Preparation method and application of bisphenol A metal salt

Abstract

The invention belongs to the field of chemical engineering, and particularly relates to a preparation method and application of bisphenol A metal salt, the preparation method comprises the following steps: S1, bisphenol A is dissolved in a solvent, a reaction reagent dissolved with metal ions is added into the solvent for a neutralization reaction, and in the reaction process, an alkaline adjusting solution is added to adjust the pH; s2, separating precipitates generated by the reaction to obtain a crude product of bisphenol A metal salt; and S3, purifying the crude product to obtain the bisphenol A metal salt. Compared with the prior art, the method has the advantages that the problems of complex process, low yield and environmental pollution of bisphenol A metal salt preparation in the prior art are solved, the purity and yield of the product can be improved, and emission of wastewater and harmful gas is reduced.

Description

Technical Field

[0001] The invention belongs to the field of chemical industry, and specifically relates to a preparation method of bisphenol A metal salt and application thereof. Background Art

[0002] Bisphenol A (BPA) is an important chemical widely used in industry, and is often used to make materials such as polycarbonate plastics and epoxy resins. These materials are widely used in many fields such as automobiles, electronic equipment, building materials and food packaging. However, with the increasing concern about environmental and health issues, the safety of bisphenol A has been strictly scrutinized, and some countries have even banned its use in certain products. Therefore, finding safer and more environmentally friendly substitutes for bisphenol A or its modified products has become a research hotspot in the chemical industry. Bisphenol A metal salts are compounds formed by the combination of bisphenol A and metal ions (such as zinc, magnesium, calcium, etc.). They have unique physical and chemical properties, especially in terms of thermal stability, antioxidant and corrosion resistance. Bisphenol A metal salts have better thermal stability than unmodified bisphenol A, can reduce decomposition at high temperatures, and reduce the risk of its release into the environment; it also has strong corrosion resistance and is suitable for use as a preservative or antioxidant in corrosive environments. In addition, bisphenol A metal salts can also improve the mechanical properties of materials, such as enhancing the impact resistance and wear resistance of polymer materials, and have a wide range of application potential.

[0003] Bisphenol A metal salt can be used as a modifier for polycarbonate plastics and epoxy resins in the plastics industry, and shows significant advantages in products with high temperature requirements; in coatings, it is used as an anti-corrosion additive to extend the service life of the coating; in the field of flame retardant materials, it can improve the material's anti-combustion performance, and is particularly suitable for indoor building materials and electronic equipment. Although bisphenol A metal salt has a wide range of application prospects, the existing preparation process still has challenges such as harsh reaction conditions, low product purity, and environmental issues. In some processes, the reaction of bisphenol A with metal salts requires high temperature and high pressure, which increases energy consumption, and side reactions can lead to the generation of impurities, affecting product purity. For example, CN110878009A discloses a method for preparing bisphenol A salt, and the preparation steps are: (1) pulverizing and mixing bisphenol A and an inorganic strong base to obtain an ultrafine mixture; (2) heating and stirring the mixture to react to obtain a crude product; (3) vacuum distilling the crude product to remove the residual excess bisphenol A, and cooling to obtain a bisphenol A salt solid powder. To address these challenges, researchers are committed to developing green synthesis processes, using aqueous or solvent-free systems to reduce energy consumption and reduce the use of organic solvents. In addition, by optimizing catalysts and introducing nanotechnology, the yield and product purity can be improved, while giving the material more excellent properties. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing bisphenol A metal salt and its application in order to solve at least one of the above problems, so as to solve the problems of complex process, low yield and environmental pollution in the prior art for preparing bisphenol A metal salt. The present invention can improve the purity and yield of the product while reducing the emission of wastewater and harmful gases.

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] The first aspect of the present invention discloses a method for preparing a bisphenol A metal salt, comprising the following steps:

[0007] S1: dissolving bisphenol A in a solvent, and adding a reaction reagent containing metal ions to the solvent to cause a neutralization reaction. During the reaction, adding an alkaline regulating solution to adjust the pH;

[0008] S2: separating the precipitate generated by the reaction to obtain a crude product of bisphenol A metal salt;

[0009] S3: Purify the crude product to obtain the bisphenol A metal salt.

[0010] Preferably, the solvent is an alcohol organic solvent and / or a ketone organic solvent and / or water.

[0011] Preferably, the solvent includes ethanol, methanol, isopropanol, acetone and water.

[0012] Preferably, the reaction reagent is a soluble hydroxide of a metal ion and / or a soluble salt of a metal ion.

[0013] Preferably, in the reaction reagent, the metal ions include sodium ions, potassium ions, zinc ions and magnesium ions, and the soluble salt includes chloride.

[0014] Preferably, it includes one or more of the following:

[0015] i) the neutralization reaction temperature is 50-100°C and the time is 2-8h;

[0016] ii) during the reaction, the bisphenol A is added in excess according to a stoichiometric ratio;

[0017] iii) During the reaction, an alkaline adjusting solution is added to adjust the pH to 7-9.

