阅读说明：本技术 一种高纯度四溴双酚a的制备工艺 (Preparation process of high-purity tetrabromobisphenol A ) 是由 王盛海 郭建树 赵震 于 2021-02-02 设计创作，主要内容包括：本发明提供一种高纯度四溴双酚A的制备方法,包括如下步骤：(1)将双酚A加入至溶剂中搅拌均匀,加入催化剂反应,反应结束后在特定温度下同时滴加溴素和双氧水,得到四溴双酚A溶液；(2)将步骤(1)制得的四溴双酚A溶液升温进行熟化反应；(3)熟化后的四溴双酚A溶液静置分水、降温结晶、抽滤、烘干得到高纯度四溴双酚A；(4)收集步骤(3)抽滤的滤液,向滤液中加水,蒸馏结晶,得到纯度＞97%的四溴双酚A产品。本发明通过降温结晶的方式得到纯度≥99.9%的高纯度四溴双酚A产品,剩余的料液用蒸馏结晶的方式得到纯度＞97%的四溴双酚A产品。(The invention provides a preparation method of high-purity tetrabromobisphenol A, which comprises the following steps: (1) adding bisphenol A into a solvent, uniformly stirring, adding a catalyst for reaction, and after the reaction is finished, simultaneously dropwise adding bromine and hydrogen peroxide at a specific temperature to obtain a tetrabromobisphenol A solution; (2) heating the tetrabromobisphenol A solution prepared in the step (1) to carry out curing reaction; (3) standing the cured tetrabromobisphenol A solution for water diversion, cooling for crystallization, filtering, and drying to obtain high-purity tetrabromobisphenol A; (4) and (4) collecting the filtrate obtained by suction filtration in the step (3), adding water into the filtrate, and carrying out distillation crystallization to obtain a tetrabromobisphenol A product with the purity of more than 97%. The invention obtains a high-purity tetrabromobisphenol A product with the purity of more than or equal to 99.9 percent by a cooling crystallization mode, and obtains a tetrabromobisphenol A product with the purity of more than 97 percent by the residual feed liquid by a distillation crystallization mode.)

1. A preparation method of high-purity tetrabromobisphenol A is characterized by comprising the following steps:

(1) adding bisphenol A into a solvent, uniformly stirring, adding a catalyst for reaction, and after the reaction is finished, simultaneously dropwise adding bromine and hydrogen peroxide at a specific temperature to obtain a tetrabromobisphenol A solution;

(2) heating the tetrabromobisphenol A solution prepared in the step (1) to carry out curing reaction;

(3) standing the cured tetrabromobisphenol A solution for water diversion, cooling for crystallization, filtering, and drying to obtain the high-purity tetrabromobisphenol A.

2. The method of claim 1, further comprising the steps of: and (4) collecting the filtrate obtained by suction filtration in the step (3), adding water into the filtrate, and carrying out distillation crystallization to obtain a tetrabromobisphenol A product with the purity of more than 97%.

3. The method of claim 1, wherein the solvent is methylene chloride; the mass ratio of the bisphenol A to the solvent is 1: 4-6.

4. The method of claim 1, wherein the ratio of bisphenol a: bromine: the molar ratio of hydrogen peroxide is 1: 2.01-2.1: 2.01-2.11.

5. The method for preparing high-purity tetrabromobisphenol A according to claim 1, wherein the dropping temperature of bromine and hydrogen peroxide is 0-30 ℃.

6. The method for preparing high-purity tetrabromobisphenol A according to claim 1, wherein the dropping temperature of bromine and hydrogen peroxide is 20-30 ℃.

7. The method of claim 1, wherein the catalyst is sulfuric acid, and the mass ratio of bisphenol A to sulfuric acid is 1: 0.001-0.01.

8. The method of claim 1, wherein the curing temperature is 30 ℃ to 40 ℃ and the curing time is 3 to 5 hours.

9. The method of claim 1, wherein the curing temperature is 30-35 ℃.

10. The method of claim 1, wherein the crystallization temperature in step (3) is 10 ℃ or less and the drying temperature is 120 ℃.

Technical Field

The invention relates to tetrabromobisphenol A, in particular to a preparation method of high-purity tetrabromobisphenol A.

