阅读说明：本技术 一种荧光增白剂cbs-351的生产工艺 (Production process of fluorescent brightener CBS-351 ) 是由 马学文 刘文平 葛德三 周建玲 于 2020-11-20 设计创作，主要内容包括：本发明涉及一种荧光增白剂CBS-351的生产工艺,具体包括如下步骤：步骤一、合成4-4’-双(二乙氧基膦酰甲基)联苯：4,4’-双氯甲基联苯与亚磷酸三乙酯在加热条件下反应生成酯化物中间体4-4’-双(二乙氧基膦酰甲基)联苯；步骤二、制CBS-351：4-4’-双(二乙氧基膦酰甲基)联苯、邻磺酸钠苯甲醛、甲醇钠反应生成CBS-351；步骤三、盐析：步骤二反应得到的CBS-351溶液经氯化钠盐析,压滤制得CBS-351粗品。本发明合成的CBS-351纯度达99％以上。(The invention relates to a production process of a fluorescent brightener CBS-351, which specifically comprises the following steps: step one, synthesizing 4-4' -bis (diethoxyphosphonomethyl) biphenyl: 4,4 '-dichloromethyl biphenyl reacts with triethyl phosphite under the heating condition to generate esterified intermediate 4-4' -bis (diethoxyphosphonomethyl) biphenyl; step two, preparing CBS-351: reacting 4-4' -bis (diethoxyphosphonomethyl) biphenyl, sodium o-sulfonate benzaldehyde and sodium methoxide to generate CBS-351; step three, salting out: and salting out the CBS-351 solution obtained by the reaction in the step two by using sodium chloride, and performing filter pressing to obtain a crude product of the CBS-351. The purity of the CBS-351 synthesized by the invention reaches more than 99 percent.)

1. The production process of the fluorescent brightener CBS-351 is characterized by comprising the following steps:

step one, synthesizing 4-4' -bis (diethoxyphosphonomethyl) biphenyl: 4,4 '-dichloromethyl biphenyl reacts with triethyl phosphite under the heating condition to generate esterified intermediate 4-4' -bis (diethoxyphosphonomethyl) biphenyl;

step two, preparing CBS-351: 4-4 '-bis (diethoxyphosphonomethyl) biphenyl, sodium o-sulfonate benzaldehyde and sodium methoxide react to generate CBS-351, namely 4, 4' -bis (2-sulfostyryl) -1, 1-biphenyl;

step three, salting out: and salting out the CBS-351 solution obtained by the reaction in the step two by using sodium chloride, and performing filter pressing to obtain a crude product of the CBS-351.

2. The process for the production of the fluorescent whitening agent CBS-351 according to claim 1, further comprising the fourth step of refining: adding water into a dissolving kettle, sequentially adding the CBS-351 crude product and activated carbon, heating the materials to 85-95 ℃, filtering the activated carbon, cooling the clear filtrate to 40 ℃, transferring the clear filtrate into a crystallization kettle, cooling to 5 ℃, separating out CBS-351 crystals, performing filter pressing, and drying filter cakes to obtain the CBS-351 finished product.

3. Process for the production of the fluorescent whitening agent CBS-351 according to claim 1,

step one, the specific operation steps for synthesizing the 4-4' -bis (diethoxyphosphonomethyl) biphenyl are as follows:

adding BCMB and triethyl phosphite into an esterification synthesis kettle according to the mass ratio of 1: 1.5-2.0 of BCMB to triethyl phosphite, heating the materials to 110 ℃ to start reaction, continuously heating to 155-175 ℃, keeping the temperature for 6-10 h, and after the reaction is finished, evaporating unreacted triethyl phosphite under reduced pressure to obtain esterification liquid containing an esterification product intermediate.

