阅读说明：本技术 一种溴化钠法制备三溴苯酚高效恒温工艺 (High-efficiency constant-temperature process for preparing tribromophenol by sodium bromide method ) 是由 吴多坤 秦善宝 单宝娜 孙盛元 孟玉花 袁淑凤 李彦卿 于 2021-08-15 设计创作，主要内容包括：本发明公开了一种溴化钠法制备三溴苯酚高效恒温工艺,包括如下步骤：a)预反应：向恒温反应釜中加入原料和溶剂,得到固液混合物A,原料包括苯酚、溴化钠、水和盐酸,溶剂为二甲基亚砜；b)滴加反应试剂：向步骤a)中的恒温反应釜中滴加过氧化氢溶液；c)反应搅拌：反应得到溶液B；d)恒温反应：将溶液B恒温水浴,得到固液混合物C；e)浓缩：将固液混合物C移入恒温蒸发浓缩器中,加入水恒温蒸发,得到固体D；f)洗涤：将固体D使用水进行洗涤,进行真空抽滤；g)烘干：将固体D置于烘箱中,烘干即可制得三溴苯酚。本发明涉及化工生产技术领域,具体为一种降低生产成本、提高原材料利用率的溴化钠法制备三溴苯酚高效恒温工艺。(The invention discloses an efficient constant-temperature process for preparing tribromophenol by a sodium bromide method, which comprises the following steps: a) pre-reaction: adding raw materials and a solvent into a constant-temperature reaction kettle to obtain a solid-liquid mixture A, wherein the raw materials comprise phenol, sodium bromide, water and hydrochloric acid, and the solvent is dimethyl sulfoxide; b) dropwise adding a reaction reagent: dropwise adding a hydrogen peroxide solution into the constant-temperature reaction kettle in the step a); c) reaction stirring: reacting to obtain a solution B; d) and (3) constant-temperature reaction: carrying out thermostatic water bath on the solution B to obtain a solid-liquid mixture C; e) concentration: transferring the solid-liquid mixture C into a constant-temperature evaporation concentrator, adding water, and evaporating at constant temperature to obtain a solid D; f) washing: washing the solid D with water, and performing vacuum filtration; g) drying: and (5) putting the solid D in an oven, and drying to obtain the tribromophenol. The invention relates to the technical field of chemical production, in particular to an efficient constant-temperature process for preparing tribromophenol by a sodium bromide method, which reduces the production cost and improves the utilization rate of raw materials.)

1. An efficient constant-temperature process for preparing tribromophenol by a sodium bromide method is characterized by comprising the following steps:

a) pre-reaction: adding raw materials and a solvent into a constant-temperature reaction kettle provided with a stirring mechanism to obtain a solid-liquid mixture A, wherein the raw materials comprise phenol, sodium bromide, water and hydrochloric acid with the concentration of 30%, and the solvent is dimethyl sulfoxide;

b) dropwise adding a reaction reagent: starting a stirrer at room temperature, and dropwise adding a 10% hydrogen peroxide solution into the constant-temperature reaction kettle in the step a);

c) reaction stirring: continuously stirring by a stirring mechanism in the constant-temperature reaction kettle, and reacting for 1-2 hours to obtain a solution B;

d) and (3) constant-temperature reaction: transferring the solution B into a constant-temperature water bath kettle, heating to 40-50 ℃, and carrying out constant-temperature water bath for 12-15 hours to obtain a solid-liquid mixture C;

e) concentration: transferring the solid-liquid mixture C into a constant-temperature evaporation concentrator, adding 2-3 times of water, adjusting the temperature, performing constant-temperature evaporation until no flowing liquid drops exist in the solid-liquid mixture C, and cooling to room temperature to obtain a solid D;

f) washing: washing the solid D for multiple times by using water, and carrying out vacuum filtration on the washed solid D;

g) drying: and spreading the washed solid D on a drying tray, putting the tray in an oven, and drying for 8-12 hours to obtain the tribromophenol.

2. The efficient constant-temperature process for preparing tribromophenol by the sodium bromide method according to claim 1, wherein the phenol and the sodium bromide in step a) are solid powders, and the weight parts of the raw materials are respectively as follows: 1-3 parts of phenol, 2-10 parts of sodium bromide, 10-20 parts of water and 7-25 parts of 30% hydrochloric acid; the adding weight portion of the 10% hydrogen peroxide solution is 10-30 portions.

3. The efficient constant-temperature process for preparing tribromophenol by the sodium bromide method according to claim 1, wherein the addition weight part of dimethyl sulfoxide in step a) is 10-20 parts.

4. The efficient constant-temperature process for preparing tribromophenol by the sodium bromide method according to claim 1, wherein the dropping speed of the 10% hydrogen peroxide solution in step b) is 0.5-1 part/min.

5. The efficient constant-temperature process for preparing tribromophenol by the sodium bromide method according to claim 1, wherein the constant-temperature evaporation temperature in step e) is 80-85 ℃.