Background

Tetrabromobisphenol A is a reactive flame retardant and an additive flame retardant, is widely used for producing flame retardant plastics, and has good flame retardant effect. As a reactive flame retardant, the flame retardant can be used for producing flame retardant resins such as epoxy resin, polycarbonate and the like; as an additive flame retardant, the flame retardant is used for producing flame retardant resins such as polystyrene resin, ABS resin, phenolic resin and the like.

Tetrabromobisphenol A can be prepared by bromination reaction of bisphenol A in different solvents, and low molecular alcohols such as methanol are commonly used solvents, but have the disadvantage that alkyl bromide, particularly methanol, is generated during the reaction, and methyl bromide is easily generated, and is forbidden as a substance damaging the ozone layer.

The invention patent with the application number of CN200310117025.1 discloses a preparation method of tetrabromobisphenol A, bisphenol A is dissolved in ethanol solvent to form ethanol solution of bisphenol A, and then catalyst sulfuric acid is added into the ethanol solution of bisphenol A; adding bromine to an ethanolic solution of bisphenol A, whereupon the bisphenol A is partially brominated and hydrogen bromide is produced; adding hydrogen peroxide into the solution to oxidize the generated hydrogen bromide into bromine, and continuing to participate in the bromination reaction of the bisphenol A until the bromination reaction is finished or the bromine is exhausted; after the low-temperature bromination reaction is finished, carrying out an intensified bromination reaction; and cooling the reaction liquid, carrying out vacuum suction filtration, and washing and drying a filter cake by using an ethanol solution and deionized water in sequence to obtain a tetrabromobisphenol A product. Although the technology solves the problem of generating methyl bromide in the production process, the yield of the tetrabromobisphenol A prepared by the technology is low, and the purity of the product is low.

The invention patent with the application number of CN201710099243.9 discloses a preparation method of tetrabromobisphenol A, which comprises the following steps: dissolving bisphenol A in a mixed solvent consisting of water and a halogenated hydrocarbon solvent to obtain a first mixture; adding sodium bromide and concentrated hydrochloric acid to the first mixture to obtain a second mixture; dropwise adding a potassium bromate solution into the second mixture under stirring to obtain a third mixture; dropwise adding hydrogen peroxide to the third mixture under stirring to obtain a fourth mixture; carrying out ultrasonic treatment on the fourth mixture for 40-50min to obtain a fifth mixture; dropwise adding a sodium sulfite solution into the fifth mixture under stirring to obtain a sixth mixed solution; standing the sixth mixed solution, removing the water phase, and dropwise adding a reducing agent into the organic phase while stirring to obtain a seventh mixed solution; and cooling and crystallizing the seventh mixed solution, and then carrying out suction filtration, washing and drying to obtain the product. The tetrabromobisphenol A prepared by the patent technology has low purity, and meanwhile, the process is complex and the production cost is high.

The invention with the application number of CN201710357593.0 discloses a method for producing tetrabromobisphenol A, which prepares a finished product of tetrabromobisphenol A through catalytic reaction, curing reaction, reduction reaction, washing process, crystallization process, centrifugal separation and vacuum drying. In the patent technology, because the solubility of tetrabromobisphenol A in chlorobenzene is higher, the product loss is higher, and the total yield of the product is lower; the yield of tetrabromobisphenol A prepared for the first time can only reach 80 percent, the yield can reach about 99 percent after the mother liquor is recycled for many times, but the product purity can be greatly reduced along with the increase of the cycle number of the mother liquor, and the chroma is higher and higher. The patented technology cannot prepare a high-purity product while satisfying high yield.

Disclosure of Invention

In order to solve the technical problems in the prior art, the invention provides a preparation method of high-purity tetrabromobisphenol A, which achieves the following aims: (1) the reaction temperature is reduced, so that the reaction time is prolonged, namely, the generation of yellow substances is reduced, and the reaction is more sufficient; (2) obtaining a high-purity product in a cooling crystallization mode; (3) the solvent is not recycled, so that the influence on the product quality due to recycling of the mother liquor is avoided, and the product quality is stable; and simultaneously, the yield of the product is improved.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

the preparation method of the high-purity tetrabromobisphenol A comprises the following steps:

(1) adding bisphenol A into a solvent, uniformly stirring, adding a catalyst, reacting for 0.5-1h, and after the reaction is finished, simultaneously dropwise adding bromine and hydrogen peroxide at a specific temperature to obtain a tetrabromobisphenol A solution;

(2) heating the tetrabromobisphenol A solution prepared in the step (1) to carry out curing reaction, wherein the reaction temperature is 30-40 ℃, preferably 30-35 ℃, and the curing time is 3-5 h;

(3) and standing the cured tetrabromobisphenol A solution for layering for 0.5h, separating out a water phase after standing, and collecting an organic phase. Adding 20g of sodium sulfite solution into the organic phase, stirring, heating to above 30 ℃, keeping the temperature for 0.5h after stirring, controlling the temperature to be 30-40 ℃ and keeping the temperature for 0.5h, standing for layering after keeping the temperature, keeping the standing time for 0.5h, separating out the aqueous phase after standing, and collecting the organic phase A. Adding 50g of water into the organic phase A, stirring for 0.5h, raising the temperature to 30-40 ℃ after stirring, standing for layering for 0.5h, separating out the water phase after standing, and collecting the organic phase B. The collected organic phase B is subjected to cooling crystallization, suction filtration and drying to obtain a product with the purity of more than or equal to 99.9 percent;

(4) and (4) collecting the filtrate obtained by suction filtration in the step (3), adding water into the filtrate, and carrying out distillation crystallization to obtain a tetrabromobisphenol A product with the purity of more than 97%.

Preferably, step (4) collects the filtrate of the suction filtration step, adds water into the filtrate for distillation crystallization, and completely evaporates the dichloromethane to obtain the tetrabromobisphenol A product with the purity of 98.5-99%.

Preferably, the solvent is dichloromethane.

Preferably, the mass ratio of the bisphenol A to the solvent is 1: 4-6.

Preferably, the bisphenol a: bromine: the molar ratio of hydrogen peroxide is 1: 2.01-2.1: 2.01-2.11.

Preferably, the dropping temperature of the bromine and the hydrogen peroxide is 0-30 ℃, preferably 20-30 ℃.

Preferably, the catalyst is sulfuric acid, and the mass ratio of the bisphenol A to the sulfuric acid is 1: 0.001-0.01.

Preferably, the crystallization temperature in the step (3) is less than or equal to 10 ℃, and the drying temperature is 120 DEG C

Compared with the prior art, the invention has the beneficial effects that:

(1) the preparation method of high-purity tetrabromobisphenol A reduces the generation of yellow substances by reducing the reaction temperature and prolonging the reaction time, and simultaneously enables the reaction to be more sufficient.

(2) According to the preparation method of the high-purity tetrabromobisphenol A, the high-purity tetrabromobisphenol A product with the purity of more than or equal to 99.9% is obtained in a cooling crystallization mode, and the tetrabromobisphenol A product with the purity of more than 97% is obtained from the rest feed liquid in a distillation crystallization mode;

(3) according to the preparation method of the high-purity tetrabromobisphenol A, the solvent is not recycled, so that the influence on the product quality due to recycling of the mother solution is avoided, and the product chromaticity is less than or equal to 10;

(4) the preparation method of high-purity tetrabromobisphenol A improves the product yield to more than 99.5 percent.

Detailed Description

In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.

Example 1

(1) Adding 22.8g of bisphenol A into 100g of dichloromethane at room temperature, starting stirring, adding 0.03g of sulfuric acid, simultaneously dropwise adding bromine and hydrogen peroxide after 0.5h, cooling the salt water, slowly heating the reaction system to 20 ℃, keeping the temperature of 20-25 ℃ for dropwise adding, wherein the bromine dropwise adding amount is 33.2g, and the hydrogen peroxide dropwise adding amount is 25.8g, so as to obtain a tetrabromobisphenol A solution.

(2) Heating the tetrabromobisphenol A solution prepared in the step (1) to carry out curing reaction, wherein the reaction temperature is 30 ℃, and the curing time is 5 hours.