4. Process for the production of the fluorescent whitening agent CBS-351 according to claim 3,

the specific operation of step two CBS-351 is as follows:

according to the mass ratio of BCMB to sodium o-sulfonate benzaldehyde to sodium methoxide of 1: 0.9-1.1: weighing each substance 0.18-0.24, respectively dissolving esterified liquid containing an esterified substance intermediate, sodium ortho-sulfonate benzaldehyde and sodium methoxide in DMF, adding into a condensation reaction kettle, reacting at 45-55 ℃ for 6-10 h to obtain CBS-351 solution, and feeding the CBS-351 solution into a heat preservation kettle for heat preservation for 20-25 h at the temperature of 45-55 ℃.

5. A process for the production of the fluorescent whitening agent CBS-351 according to claim 4, characterized in that the specific operation of the third salting-out step is as follows:

and after the heat preservation of the CBS-351 solution is finished, carrying out reduced pressure distillation, distilling out DMF and methanol, adding refined mother liquor until all materials in the kettle are dissolved, pumping into a salting-out kettle, adding sodium chloride, then cooling to 40 ℃, precipitating CBS-351, then cooling the materials in the cooling kettle to 5 ℃, and carrying out filter pressing to obtain a filter cake, namely a crude CBS-351 product.

6. The process for the production of the fluorescent whitening agent CBS-351 according to claim 1, wherein the 4, 4' -bischloromethylbiphenyl used in the first step is prepared by the following method:

step (1), synthesizing 4, 4' -dichloromethyl biphenyl: with cyclohexane as a solvent, reacting biphenyl, paraformaldehyde and hydrogen chloride to generate BCMB (4, 4' -bischloromethylbiphenyl) under the action of a composite catalyst;

the composite catalyst is a mixture of a 4A molecular sieve and monochloroacetic acid in a mass ratio of 1: 2-5; stirring and ultrasonic waves are applied simultaneously in the reaction process;

step (2), BCMB washing: filtering the reaction solution obtained in the step one, primarily washing with purified water, distilling to remove cyclohexane, crystallizing at low temperature, and centrifuging to obtain a BCMB crude product;

and (3) refining and drying BCMB: and dissolving the BCMB crude product by using toluene, filtering insoluble impurities, crystallizing at low temperature again, centrifuging, and drying a filter cake to obtain the BCMB finished product.

7. Process for the production of the fluorescent whitening agent CBS-351 according to claim 6,

the specific operation for synthesizing 4, 4' -bischloromethylbiphenyl in step (1) is as follows: according to the mass ratio of biphenyl to paraformaldehyde to the composite catalyst to the solvent of 1: 0.5-1.5: 0.05-0.15: 3.0-3.5, adding a solvent into a reaction kettle, adding biphenyl into the reaction kettle under the stirring condition, stirring for 15-25 min, continuing to add polyformaldehyde and a composite catalyst into the reaction kettle, controlling the temperature of the materials to be 20-40 ℃, starting ultrasonic waves while stirring, introducing HCl gas to ensure that tail gas is generated, stirring for 5-8 h, stopping ventilation, finishing the reaction, and filtering to obtain a BCMB solution for later use; the composite catalyst is a mixture of a 4A molecular sieve and monochloroacetic acid in a mass ratio of 1: 2-5.

8. The production process of the fluorescent brightener CBS-351 as claimed in claim 7, wherein the solvent is cyclohexane, and the power of the ultrasonic waves is 800-1200W; the stirring speed is 15-35 r/min when the ultrasonic waves and the stirring are simultaneously applied.

9. The process for the production of the fluorescent whitening agent CBS-351 according to claim 7, wherein the water washing of step (2) is carried out by the following steps: adding purified water into a washing kettle according to the mass ratio of the solvent to the purified water of 1: 1.0-1.5, adding the BCMB solution into the washing kettle, stirring for 15-25 min, standing until layering, discharging a water phase, pumping an organic phase into a distillation kettle, distilling at normal pressure to 100 ℃, distilling at negative pressure for 10min, recovering the solvent, after the distillation is finished, sending the material to a washing crystallization kettle, crystallizing at the low temperature of less than or equal to 20 ℃, and centrifuging to obtain a BCMB crude product.