[0018] Preferably, the alkaline regulating solution comprises sodium hydroxide, ammonia water and sodium bicarbonate.

[0019] Preferably, the separation comprises filtration and evaporation.

[0020] Preferably, the purification comprises recrystallization.

[0021] The second aspect of the present invention discloses a method for preparing any of the above-mentioned bisphenol A metal salts and its application in the fields of plastics industry, coatings and flame retardant materials.

[0022] The working principle of the present invention is:

[0023] The method comprises mixing bisphenol A and a solution containing metal ions in a solvent to carry out a neutralization reaction, and then adjusting the pH value to precipitate the product, and filtering and purifying to obtain a high-purity bisphenol A metal salt.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The invention simplifies the preparation process, improves the purity and yield of the product and reduces the pollution caused by the discharge of wastewater and harmful gases. The method is applicable to the preparation of various bisphenol A metal salts such as bisphenol A sodium salt, potassium salt, zinc salt, magnesium salt, etc., and these products have broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is a schematic flow diagram of the preparation method of Example 1;

[0027] Figure 2 This is the H NMR spectrum of the bisphenol A sodium salt prepared in Example 1. DETAILED DESCRIPTION

[0028] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0029] In the following description, unless otherwise specified, the reagents used are conventional commercially available products, and the methods used are well known in the art.

[0030] Raw material preparation: prepare the required reaction raw materials, including bisphenol A, reaction reagents dissolved with metal ions, as well as solvents and alkaline adjustment solutions.

[0031] Neutralization reaction: Dissolve bisphenol A in a solvent and add a reaction reagent containing metal ions. While stirring evenly, control the reaction temperature between 50-100°C to allow bisphenol A and the metal salt to undergo a neutralization reaction for 2-8 hours to generate bisphenol A metal salt.

[0032] Acid-base adjustment: During the reaction, the pH value of the solution is adjusted to between 7 and 9 by adding an alkaline adjustment solution to promote the reaction.

[0033] Product separation: After the reaction is completed, the generated precipitate is separated from the reaction solution by filtering or evaporating the solvent. The precipitate is the crude product of bisphenol A metal salt.

[0034] Product purification: The separated crude product is treated by recrystallization or other appropriate purification methods to further remove impurities and improve product purity.

[0035] Product detection: Infrared spectroscopy (IR), nuclear magnetic resonance (NMR), acid-base titration and other detection methods are used to characterize the generated bisphenol A metal salt to confirm its purity and structural correctness.

[0036] in,

[0037] Reaction reagents containing dissolved metal ions: soluble hydroxides of metal ions and / or soluble salts of metal ions; specifically, the metal ions include sodium ions, potassium ions, zinc ions and magnesium ions, and the soluble salts include chlorides; more specifically, for example, sodium hydroxide, calcium hydroxide or zinc chloride.

[0038] Solvent: alcohol organic solvent and / or ketone organic solvent and / or water; specifically, the alcohol organic solvent may be ethanol, methanol, isopropanol, etc., and the ketone organic solvent may be acetone, etc.

[0039] Alkaline adjusting solution: sodium hydroxide, ammonia water, sodium bicarbonate.

[0040] Recrystallization: The solvent is ethanol, methanol or isopropanol.

[0041] Nuclear magnetic resonance: The deuterated reagents used are deuterated chloroform, deuterated DMSO and deuterated acetone.

[0042] The structure of the prepared bisphenol A metal salt is shown below:

[0043]

[0044] The reaction temperature is 50-100°C, and can be 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, ..., 95°C, 100°C, etc., and all ranges and sub-ranges between the above values. Too high a reaction temperature will increase the formation of by-products, and too low a reaction temperature will reduce the reaction rate.

[0045] The equivalent of bisphenol A in the reaction is 1 to 2 equivalents of the effective functional groups of the metal salt used, which can be understood here as the molar ratio of bisphenol A to the effective functional groups of the metal salt is (1 to 2): 1. For example, the amount of bisphenol A used can be 1 equivalent, 1.2 equivalents, 1.4 equivalents, 1.6 equivalents, 1.8 equivalents and 2 equivalents of the effective functional groups of the metal salt, as well as all ranges and sub-ranges between the above values.

[0046] The reaction time is 2 to 8 hours, for example, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, ..., 7.5 hours and 8 hours, and all ranges and subranges between the above values.

[0047] In the above embodiments, any of the above ranges may be combined with any other ranges.

[0048] Example 1

[0049] Preparation of bisphenol A sodium salt, such as Figure 1 As shown:

[0050] Dissolve 22.8g (0.1mol) of bisphenol A in 100ml of ethanol, add 8.0g (0.2mol) of sodium hydroxide to the solution and stir evenly. Under stirring, adjust the pH of the solution to 8.0, maintain the reaction temperature at 60°C, and the reaction time is 4 hours. After the reaction is completed, separate the solid product by vacuum filtration and wash with an appropriate amount of ethanol to obtain a crude product. Finally, further purify by recrystallization to obtain 26.9g of high-purity bisphenol A sodium salt with a yield of 98.9%. The product is detected by nuclear magnetic hydrogen spectrum, such as Figure 2 As shown, the chemical shifts of 6.70 and 6.69 ppm are two groups of signals of bisphenol A sodium salt aromatic group, and the chemical shift of 1.48 is the methyl signal of bisphenol A sodium salt. In the NMR spectrum, there is no impurity signal, and the purity of the product is close to 100%.