(3) And standing the cured tetrabromobisphenol A solution for layering for 0.5h, separating out a water phase after standing, and collecting an organic phase. Adding 20g of sodium sulfite solution into the organic phase, stirring, controlling the concentration of the sodium sulfite solution to be 10%, stirring for 0.5h, controlling the temperature to be 32 ℃ after stirring, keeping the temperature for 0.5h, standing for layering after keeping the temperature, separating the aqueous phase after standing, and collecting the organic phase A. Adding 50g of water into the organic phase A, stirring for 0.5h, heating to 33 ℃ after stirring is finished, standing for layering for 0.5h, separating out the water phase after standing is finished, and collecting the organic phase B. And cooling the collected organic phase B to 8 ℃ for crystallization, and performing suction filtration and drying to obtain a tetrabromobisphenol A product with the purity of 99.95 percent and the chroma of 5.

(4) And collecting the filtrate obtained in the suction filtration step, adding 70g of water into the filtrate, distilling and crystallizing, and completely distilling off dichloromethane to obtain a tetrabromobisphenol A product with the purity of 98.85 percent and the chroma of 20.

The total amount of the product was 54.34g, and the yield was 99.89%.

Example 2

(1) Adding 22.8g of bisphenol A into 100g of dichloromethane at room temperature, starting stirring, adding 0.05g of sulfuric acid, simultaneously dropwise adding bromine and hydrogen peroxide after 0.5h, cooling the salt water, slowly heating the reaction system to 20 ℃, keeping the temperature of 20-25 ℃ for dropwise adding, wherein the bromine dropwise adding amount is 33.2g, and the hydrogen peroxide dropwise adding amount is 25.8g, so as to obtain a tetrabromobisphenol A solution.

(2) Heating the tetrabromobisphenol A solution prepared in the step (1) to carry out curing reaction, wherein the reaction temperature is 30 ℃, and the curing time is 4.5 h.

(3) And standing the cured tetrabromobisphenol A solution for layering for 0.5h, separating out a water phase after standing, and collecting an organic phase. Adding 20g of sodium sulfite solution into the organic phase, stirring, controlling the concentration of the sodium sulfite solution to be 10%, stirring for 0.5h, controlling the temperature to be 32 ℃ after stirring, keeping the temperature for 0.5h, standing for layering after keeping the temperature, separating the aqueous phase after standing, and collecting the organic phase A. Adding 50g of water into the organic phase A, stirring for 0.5h, heating to 33 ℃ after stirring is finished, standing for layering for 0.5h, separating out the water phase after standing is finished, and collecting the organic phase B. And cooling the collected organic phase B to 8 ℃ for crystallization, and performing suction filtration and drying to obtain a tetrabromobisphenol A product with the purity of 99.94 percent and the chroma of 5.

(4) And collecting the filtrate obtained in the suction filtration step, adding 70g of water into the filtrate, distilling and crystallizing, and completely distilling off dichloromethane to obtain a tetrabromobisphenol A product with the purity of 98.84% and the chroma of 20.

The total amount of the obtained product was 54.32g, and the yield was 99.85%.

Example 3

(1) Adding 22.8g of bisphenol A into 110g of dichloromethane at room temperature, starting stirring, adding 0.10g of sulfuric acid, simultaneously dropwise adding bromine and hydrogen peroxide after 0.5h, cooling the salt water, slowly heating the reaction system to 25 ℃, keeping the temperature of 25-30 ℃ for dropwise adding, wherein the bromine dropwise adding amount is 32.6g, and the hydrogen peroxide dropwise adding amount is 25.5g, so as to obtain a tetrabromobisphenol A solution.

(2) Heating the tetrabromobisphenol A solution prepared in the step (1) to carry out curing reaction, wherein the reaction temperature is 35 ℃, and the curing time is 4 hours.

(3) And standing the cured tetrabromobisphenol A solution for layering for 0.5h, separating out a water phase after standing, and collecting an organic phase. Adding 20g of sodium sulfite solution into the organic phase, stirring, controlling the concentration of the sodium sulfite solution to be 10%, stirring for 0.5h, controlling the temperature to be 32 ℃ after stirring, keeping the temperature for 0.5h, standing for layering after keeping the temperature, separating the aqueous phase after standing, and collecting the organic phase A. Adding 50g of water into the organic phase A, stirring for 0.5h, heating to 33 ℃ after stirring is finished, standing for layering for 0.5h, separating out the water phase after standing is finished, and collecting the organic phase B. And cooling the collected organic phase B to 4 ℃ for crystallization, and performing suction filtration and drying to obtain a tetrabromobisphenol A product with the purity of 99.94 percent and the chromaticity of 10.