6. The efficient constant-temperature process for preparing tribromophenol by the sodium bromide method according to claim 1, wherein the step f) is carried out until the pH of the washing water is 6-6.5.

7. The efficient constant-temperature process for preparing tribromophenol by the sodium bromide method according to claim 1, wherein the oven in step g) is kept at a constant temperature of 80 ℃.

Technical Field

The invention relates to the technical field of chemical production, in particular to an efficient constant-temperature process for preparing tribromophenol by a sodium bromide method.

Background

The fire hazard can bring huge losses of material economy and the like to people, the flame retardant material can effectively inhibit the fire from spreading, the flame retardant material has great demand on the flame retardant material in the international market, the demand on the flame retardant material in industrial production is increased year by year, tribromophenol is an important basic material for synthesizing the flame retardant, and the reactive flame retardant synthesized by using the tribromophenol can be suitable for various materials such as epoxy resin, polyurethane and the like, and has good economy and development prospect.

The traditional tribromophenol synthesis process takes phenol and hydrobromic acid as basic materials, but hydrobromic acid has great harm, and the preparation process has strict requirements on equipment and flow, and the synthesis cost is high.

Disclosure of Invention

Aiming at the situation, in order to make up for the existing defects, the invention provides the high-efficiency constant-temperature process for preparing tribromophenol by the sodium bromide method, which reduces the production cost and improves the utilization rate of raw materials.

The invention provides the following technical scheme: the invention relates to an efficient constant-temperature process for preparing tribromophenol by a sodium bromide method, which specifically comprises the following steps:

a) pre-reaction: adding raw materials and a solvent into a constant-temperature reaction kettle provided with a stirring mechanism to obtain a solid-liquid mixture A, wherein the raw materials comprise phenol, sodium bromide, water and hydrochloric acid with the concentration of 30%, and the solvent is dimethyl sulfoxide;

b) dropwise adding a reaction reagent: starting a stirrer at room temperature, and dropwise adding a 10% hydrogen peroxide solution into the constant-temperature reaction kettle in the step a);

c) reaction stirring: continuously stirring by a stirring mechanism in the constant-temperature reaction kettle, and reacting for 1-2 hours to obtain a solution B;

d) and (3) constant-temperature reaction: transferring the solution B into a constant-temperature water bath kettle, heating to 40-50 ℃, and carrying out constant-temperature water bath for 12-15 hours to obtain a solid-liquid mixture C;

e) concentration: transferring the solid-liquid mixture C into a constant-temperature evaporation concentrator, adding 2-3 times of water, adjusting the temperature, performing constant-temperature evaporation until no flowing liquid drops exist in the solid-liquid mixture C, and cooling to room temperature to obtain a solid D;

f) washing: washing the solid D for multiple times by using water, and carrying out vacuum filtration on the washed solid D;

g) drying: and spreading the washed solid D on a drying tray, putting the tray in an oven, and drying for 8-12 hours to obtain the tribromophenol.

Further, the phenol and the sodium bromide in the step a) are solid powder, and the weight parts of the raw materials are respectively as follows: 1-3 parts of phenol, 2-10 parts of sodium bromide, 10-20 parts of water and 7-25 parts of 30% hydrochloric acid; the adding weight portion of the 10% hydrogen peroxide solution is 10-30 portions.

Further, the adding weight part of the dimethyl sulfoxide in the step a) is 10-20 parts.

Further, the dropping speed of the 10% hydrogen peroxide solution in the step b) is 0.5 to 1 part/min.

Further, the constant temperature evaporation temperature in the step e) is 80-85 ℃.

Further, said step f) is washed until the pH of the wash water is 6-6.5.

Further, the temperature in the oven is kept constant at 80 ℃ in the step g).

The invention with the structure has the following beneficial effects: according to the efficient constant-temperature process for preparing tribromophenol by the sodium bromide method, the traditional hydrobromic acid with high risk and high price is abandoned in selection of raw materials, and sodium bromide is adopted to replace the hydrobromic acid for process synthesis, so that the requirements on reaction equipment and storage equipment can be effectively reduced, the synthesis steps are more efficient, the utilization rate of the raw materials in the obtained final product is high, and fewer byproducts are generated.

Detailed Description

The invention is further illustrated by the following examples.

