of the implementation of the present invention, not all of the implementation. Based on the implementation of the present invention, all other implementations obtained by ordinary technicians in this field without creative work are within the protection scope of the present invention. Example 1

[0020] A quaternary ammonium salt compound, the chemical structural formula is:

[0021] The synthesis method is as follows: In a two-necked flask with a magnet and a condenser, add 20 mL of ethylene glycol and raise the temperature to 80°C. Next, add 3.2 mmol of 1,3,5-tri(4-pyridyl)benzene to the flask to ensure that it is completely dissolved in ethylene glycol. After complete dissolution, add 9.6 mmol of 3-chloro-1-propanol and adjust the temperature to 170°C. Keep the reaction at 170°C for 1 hour. After the reaction is completed, cool the solution in the flask to room temperature and purify it by column chromatography to obtain the pure target compound.

[0022] Nuclear magnetic resonance spectrum NMR (500MHz, DMSO- d 6 , 22℃): 9.08(6H,ArH), 8.96(6H,ArH), 8.04(3H,ArH), 5.01(6H,CH2), 4.33(3H,OH), 3.49(6H,CH2), 2.22(6H,CH2). Example 2

[0023] A quaternary ammonium salt compound, the chemical structural formula is:

[0024] The synthesis method is as follows: In a two-necked flask with a magnet and a condenser, add 20 mL of ethylene glycol and raise the temperature to 80°C. Next, add 3.2 mmol of 1,3,5-tri(4-pyridyl)benzene to the flask to ensure that it is completely dissolved in ethylene glycol. After complete dissolution, add 9.6 mmol of 2-chloroethoxyethanol and adjust the temperature to 170°C. Keep the reaction at 170°C for 1 hour. After the reaction is completed, cool the solution in the flask to room temperature and purify it by column chromatography to obtain the pure target compound.

[0025] Nuclear magnetic resonance spectrum NMR (500MHz, DMSO- d 6 , 22℃): 9.09(6H,ArH), 8.98(6H,ArH), 8.07(3H,ArH), 5.02(3H, OH), 4.36(6H,CH2), 4.11(6H,CH2), 3.70(6H,CH2), 3.54(6H,CH2). Example 3

[0026] A quaternary ammonium salt compound, the chemical structural formula is:

[0027] The synthesis method is as follows: In a two-necked flask with a magnet and a condenser, add 20 mL of ethylene glycol and raise the temperature to 80°C. Next, add 3.2 mmol of 1,3,5-tri(4-pyridyl)benzene to the flask to ensure that it is completely dissolved in ethylene glycol. After complete dissolution, add 9.6 mmol of 3-chloro-1,2-propanediol and adjust the temperature to 170°C. Keep the reaction at 170°C for 1 hour. After the reaction is completed, cool the solution in the flask to room temperature and purify it by column chromatography to obtain the pure target compound.

[0028] Nuclear magnetic resonance spectrum NMR (500MHz, DMSO- d 6 , 22℃): 9.08(6H,ArH), 8.96(6H,ArH), 8.04(3H,ArH), 5.37(3H,OH), 5.29(6H,CH2), 4.01(3H,OH), 3.60(3H,CH), 3.59(6H,CH2). Example 4

[0029] A quaternary ammonium salt compound, the chemical structural formula is:

[0030] The synthesis method is as follows: In a two-necked flask with a magnet and a condenser, add 20 mL of ethylene glycol and raise the temperature to 80°C. Next, add 3.2 mmol of 1,3,5-tri(4-pyridyl)benzene to the flask to ensure that it is completely dissolved in ethylene glycol. After complete dissolution, add 9.6 mmol of 3-chloro-1-phenyl-1-propanol and adjust the temperature to 170°C. Keep the reaction at 170°C for 1 hour. After the reaction is completed, cool the solution in the flask to room temperature and purify it by column chromatography to obtain the pure target compound.