(4) And collecting the filtrate obtained in the suction filtration step, adding 70g of water into the filtrate, distilling and crystallizing, and completely distilling off dichloromethane to obtain a tetrabromobisphenol A product with the purity of 98.8% and the chroma of 20.

In total, 54.3g of product was obtained in a yield of 99.82%.

Example 4

(1) Adding 22.8g of bisphenol A into 110g of dichloromethane at room temperature, starting stirring, adding 0.15g of sulfuric acid, simultaneously dropwise adding bromine and hydrogen peroxide after 0.5h, cooling the salt water, slowly heating the reaction system to 20 ℃, keeping the temperature of 20-25 ℃ for dropwise adding, wherein the bromine dropwise adding amount is 32.6g, and the hydrogen peroxide dropwise adding amount is 25.5g, so as to obtain a tetrabromobisphenol A solution.

(2) Heating the tetrabromobisphenol A solution prepared in the step (1) to carry out curing reaction, wherein the reaction temperature is 35 ℃, and the curing time is 3.5 hours.

(3) And standing the cured tetrabromobisphenol A solution for layering for 0.5h, separating out a water phase after standing, and collecting an organic phase. Adding 20g of sodium sulfite solution into the organic phase, stirring, controlling the concentration of the sodium sulfite solution to be 10%, stirring for 0.5h, controlling the temperature to be 38 ℃ after stirring, keeping the temperature for 0.5h, standing for layering after heat preservation, separating the aqueous phase after standing, and collecting the organic phase A. Adding 50g of water into the organic phase A, stirring for 0.5h, heating to 40 ℃ after stirring is finished, standing for layering for 0.5h, separating out the water phase after standing is finished, and collecting the organic phase B. And cooling the collected organic phase B to 8 ℃ for crystallization, and performing suction filtration and drying to obtain a tetrabromobisphenol A product with the purity of 99.92 percent and the chromaticity of 5.

(4) And collecting the filtrate obtained in the suction filtration step, adding 70g of water into the filtrate, distilling and crystallizing, and completely distilling off dichloromethane to obtain a tetrabromobisphenol A product with the purity of 98.75% and the chroma of 20.

The total amount of the product was 54.28g, and the yield was 99.78%.

Example 5

(1) Adding 22.8g of bisphenol A into 120g of dichloromethane at room temperature, starting stirring, adding 0.20g of sulfuric acid, simultaneously dropwise adding bromine and hydrogen peroxide after 0.5h, cooling the salt water, slowly heating the reaction system to 25 ℃, keeping the temperature of 25-30 ℃ for dropwise adding, wherein the bromine dropwise adding amount is 32.4g, and the hydrogen peroxide dropwise adding amount is 25.1g, so as to obtain a tetrabromobisphenol A solution.

(2) Heating the tetrabromobisphenol A solution prepared in the step (1) to carry out curing reaction, wherein the reaction temperature is 40 ℃, and the curing time is 3 hours.

(3) And standing the cured tetrabromobisphenol A solution for layering for 0.5h, separating out a water phase after standing, and collecting an organic phase. Adding 20g of sodium sulfite solution into the organic phase, stirring, controlling the concentration of the sodium sulfite solution to be 10%, stirring for 0.5h, controlling the temperature to be 38 ℃ after stirring, keeping the temperature for 0.5h, standing for layering after heat preservation, separating the aqueous phase after standing, and collecting the organic phase A. Adding 50g of water into the organic phase A, stirring for 0.5h, heating to 40 ℃ after stirring is finished, standing for layering for 0.5h, separating out the water phase after standing is finished, and collecting the organic phase B. And cooling the collected organic phase B to 8 ℃ for crystallization, and performing suction filtration and drying to obtain a tetrabromobisphenol A product with the purity of 99.91 percent and the chromaticity of 5.

(4) And collecting the filtrate obtained in the suction filtration step, adding 70g of water into the filtrate, distilling and crystallizing, and completely distilling off dichloromethane to obtain a tetrabromobisphenol A product with the purity of 98.7 percent and the chroma of 20.

The total amount was 54.25g, and the yield was 99.72%.

All percentages used in the present invention are mass percentages unless otherwise indicated.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.