阅读说明：本技术 一种低成本且环保的双酚s的制备工艺 (Low-cost and environment-friendly bisphenol S preparation process ) 是由 姚振峰 李松 孙海琴 于 2021-07-23 设计创作，主要内容包括：本发明公开了一种低成本且环保的双酚S的制备工艺,直接用苯酚代替均三甲苯,苯酚既是反应物又作为溶剂使用,在磺化反应过程中,分次加入苯酚,通过蒸馏将反应产生的水带出,达到反应完全的目的,并在制备过程中制备了一种耐腐蚀涂料,当耐腐蚀涂料喷涂在反应釜内部时强化填料的上N原子和O原子能够与金属离子相互作用形成螯合物,吸附在金属基体表面,使得漆膜的附着效果更好,同时防止硫酸侵蚀,纳米二氧化硅和石墨烯的存在进一步加强的涂料的耐腐蚀性,使得反应釜的耐酸性能更高,进一步减少了制备成本。(The invention discloses a low-cost and environment-friendly preparation process of bisphenol S, which directly uses phenol to replace mesitylene, wherein the phenol is used as a reactant and a solvent, the phenol is added in several times in the sulfonation reaction process, water generated by the reaction is taken out through distillation, the purpose of complete reaction is achieved, and an anti-corrosion coating is prepared in the preparation process.)

1. A preparation process of low-cost and environment-friendly bisphenol S is characterized by comprising the following steps: the method comprises the following steps:

step S1: adding phenol into a reaction kettle, stirring and adding concentrated sulfuric acid under the conditions that the rotating speed is 200-plus-300 r/min and the temperature is 110-plus-120 ℃, and reacting for 1-1.5h under the condition that the temperature is 120-plus-130 ℃;

step S2: adding phenol again, and reacting at the temperature of 150-160 ℃;

step S3: after the reaction is finished, distilling at the temperature of 110-120 ℃ to remove water generated by the reaction, and distilling at the temperature of 185 ℃ to recover phenol to obtain the bisphenol S.

2. The process according to claim 1, wherein the bisphenol S is prepared by the following steps: the molar ratio of the phenol to the concentrated sulfuric acid used in the step S1 is 1:1.1, the mass fraction of the concentrated sulfuric acid is 95%, and the phenol used in the step S2 is the same as that used in the step S1.

3. The process according to claim 1, wherein the bisphenol S is prepared by the following steps: the side wall of the inner wall of the reaction kettle is sprayed with a corrosion-resistant coating, and the corrosion-resistant coating comprises the following raw materials in parts by weight: 70-80 parts of acrylic resin, 1.5-3 parts of polyacrylic acid, 10-15 parts of reinforcing filler, 1-1.5 parts of defoaming agent, 2-5 parts of film-forming assistant and 1-1.5 parts of flatting agent;

the corrosion-resistant coating is prepared by mixing the raw materials.

4. The process according to claim 3, wherein the bisphenol S is prepared by the following steps: the defoaming agent is one or a mixture of more of fatty acid methyl ester, silicone oil and polydimethylsiloxane in any proportion, the film-forming aid is one or a mixture of more of propylene glycol butyl ether, propylene glycol methyl ether acetate and propylene glycol ethyl ether in any proportion, and the leveling agent is one or a mixture of two of polydimethylsiloxane and silicone oil in any proportion.

5. The process according to claim 3, wherein the bisphenol S is prepared by the following steps: the reinforcing filler is prepared by the following steps:

step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring, adding potassium permanganate, reacting, heating, stirring, adding deionized water, reacting, adding hydrogen peroxide until no bubbles are generated, washing the reaction solution until no SO is generated in the reaction solution₄ ^2-Performing ion filtration, drying a filter cake to obtain graphene oxide, dispersing the graphene oxide in deionized water, adding tetraethoxysilane and ethanol, reacting, filtering and drying to obtain modified graphene;

step A2: adding 3, 5-dinitrotoluene, tin powder and hydrochloric acid into a reaction kettle, reacting to obtain an intermediate 1, adding quinoline acrylate, triethylamine and anhydrous chloroform into the reaction kettle, dropwise adding acryloyl chloride under the condition of ice water bath, protecting with nitrogen, reacting to obtain an intermediate 2, adding the intermediate 1, the intermediate 2 and trifluoroethanol into the reaction kettle, and reacting to obtain an intermediate 3;