Example 1

An efficient constant-temperature process for preparing tribromophenol by a sodium bromide method specifically comprises the following steps:

a) pre-reaction: adding raw materials and a solvent into a constant-temperature reaction kettle provided with a stirring mechanism to obtain a solid-liquid mixture A, wherein the raw materials comprise 1-3 parts of phenol, 2-10 parts of sodium bromide, 10-20 parts of water and 7-25 parts of hydrochloric acid with the concentration of 30%, the solvent is dimethyl sulfoxide, and the adding weight parts of the dimethyl sulfoxide are 10-20 parts (the parts are the same as the parts in weight);

b) dropwise adding a reaction reagent: starting a stirrer at room temperature, and dropwise adding 10% hydrogen peroxide solution into the constant-temperature reaction kettle in the step a), wherein the hydrogen peroxide is added in 10-30 parts by weight and the dropwise adding speed is 0.5-1 part/min;

c) reaction stirring: continuously stirring by a stirring mechanism in the constant-temperature reaction kettle, and reacting for 1-2 hours to obtain a solution B;

d) and (3) constant-temperature reaction: transferring the solution B into a constant-temperature water bath kettle, heating to 40-50 ℃, and carrying out constant-temperature water bath for 12-15 hours to obtain a solid-liquid mixture C;

e) concentration: transferring the solid-liquid mixture C into a constant-temperature evaporation concentrator, adding 2-3 times of water, adjusting the temperature to 80-85 ℃, performing constant-temperature evaporation until no flowing liquid drops exist in the solid-liquid mixture C, and cooling to room temperature to obtain a solid D;

f) washing: washing the solid D for multiple times by using water until the pH value of the washing water is 6-6.5, and carrying out vacuum filtration on the washed solid D;

g) drying: and spreading the washed solid D on a drying tray, placing the tray in an oven, keeping the temperature of the oven at 80 ℃, and drying for 8-12 hours to obtain tribromophenol.

Example 2

An efficient constant-temperature process for preparing tribromophenol by a sodium bromide method specifically comprises the following steps:

a) pre-reaction: adding raw materials and a solvent into a constant-temperature reaction kettle provided with a stirring mechanism to obtain a solid-liquid mixture A, wherein the raw materials comprise 1-2 parts of phenol, 4-6 parts of sodium bromide, 12-18 parts of water and 10-15 parts of hydrochloric acid with the concentration of 30%, the solvent is dimethyl sulfoxide, and the adding weight part of the dimethyl sulfoxide is 10-15 parts;

b) dropwise adding a reaction reagent: starting a stirrer at room temperature, and dropwise adding a 10% hydrogen peroxide solution into the constant-temperature reaction kettle in the step a), wherein the hydrogen peroxide is added in 12-20 parts by weight and the dropwise adding speed is 0.5-0.8 part/min;

c) reaction stirring: continuously stirring by a stirring mechanism in the constant-temperature reaction kettle, and reacting for 1-2 hours to obtain a solution B;

d) and (3) constant-temperature reaction: transferring the solution B into a constant-temperature water bath kettle, heating to 40-50 ℃, and carrying out constant-temperature water bath for 12-14 hours to obtain a solid-liquid mixture C;

e) concentration: transferring the solid-liquid mixture C into a constant-temperature evaporation concentrator, adding 2-3 times of water, adjusting the temperature to 80-85 ℃, performing constant-temperature evaporation until no flowing liquid drops exist in the solid-liquid mixture C, and cooling to room temperature to obtain a solid D;

f) washing: washing the solid D for multiple times by using water until the pH value of the washing water is 6.2-6.5, and carrying out vacuum filtration on the washed solid D;

g) drying: and spreading the washed solid D on a drying tray, placing the tray in an oven, keeping the temperature of the oven at 80 ℃, and drying for 8-10 hours to obtain the tribromophenol.

Example 3

An efficient constant-temperature process for preparing tribromophenol by a sodium bromide method specifically comprises the following steps:

a) pre-reaction: adding raw materials and a solvent into a constant-temperature reaction kettle provided with a stirring mechanism to obtain a solid-liquid mixture A, wherein the raw materials comprise 1 part of phenol, 5 parts of sodium bromide, 15 parts of water and 12 parts of hydrochloric acid with the concentration of 30%, the solvent is dimethyl sulfoxide, and the adding weight part of the dimethyl sulfoxide is 15 parts;

b) dropwise adding a reaction reagent: starting a stirrer at room temperature, and dropwise adding 10% hydrogen peroxide solution into the constant-temperature reaction kettle in the step a), wherein the hydrogen peroxide is added in 15 parts by weight and the dropwise adding speed is 0.5 part/min;

c) reaction stirring: continuously stirring by a stirring mechanism in the constant-temperature reaction kettle, and reacting for 1 hour to obtain a solution B;

d) and (3) constant-temperature reaction: transferring the solution B into a constant-temperature water bath kettle, heating to 45 ℃, and carrying out constant-temperature water bath for 12 hours to obtain a solid-liquid mixture C;

e) concentration: transferring the solid-liquid mixture C into a constant-temperature evaporation concentrator, adding 2 times of water, adjusting the temperature to 80 ℃, performing constant-temperature evaporation until no flowing liquid drops exist in the solid-liquid mixture C, and cooling to room temperature to obtain a solid D;

f) washing: washing the solid D for multiple times by using water until the pH value of the washing water is 6.5, and carrying out vacuum filtration on the washed solid D;

g) drying: and spreading the washed solid D on a drying tray, placing the tray in an oven, keeping the temperature of the oven at 80 ℃, and drying for 8 hours to obtain the tribromophenol.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.