[0031] Nuclear magnetic resonance spectrum NMR (500MHz, DMSO- d 6 , 22℃): 9.13(6H,ArH), 9.02(6H,ArH), 8.11(3H,ArH), 7.32(6H,ArH), 7.25(9H,ArH), 5.01(6H,CH2), 4.71(3H, OH), 4.41(3H,CH), 2.51(6H,CH2). Example 5

[0032] A quaternary ammonium salt compound, the chemical structural formula is:

[0033] The synthesis method is as follows: In a two-necked flask with a magnet and a condenser, add 20 mL of ethylene glycol and raise the temperature to 80°C. Next, add 3.2 mmol of 1,3,5-tri(4-pyridyl)benzene to the flask to ensure that it is completely dissolved in ethylene glycol. After complete dissolution, add 9.6 mmol of triethylene glycol monochlorohydrin and adjust the temperature to 170°C. Keep the reaction at 170°C for 1 hour. After the reaction is completed, cool the solution in the flask to room temperature and purify it by column chromatography to obtain the pure target compound.

[0034] Nuclear magnetic resonance spectrum NMR (500MHz, DMSO- d 6 , 22℃): 9.11(6H,ArH), 8.99(6H,ArH), 8.06(3H,ArH), 4.33(6H,CH2), 4.21(6H,CH2),3.75(3H, OH), 3.67(6H,CH2), 3.58(6H,CH2), 3.52(6H,CH2), 3.50(6H,CH2). Example 6

[0035] A quaternary ammonium salt compound, the chemical structural formula is:

[0036] The synthesis method is as follows: In a two-necked flask with a magnet and a condenser, add 20 mL of ethylene glycol and raise the temperature to 80°C. Next, add 3.2 mmol of 1,3,5-tri(4-pyridyl)benzene to the flask to ensure that it is completely dissolved in ethylene glycol. After complete dissolution, add 9.6 mmol of triethylene glycol monochlorohydrin and adjust the temperature to 160°C. Keep the reaction at 170°C for 1 hour. After the reaction is completed, cool the solution in the flask to room temperature and purify it by column chromatography to obtain the pure target compound. Example 7

[0037] A quaternary ammonium salt compound, the chemical structural formula is:

[0038] The synthesis method is as follows: In a two-necked flask with a magnet and a condenser, add 20 mL of ethylene glycol and raise the temperature to 80°C. Next, add 3.2 mmol of 1,3,5-tri(4-pyridyl)benzene to the flask to ensure that it is completely dissolved in ethylene glycol. After complete dissolution, add 9.6 mmol of triethylene glycol monochlorohydrin and adjust the temperature to 180°C. Keep the reaction at 170°C for 1 hour. After the reaction is completed, cool the solution in the flask to room temperature and purify it by column chromatography to obtain the pure target compound. Example 8

[0039] A quaternary ammonium salt compound, the chemical structural formula is:

[0040] The synthesis method is as follows: In a two-necked flask with a magnet and a condenser, add 20 mL of ethylene glycol and raise the temperature to 80°C. Next, add 3.2 mmol of 1,3,5-tri(4-pyridyl)benzene to the flask to ensure that it is completely dissolved in ethylene glycol. After complete dissolution, add 9.6 mmol of triethylene glycol monochlorohydrin and adjust the temperature to 170°C. Keep the reaction at 170°C for 0.5 hours. After the reaction is completed, cool the solution in the flask to room temperature and purify it by column chromatography to obtain the pure target compound. Example 9

[0041] A quaternary ammonium salt compound, the chemical structural formula is:

[0042] The synthesis method is as follows: In a two-necked flask with a magnet and a condenser, add 20 mL of ethylene glycol and raise the temperature to 80°C. Next, add 3.2 mmol of 1,3,5-tri(4-pyridyl)benzene to the flask to ensure that it is completely dissolved in ethylene glycol. After complete dissolution, add 9.6 mmol of triethylene glycol monochlorohydrin and adjust the temperature to 170°C. Keep the reaction at 170°C for 2 hours. After the reaction is completed, cool the solution in the flask to room temperature and purify it by column chromatography to obtain the pure target compound. Example 10

[0043] The quaternary ammonium salt compound synthesized in Example 2 was subjected to surface tension test, and the test process and results are as follows: Quaternary ammonium salt polymer solutions of different concentrations were prepared using ultrapure water, and the surface tension was measured by the hanging ring method at 25°C. The critical micelle concentration (CMC) of the cationic surfactant prepared in Example 2 was 8.4×10- 4 mol / L, and the commonly used surfactant sodium dodecyl sulfate (CMC=9.0×10 -3 mol / L), and the lowest surface tension reached 35.71mN / m, indicating that it has excellent surface activity. Embodiment 11