step A3: adding the intermediate 3, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle for reaction to obtain an intermediate 4, adding the intermediate 4, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle for reflux reaction to obtain an intermediate 5, adding the intermediate 5, toluene-3, 5-diisocyanate and dichloromethane into the reaction kettle, introducing nitrogen for protection, stirring, adding triethylamine, and reacting to obtain an intermediate 6;

step A4: adding modified graphene, 2-dimethylolbutyric acid, ethylenediamine and deionized water into a reaction kettle, stirring and adding 1-hydroxybenzotriazole for reaction to prepare a modified carrier, adding an intermediate 6, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle for reaction to prepare an intermediate 7, adding the intermediate 7, the modified carrier, sodium powder and toluene into the reaction kettle, introducing nitrogen for protection, reacting to prepare an intermediate 8, adding the intermediate 8, bisphenol A epoxy resin E-44 and acetone into the reaction kettle, heating, adding triethylamine, reacting, filtering and drying to prepare the reinforced filler.

6. The process according to claim 5, wherein the bisphenol S is prepared by the following steps: the using amount ratio of the graphite, the sodium nitrate, the concentrated sulfuric acid, the potassium permanganate, the deionized water and the hydrogen peroxide in the step A1 is 4g:2g:98mL:25g:100mL:15mL, the mass fraction of the concentrated sulfuric acid is 95%, and the using amount ratio of the graphene oxide, the deionized water, the tetraethoxysilane and the ethanol is 5g:20mL:2mL:10 mL.

7. The process according to claim 5, wherein the bisphenol S is prepared by the following steps: the dosage ratio of the 3, 5-dinitrotoluene, the tin powder and the hydrochloric acid in the step A2 is 3g:2.8g:20mL, the mass fraction of the concentrated hydrochloric acid is 37%, the dosage ratio of the quinoline acrylate, the triethylamine, the anhydrous chloroform and the acryloyl chloride is 35mmol:42mmol:30mL:38mmol, and the dosage ratio of the intermediate 1, the intermediate 2 and the trifluoroethanol is 1mmol:2mmol:10 mL.

8. The process according to claim 5, wherein the bisphenol S is prepared by the following steps: the dosage ratio of the intermediate 3, the nitrogen-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride in the step A3 is 0.1mol:0.1mol:0.25g:200mL, the dosage ratio of the intermediate 4, the potassium carbonate, the deionized water and the tetraethylammonium bromide is 3.5g:9g:80mL:5mL, and the dosage molar ratio of the intermediate 5, the toluene-3, 5-diisocyanate and the triethylamine is 1:1.1: 1.

9. The process according to claim 5, wherein the bisphenol S is prepared by the following steps: the dosage mass ratio of the modified graphene, the 2, 2-dimethylolbutyric acid and the ethylenediamine in the step A4 is 5g:0.01mol:0.01mol, the dosage mass ratio of the intermediate 6, the nitrogen-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride is 0.1mol:0.12mol:0.25g:200mL, the dosage mass ratio of the intermediate 7, the modified carrier, the sodium powder and the toluene is 0.01mol:3g:0.01mol:30mL, and the dosage mass ratio of the intermediate 8, the bisphenol A epoxy resin E-44, the acetone and the triethylamine is 5g:1.2g:50mL:2.8 g.

Technical Field

The invention relates to the technical field of chemical synthesis, in particular to a low-cost and environment-friendly preparation process of bisphenol S.

Background

Bisphenol S, whose chemical name is 4, 4' -dihydroxy diphenyl sulfone, sometimes abbreviated as BPS, is an important synthetic raw material for pesticides, dyes, auxiliaries and high molecular compounds. In bisphenol S production process, need add phenol and concentrated sulfuric acid to reation kettle in carry out sulfonation reaction, the stirring reaction liquid that will not stop during the reaction so that its reaction is abundant, because the area of stirring vane and reaction liquid contact is not enough, the stirring is not enough even, often leads to the reaction thoroughly inadequately, if can not in time strike off in addition the raw materials that glue on cauldron body side wall, easily produces high temperature carbon deposition phenomenon to influence reaction efficiency, reduce material utilization ratio.