[0051] Example 2

[0052] Preparation of bisphenol A potassium salt:

[0053] The reaction was adjusted based on Example 1, except that sodium hydroxide was replaced with potassium hydroxide. After the reaction was completed, the solid product was separated by vacuum filtration and washed with an appropriate amount of ethanol to obtain a crude product. Finally, it was further purified by recrystallization to obtain 29.8 g of high-purity bisphenol A potassium salt with a yield of 98.1%.

[0054] Example 3

[0055] Preparation of bisphenol A sodium salt:

[0056] The method was adjusted based on Example 1, except that the reaction temperature was adjusted to 50°C. After the reaction was completed, the solid product was separated by vacuum filtration and washed with an appropriate amount of ethanol to obtain a crude product. Finally, the product was further purified by recrystallization to obtain 26.8 g of high-purity sodium salt of bisphenol A with a yield of 98.5%.

[0057] Example 4

[0058] Preparation of bisphenol A sodium salt:

[0059] The method was adjusted based on Example 1, except that the effective functional group number equivalent was adjusted to 1.2 times. After the reaction was completed, the solid product was separated by vacuum filtration and washed with an appropriate amount of ethanol to obtain a crude product. Finally, it was further purified by recrystallization to obtain 25.8 g of high-purity bisphenol A sodium salt with a yield of 94.9%.

[0060] Example 5

[0061] The method was adjusted on the basis of Example 1, except that the pH value during the reaction was controlled to be 9. Finally, the product was further purified by recrystallization to obtain 24.3 g of high-purity sodium salt of bisphenol A with a yield of 89.4%.

[0062] Example 6

[0063] The method was adjusted based on Example 1, except that the reaction time was controlled to be 8 hours during the reaction. Finally, the product was further purified by recrystallization to obtain 26.3 g of high-purity sodium salt of bisphenol A with a yield of 96.7%.

[0064] Comparative Example

[0065] Dissolve 22.8g (0.1mol) of bisphenol A in 100ml of ethanol, add 8.0g (0.2mol) of sodium hydroxide to the solution and stir evenly. Under stirring, adjust the pH of the solution to 8.0, maintain the reaction temperature at 30°C, and the reaction time is 4 hours. After the reaction is completed, separate the solid product by vacuum filtration and wash with an appropriate amount of ethanol to obtain a crude product. Finally, further purify by recrystallization to obtain 6.9g of high-purity bisphenol A sodium salt with a yield of 25.4%.

[0066] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A method for preparing a bisphenol A metal salt, characterized in that: The steps include: S1: dissolving bisphenol A in a solvent, and adding a reaction reagent containing metal ions to the solvent to cause a neutralization reaction. During the reaction, adding an alkaline regulating solution to adjust the pH; S2: separating the precipitate generated by the reaction to obtain a crude product of bisphenol A metal salt; S3: Purify the crude product to obtain the bisphenol A metal salt.

2. The method for preparing a bisphenol A metal salt according to claim 1, characterized in that: The solvent is an alcohol organic solvent and / or a ketone organic solvent and / or water.

3. The method for preparing a bisphenol A metal salt according to claim 2, characterized in that: The solvent includes ethanol, methanol, isopropanol, acetone and water.

4. The method for preparing a bisphenol A metal salt according to claim 1, characterized in that: The reaction reagent is a soluble hydroxide of a metal ion and / or a soluble salt of a metal ion.

5. The method for preparing a bisphenol A metal salt according to claim 4, characterized in that: In the reaction reagent, the metal ions include sodium ions, potassium ions, zinc ions and magnesium ions, and the soluble salt includes chloride.

6. The method for preparing a bisphenol A metal salt according to claim 1, characterized in that: Include one or more of the following: i) the neutralization reaction temperature is 50-100°C and the time is 2-8h; ii) during the reaction, the bisphenol A is added in excess according to a stoichiometric ratio; iii) During the reaction, an alkaline adjusting solution is added to adjust the pH to 7-9.

7. The method for preparing a bisphenol A metal salt according to claim 1, characterized in that: The alkaline regulating solution comprises sodium hydroxide, ammonia water and sodium bicarbonate.

8. The method for preparing a bisphenol A metal salt according to claim 1, characterized in that: The separation includes filtration and evaporation.

9. The method for preparing a bisphenol A metal salt according to claim 1, characterized in that: The purification comprises recrystallization.

10. Application of the method for preparing bisphenol A metal salt according to any one of claims 1 to 9 in the fields of plastics industry, coatings and flame retardant materials.

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