[0044] The quaternary ammonium salt polymer synthesized in Example 2 was used as a brightener for cyanide-free gold plating, and was used in combination with a gold plating complexing agent as a test example for cyanide-free gold plating. First, a cyanide-free gold plating solution containing the quaternary ammonium salt polymer of Example 1 as a brightener was prepared, and the plating solution composition was as follows: sodium sulfite (40 g / L), sodium sulfate (15 g / L), sodium dihydrogen phosphate (15 g / L), potassium sodium tartrate (20 g / L), potassium pyrophosphate (20 g / L), sodium gold sulfite (12 g / L, measured in gold), and the brightener was the polymer in Example 1 (0.6 ppm). Then, a 0.08 dm 2 The brass sheet was placed in the above-mentioned cyanide-free gold plating solution at a plating temperature of 55°C, a pH value of 8.5, and a current density of 0.4A / dm 2 The electroplating was carried out for 3.5 hours under the conditions of , and the surface of the plated sheet was in a mirror-bright state. Comparative Example 1

[0045] First, prepare a cyanide-free gold plating solution without brightener. The composition of the plating solution is as follows: sodium sulfite (40g / L), sodium sulfate (15g / L), sodium dihydrogen phosphate (15g / L), potassium sodium tartrate (20g / L), potassium pyrophosphate (20g / L), sodium gold sulfite (12g / L, measured in gold). Then, a surface area of ​​0.08dm 2 The brass sheet was placed in the above-mentioned cyanide-free gold plating solution at a plating temperature of 55°C, a pH value of 8.5, and a current density of 0.4A / dm 2 The electroplating was carried out for 3.5 hours under the conditions of , thereby obtaining a matte plated sheet.

[0046] Although the embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and cannot be understood as limiting the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and purpose of the present invention. The protection scope of the present invention is defined by the claims and their equivalent technical solutions.

Claims

1. A quaternary ammonium salt compound with tripyridylbenzene as a skeleton, characterized in that: Its structure is shown below: ， In the formula, A is an alkylene group having 1 to 6 carbon atoms, or a cycloalkylene group having 3 to 6 carbon atoms, or a group in which the hydrogen atoms in the aforementioned alkylene group or cycloalkylene group are replaced, or a repeating unit having the structure -OCH2-CH2-, and the number of repeating units is 1 to 4; X is Cl, Br or I.

2. The compound according to claim 1, characterized in that Its structure is one of the following: ， ， ， ， ， 。 3. The method for preparing the compound according to claim 1 or 2, characterized in that: The following steps are involved: S1. dissolving 1,3,5-tri(4-pyridyl)benzene in an organic solvent to obtain a 1,3,5-tri(4-pyridyl)benzene solution; S2: adding a compound containing both halogen and hydroxyl to a 1,3,5-tri(4-pyridyl)benzene solution and heating for reaction; After the reaction is completed, the solution is cooled and purified by column chromatography to obtain the compound product.

4. The preparation method according to claim 3, characterized in that: The organic solvent in step S1 is one or more of ethylene glycol, propylene glycol, glycerol, and ethylene glycol monomethyl ether.

5. The preparation method according to claim 3, characterized in that: The compound containing both halogen and hydroxyl in step S2 is 3-chloro-1-propanol, 2-chloroethoxyethanol, 3-chloro-1,2-propylene glycol, 3-chloro-1-phenyl-1-propanol or triethylene glycol monochlorohydrin.

6. The preparation method according to claim 3, characterized in that: In step S2, the reaction temperature is 160-180° C., and the reaction time is 0.5-2 h.

7. The preparation method according to claim 3, characterized in that: In step S2, the molar ratio of the compound containing both halogen and hydroxyl to 1,3,5-tri(4-pyridyl)benzene is (2.9-3.1):

1.

8. Use of the compound according to claim 1 or 2 as a surfactant.

9. Use of the compound according to claim 1 or 2 as an additive for electroplating solution.

10. The use according to claim 9, characterized in that The electroplating solution is composed of: 20-50 g / L of sulfite, 10-15 g / L of sodium gold sulfite in terms of gold element, 10-20 g / L of sulfate, 10-20 g / L of phosphate, 10-30 g / L of pyrophosphate, 10-30 g / L of tartrate, and 0.1-1.0 mg / L of the compound according to claim 1 or 2.

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