In the prior art, phenol and sulfuric acid are refluxed in mesitylene, water generated in the sulfonation reaction process is continuously separated, and the product bisphenol S is obtained by cooling and centrifuging after the reaction is finished.

The existing production process uses a mesitylene solvent with higher price, needs distillation, recovery and reuse, has low utilization rate of raw materials, and has certain waste in energy consumption and waste water and waste gas discharge. In addition, acidic substances are required to be used in the preparation process, so that the reaction kettle is seriously corroded, and further the production cost is increased.

Disclosure of Invention

The invention aims to provide a low-cost and environment-friendly bisphenol S preparation process.

The purpose of the invention can be realized by the following technical scheme:

a low-cost and environment-friendly bisphenol S preparation process comprises the following steps:

step S1: adding phenol into a reaction kettle, stirring and adding concentrated sulfuric acid under the conditions that the rotating speed is 200-plus-300 r/min and the temperature is 110-plus-120 ℃, and reacting for 1-1.5h under the condition that the temperature is 120-plus-130 ℃;

step S2: adding phenol again, and reacting at the temperature of 150-160 ℃;

step S3: after the reaction is finished, distilling at the temperature of 110-120 ℃ to remove water generated by the reaction, and distilling at the temperature of 185 ℃ to recover phenol to obtain the bisphenol S.

Further, the molar ratio of the phenol to the concentrated sulfuric acid used in the step S1 is 1:1.1, the mass fraction of the concentrated sulfuric acid is 95%, and the phenol used in the step S2 is the same as that used in the step S1.

Further, the side wall of the inner wall of the reaction kettle is sprayed with a corrosion-resistant coating, and the corrosion-resistant coating comprises the following raw materials in parts by weight: 70-80 parts of acrylic resin, 1.5-3 parts of polyacrylic acid, 10-15 parts of reinforcing filler, 1-1.5 parts of defoaming agent, 2-5 parts of film-forming assistant and 1-1.5 parts of flatting agent;

the corrosion-resistant coating is prepared by mixing the raw materials.

Further, the defoaming agent is one or more of fatty acid methyl ester, silicone oil and polydimethylsiloxane which are mixed in any proportion, the film-forming aid is one or more of propylene glycol butyl ether, propylene glycol methyl ether acetate and propylene glycol ethyl ether which are mixed in any proportion, and the leveling agent is one or two of polydimethylsiloxane and silicone oil which are mixed in any proportion.

Further, the reinforcing filler is prepared by the following steps:

step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotating speed is 150-plus-200 r/min and the temperature is 0-5 ℃, reacting for 2-3h, heating to the temperature of 30-40 ℃, stirring for 3-5h, adding deionized water, reacting for 30-40min under the temperature of 90-95 ℃, adding hydrogen peroxide until no bubbles are generated, washing the reaction solution until the reaction solution is free of SO₄ ^2-Performing ion filtration and drying the filter cake to obtain graphene oxide, dispersing the graphene oxide in deionized water, adding tetraethoxysilane and ethanol, reacting for 3-4h at the rotation speed of 150-;

step A2: adding 3, 5-dinitrotoluene, tin powder and hydrochloric acid into a reaction kettle, stirring for 1-1.5h under the condition that the rotation speed is 150-200r/min, adjusting the pH value of a reaction solution to 10-11 to prepare an intermediate 1, adding acrylic quinoline ester, triethylamine and anhydrous chloroform into the reaction kettle, dropwise adding acryloyl chloride under the condition of ice-water bath, protecting with nitrogen, reacting for 10-15h to prepare an intermediate 2, adding the intermediate 1, the intermediate 2 and trifluoroethanol into the reaction kettle, and reacting for 40-50h under the conditions that the rotation speed is 120-150r/min and the temperature is 50-55 ℃ to prepare an intermediate 3;

the reaction process is as follows:

step A3: adding the intermediate 3, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 8-10h at the temperature of 80-90 ℃ to obtain an intermediate 4, adding the intermediate 4, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, performing reflux reaction for 2-3h to obtain an intermediate 5, adding the intermediate 5, toluene-3, 5-diisocyanate and dichloromethane into the reaction kettle, introducing nitrogen for protection, stirring at the rotation speed of 120-150r/min at the temperature of 80-85 ℃, adding triethylamine, and reacting to obtain an intermediate 6;

the reaction process is as follows:

step A4: adding modified graphene, 2-dimethylolbutyric acid, ethylenediamine and deionized water into a reaction kettle, stirring and adding 1-hydroxybenzotriazole under the condition of the rotation speed of 150-200r/min to react to obtain a modified carrier, adding an intermediate 6, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 8-10h at the temperature of 80-90 ℃ to obtain an intermediate 7, adding the intermediate 7, the modified carrier, sodium powder and toluene into the reaction kettle, introducing nitrogen for protection, reacting for 8-10h at the temperature of 3-5 ℃ to obtain an intermediate 8, adding the intermediate 8, bisphenol A epoxy resin E-44 and acetone into the reaction kettle, reacting at the rotation speed of 200-300r/min, adding triethylamine at the temperature of 80-85 ℃, reacting for 3-5h, filtering and drying to obtain the reinforced filler.

The reaction process is as follows:

further, the using amount ratio of the graphite, the sodium nitrate, the concentrated sulfuric acid, the potassium permanganate, the deionized water and the hydrogen peroxide in the step A1 is 4g:2g:98mL:25g:100mL:15mL, the mass fraction of the concentrated sulfuric acid is 95%, and the using amount ratio of the graphene oxide, the deionized water, the ethyl orthosilicate and the ethanol is 5g:20mL:2mL:10 mL.

Further, the dosage ratio of the 3, 5-dinitrotoluene, the tin powder and the hydrochloric acid in the step A2 is 3g:2.8g:20mL, the mass fraction of the concentrated hydrochloric acid is 37%, the dosage ratio of the acrylic acid quinoline ester, the triethylamine, the anhydrous chloroform and the acryloyl chloride is 35mmol:42mmol:30mL:38mmol, and the dosage ratio of the intermediate 1, the intermediate 2 and the trifluoroethanol is 1mmol:2mmol:10 mL.

Further, the amount ratio of the intermediate 3, the N-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride in the step A3 is 0.1mol:0.1mol:0.25g:200mL, the amount ratio of the intermediate 4, the potassium carbonate, the deionized water and the tetraethylammonium bromide is 3.5g:9g:80mL:5mL, and the amount ratio of the intermediate 5, the toluene-3, 5-diisocyanate and the triethylamine is 1:1.1: 1.

Further, the amount of the modified graphene, the 2, 2-dimethylolbutyric acid and the ethylenediamine in the step A4 is 5g:0.01mol:0.01mol, the amount of the intermediate 6, the nitrogen-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride is 0.1mol:0.12mol:0.25g:200mL, the amount of the intermediate 7, the modified carrier, the sodium powder and the toluene is 0.01mol:3g:0.01mol:30mL, and the amount of the intermediate 8, the bisphenol A epoxy resin E-44, the acetone and the triethylamine is 5g:1.2g:50mL:2.8 g.

The invention has the beneficial effects that: in the process of preparing bisphenol S, the invention directly uses phenol to replace mesitylene, the phenol is used as a reactant and a solvent, in the sulfonation reaction process, the phenol is added in several times, water generated by the reaction is taken out through distillation to achieve the purpose of complete reaction, the phenol distilled in several times is directly recycled and reused, the wastewater is biochemically treated to reach the standard and discharged, the treatment of waste gas and waste liquid caused by centrifugal separation is reduced, the variety of the used benzene is reduced, the pressure of wastewater treatment is reduced, the reaction yield is improved, in addition, a reaction kettle coated with corrosion-resistant coating is used in the preparation process, the corrosion-resistant coating contains reinforced filler, the reinforced filler is treated by taking graphite as a raw material to prepare graphene oxide, the graphene oxide is hydrolyzed by ethyl orthosilicate, nano silicon dioxide is embedded in a groove of the graphene oxide, and then the 3, 5-dinitrotoluene is reduced, preparing an intermediate 1, reacting acrylic acid quinoline ester with acryloyl chloride to prepare an intermediate 2, reacting the intermediate 1 with the intermediate 2 to prepare an intermediate 3, reacting the intermediate 3 with nitrogen-bromosuccinimide to prepare an intermediate 4, further processing the intermediate 4 to prepare an intermediate 5, reacting the intermediate 5 with toluene-3, 5-diisocyanate to prepare an intermediate 9, reacting modified graphene with 2, 2-dimethylolbutyric acid to prepare a modified carrier, treating the intermediate 6 with nitrogen-bromosuccinimide to prepare an intermediate 7, reacting the intermediate 7 with the modified carrier to prepare an intermediate 8, reacting an isocyanate group on the intermediate 8 with a hydroxyl group on bisphenol A epoxy resin E-44 to prepare the reinforced filler, when the corrosion-resistant coating is sprayed inside the reaction kettle, the upper N atom and the O atom of the reinforcing filler can interact with metal ions to form a chelate, and the chelate is adsorbed on the surface of a metal matrix, so that the adhesion effect of a paint film is better, the corrosion resistance of the coating is further enhanced by the existence of nano silicon dioxide and graphene, the acid resistance of the reaction kettle is higher, and the preparation cost is further reduced.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A low-cost and environment-friendly bisphenol S preparation process comprises the following steps:

step S1: adding phenol into a reaction kettle, stirring and adding concentrated sulfuric acid under the conditions that the rotating speed is 200r/min and the temperature is 110 ℃, and reacting for 1h under the condition that the temperature is 120 ℃;

step S2: adding phenol again, and reacting at 150 ℃;

step S3: after the reaction, water produced by the reaction was distilled off at a temperature of 110 ℃ and phenol was recovered by distillation at 185 ℃ to obtain bisphenol S.

The side wall of the inner wall of the reaction kettle is sprayed with a corrosion-resistant coating, and the corrosion-resistant coating comprises the following raw materials in parts by weight: 70 parts of acrylic resin, 1.5 parts of polyacrylic acid, 10 parts of reinforcing filler, 1 part of fatty acid methyl ester, 2 parts of propylene glycol butyl ether and 1 part of silicone oil;

the corrosion-resistant coating is prepared by mixing the raw materials.

The reinforcing filler is prepared by the following steps:

step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotating speed is 150r/min and the temperature is 0 ℃, reacting for 2 hours, heating to 30 ℃, stirring for 3 hours, adding deionized water, reacting for 30 minutes under the condition that the temperature is 90 ℃, adding hydrogen peroxide until no bubbles are generated, washing the reaction solution until no bubbles are generated, andthe reaction solution is free of SO₄ ^2-Performing ion filtration and drying a filter cake to obtain graphene oxide, dispersing the graphene oxide in deionized water, adding tetraethoxysilane and ethanol, reacting for 3 hours at the rotation speed of 150r/min and the temperature of 60 ℃, and filtering and drying to obtain modified graphene;

step A2: adding 3, 5-dinitrotoluene, tin powder and hydrochloric acid into a reaction kettle, stirring for 1h at the rotation speed of 150r/min, adjusting the pH value of a reaction solution to 10 to prepare an intermediate 1, adding quinoline acrylate, triethylamine and anhydrous chloroform into the reaction kettle, dropwise adding acryloyl chloride under the ice water bath condition, protecting with nitrogen, reacting for 10h to prepare an intermediate 2, adding the intermediate 1, the intermediate 2 and trifluoroethanol into the reaction kettle, and reacting for 40h at the rotation speed of 120r/min and the temperature of 50 ℃ to prepare an intermediate 3;

step A3: adding the intermediate 3, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 8 hours at the temperature of 80 ℃ to obtain an intermediate 4, adding the intermediate 4, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, performing reflux reaction for 2 hours to obtain an intermediate 5, adding the intermediate 5, toluene-3, 5-diisocyanate and dichloromethane into the reaction kettle, introducing nitrogen for protection, stirring and adding triethylamine under the conditions that the rotating speed is 120r/min and the temperature is 80 ℃, and reacting to obtain an intermediate 6;

step A4: adding modified graphene, 2-dimethylolbutyric acid, ethylenediamine and deionized water into a reaction kettle, stirring and adding 1-hydroxybenzotriazole under the condition that the rotating speed is 150r/min, reacting to obtain a modified carrier, adding an intermediate 6, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 8 hours under the condition that the temperature is 80 ℃ to obtain an intermediate 7, adding the intermediate 7, the modified carrier, sodium powder and toluene into the reaction kettle, introducing nitrogen for protection, reacting for 8 hours under the condition that the temperature is 3 ℃ to obtain an intermediate 8, adding the intermediate 8, bisphenol A epoxy resin E-44 and acetone into the reaction kettle, adding triethylamine under the conditions that the rotating speed is 200r/min and the temperature is 80 ℃ to react for 3 hours, filtering and drying to obtain the reinforced filler.

Example 2

A low-cost and environment-friendly bisphenol S preparation process comprises the following steps:

step S1: adding phenol into a reaction kettle, stirring and adding concentrated sulfuric acid under the conditions that the rotating speed is 200r/min and the temperature is 120 ℃, and reacting for 1.5 hours under the condition that the temperature is 120 ℃;

step S2: adding phenol again, and reacting at 150 ℃;

step S3: after the reaction, water produced by the reaction was distilled off at a temperature of 120 ℃ and phenol was recovered by distillation at 185 ℃ to obtain bisphenol S.

The side wall of the inner wall of the reaction kettle is sprayed with a corrosion-resistant coating, and the corrosion-resistant coating comprises the following raw materials in parts by weight: 75 parts of acrylic resin, 2 parts of polyacrylic acid, 13 parts of reinforcing filler, 1.2 parts of fatty acid methyl ester, 4 parts of propylene glycol butyl ether and 1.2 parts of silicone oil;

the corrosion-resistant coating is prepared by mixing the raw materials.

The reinforcing filler is prepared by the following steps:

step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotating speed is 150r/min and the temperature is 5 ℃, reacting for 2 hours, heating to 40 ℃, stirring for 3 hours, adding deionized water, reacting for 30 minutes under the condition that the temperature is 95 ℃, adding hydrogen peroxide until no bubbles are generated, washing the reaction solution until the reaction solution is free of SO₄ ^2-Performing ion filtration and drying a filter cake to obtain graphene oxide, dispersing the graphene oxide in deionized water, adding tetraethoxysilane and ethanol, reacting for 4 hours at the rotation speed of 200r/min and the temperature of 60 ℃, and filtering and drying to obtain modified graphene;

step A2: adding 3, 5-dinitrotoluene, tin powder and hydrochloric acid into a reaction kettle, stirring for 1.5h under the condition that the rotation speed is 150r/min, adjusting the pH value of a reaction solution to 10 to prepare an intermediate 1, adding quinoline acrylate, triethylamine and anhydrous chloroform into the reaction kettle, dropwise adding acryloyl chloride under the condition of ice water bath, protecting with nitrogen, reacting for 15h to prepare an intermediate 2, adding the intermediate 1, the intermediate 2 and trifluoroethanol into the reaction kettle, and reacting for 40h under the conditions that the rotation speed is 120r/min and the temperature is 55 ℃ to prepare an intermediate 3;

step A3: adding the intermediate 3, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 8 hours at the temperature of 90 ℃ to obtain an intermediate 4, adding the intermediate 4, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, performing reflux reaction for 3 hours to obtain an intermediate 5, adding the intermediate 5, toluene-3, 5-diisocyanate and dichloromethane into the reaction kettle, introducing nitrogen for protection, stirring and adding triethylamine at the rotation speed of 120r/min and the temperature of 85 ℃ to react to obtain an intermediate 6;

step A4: adding modified graphene, 2-dimethylolbutyric acid, ethylenediamine and deionized water into a reaction kettle, stirring and adding 1-hydroxybenzotriazole under the condition that the rotating speed is 150r/min, reacting to obtain a modified carrier, adding an intermediate 6, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 8 hours under the condition that the temperature is 90 ℃ to obtain an intermediate 7, adding the intermediate 7, the modified carrier, sodium powder and toluene into the reaction kettle, introducing nitrogen for protection, reacting for 8 hours under the condition that the temperature is 5 ℃ to obtain an intermediate 8, adding the intermediate 8, bisphenol A epoxy resin E-44 and acetone into the reaction kettle, adding triethylamine under the conditions that the rotating speed is 300r/min and the temperature is 80 ℃ to react for 5 hours, filtering and drying to obtain the reinforced filler.

Example 3

A low-cost and environment-friendly bisphenol S preparation process comprises the following steps:

step S1: adding phenol into a reaction kettle, stirring and adding concentrated sulfuric acid under the conditions that the rotating speed is 300r/min and the temperature is 120 ℃, and reacting for 1.5 hours under the condition that the temperature is 130 ℃;

step S2: adding phenol again, and reacting at 160 ℃;

step S3: after the reaction, water produced by the reaction was distilled off at a temperature of 120 ℃ and phenol was recovered by distillation at 185 ℃ to obtain bisphenol S.

The side wall of the inner wall of the reaction kettle is sprayed with a corrosion-resistant coating, and the corrosion-resistant coating comprises the following raw materials in parts by weight: 80 parts of acrylic resin, 3 parts of polyacrylic acid, 15 parts of reinforcing filler, 1.5 parts of fatty acid methyl ester, 5 parts of propylene glycol butyl ether and 1.5 parts of silicone oil;

the corrosion-resistant coating is prepared by mixing the raw materials.

The reinforcing filler is prepared by the following steps:

step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring and adding potassium permanganate under the conditions that the rotating speed is 200r/min and the temperature is 5 ℃, reacting for 3 hours, heating to 40 ℃, stirring for 5 hours, adding deionized water, reacting for 40 minutes under the condition that the temperature is 95 ℃, adding hydrogen peroxide until no bubbles are generated, washing the reaction solution until the reaction solution is free of SO₄ ^2-Performing ion filtration and drying a filter cake to obtain graphene oxide, dispersing the graphene oxide in deionized water, adding tetraethoxysilane and ethanol, reacting for 4 hours at the rotation speed of 200r/min and the temperature of 70 ℃, and filtering and drying to obtain modified graphene;

step A2: adding 3, 5-dinitrotoluene, tin powder and hydrochloric acid into a reaction kettle, stirring for 1.5h under the condition of the rotation speed of 200r/min, adjusting the pH value of a reaction solution to be 11 to prepare an intermediate 1, adding acrylic quinoline ester, triethylamine and anhydrous chloroform into the reaction kettle, dropwise adding acryloyl chloride under the condition of ice water bath, protecting with nitrogen, reacting for 15h to prepare an intermediate 2, adding the intermediate 1, the intermediate 2 and trifluoroethanol into the reaction kettle, and reacting for 50h under the conditions of the rotation speed of 150r/min and the temperature of 55 ℃ to prepare an intermediate 3;

step A3: adding the intermediate 3, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 10 hours at the temperature of 90 ℃ to obtain an intermediate 4, adding the intermediate 4, potassium carbonate, deionized water and tetraethylammonium bromide into the reaction kettle, performing reflux reaction for 3 hours to obtain an intermediate 5, adding the intermediate 5, toluene-3, 5-diisocyanate and dichloromethane into the reaction kettle, introducing nitrogen for protection, stirring and adding triethylamine at the rotation speed of 150r/min and the temperature of 85 ℃ to react to obtain an intermediate 6;

step A4: adding modified graphene, 2-dimethylolbutyric acid, ethylenediamine and deionized water into a reaction kettle, stirring and adding 1-hydroxybenzotriazole under the condition of the rotating speed of 200r/min to react to prepare a modified carrier, adding an intermediate 6, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 10 hours at the temperature of 90 ℃ to prepare an intermediate 7, adding the intermediate 7, the modified carrier, sodium powder and toluene into the reaction kettle, introducing nitrogen for protection, reacting for 10 hours at the temperature of 5 ℃ to prepare an intermediate 8, adding the intermediate 8, bisphenol A epoxy resin E-44 and acetone into the reaction kettle, adding triethylamine under the conditions of the rotating speed of 300r/min and the temperature of 85 ℃ to react for 5 hours, filtering and drying to obtain the reinforced filler.

Comparative example 1

Compared with the corrosion-resistant coating in example 1, the corrosion-resistant coating in the comparative example is prepared by replacing graphene and reinforcing filler with the same steps.

Comparative example 2

This comparative example is a corrosion resistant coating disclosed in chinese patent CN 103173100A.

The corrosion resistant coatings of examples 1-3 and comparative examples 1-2 were coated on an iron plate, immersed in a sulfuric acid solution with a mass fraction of 5% at a temperature of 25 ℃ for 50, 100, 200, and 300 hours, and the conditions of the paint film and the iron plate were observed, with the results shown in table 1 below;

TABLE 1

From the above table 1, it can be seen that the corrosion-resistant coatings prepared in the embodiments 1-3 have no paint film bubbling and dropping after being soaked in sulfuric acid for 300 hours, and the iron plate has no corrosion, and the corrosion-resistant coatings prepared by the invention have good acid corrosion resistance.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.