10. The process for the production of the fluorescent whitening agent CBS-351 according to claim 7, wherein the ratio of BCMB to toluene by mass is 1: 4-6, firstly adding toluene into a refined water washing kettle, then adding a BCMB crude product, heating materials in the kettle to 100 ℃, detecting the pH value of the solution to be neutral after the BCMB is dissolved, and filtering insoluble impurities to obtain a toluene solution of the BCMB; and then, cooling the toluene solution of the BCMB to 40-60 ℃, then sending the solution to a refining crystallization kettle, carrying out low-temperature crystallization at the temperature of less than or equal to 10 ℃, centrifuging, and drying a filter cake to obtain the BCMB finished product.

Technical Field

The invention belongs to the field of fluorescent brightener preparation, and particularly relates to a production process of a fluorescent brightener CBS-351.

Background

The fluorescent whitening agent CBS-351, namely 4, 4' -bis (2-sulfostyryl) -1, 1-biphenyl, is a whitening agent for detergent with excellent performance, has the characteristics of safety, no toxicity, strong whitening capability, high speed, high efficiency, good stability, particularly good solubility and dispersibility, good accumulation effect and the like, and is known as a super fluorescent whitening agent. The fluorescent brightener is widely applied to foreign detergent products and becomes a leading fluorescent brightener product in developed countries; at present, domestic fluorescent brightener CBS-351 is still imported mainly, and although a few manufacturers produce the fluorescent brightener CBS-351, the quality and the quantity of the fluorescent brightener CBS-351 cannot meet the market needs mainly because the fluorescent brightener CBS-351 has the following characteristics: (1) the purity and yield of 4, 4' -dichloromethyl biphenyl, which is a key step affecting the quality and cost of BCS-351, are low, so that the purity of a CBS-351 finished product is limited; (2) the crude CBS-351 product generated by the reaction of 4-4' -bis (diethoxyphosphonomethyl) biphenyl, sodium o-sulfonate benzaldehyde and sodium methoxide is difficult to refine, the cost is high, the steps are complicated, and the refined product has low purity.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a production process of a fluorescent brightener CBS-351.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a production process of a fluorescent brightener CBS-351 specifically comprises the following steps:

step one, synthesizing 4-4' -bis (diethoxyphosphonomethyl) biphenyl: 4,4 '-dichloromethyl biphenyl reacts with triethyl phosphite under the heating condition to generate esterified intermediate 4-4' -bis (diethoxyphosphonomethyl) biphenyl;

step two, preparing CBS-351: 4-4 '-bis (diethoxyphosphonomethyl) biphenyl, sodium o-sulfonate benzaldehyde and sodium methoxide react to generate CBS-351, namely 4, 4' -bis (2-sulfostyryl) -1, 1-biphenyl;

step three, salting out: and salting out the CBS-351 solution obtained by the reaction in the step two by using sodium chloride, and performing filter pressing to obtain a crude product of the CBS-351.

Further, the production process of the fluorescent brightener CBS-351 also comprises the fourth step of refining: adding water into a dissolving kettle, sequentially adding the CBS-351 crude product and activated carbon, heating the materials to 85-95 ℃, filtering the activated carbon, cooling the clear filtrate to 40 ℃, transferring the clear filtrate into a crystallization kettle, cooling to 5 ℃, separating out CBS-351 crystals, performing filter pressing, and drying filter cakes to obtain the CBS-351 finished product.

Further, the specific operation steps for synthesizing the 4-4' -bis (diethoxyphosphonomethyl) biphenyl in the first step are as follows:

adding BCMB and triethyl phosphite into an esterification synthesis kettle according to the mass ratio of 1: 1.5-2.0 of BCMB to triethyl phosphite, heating the materials to 110 ℃ to start reaction, continuously heating to 155-175 ℃, keeping the temperature for 6-10 h, and after the reaction is finished, evaporating unreacted triethyl phosphite under reduced pressure to obtain esterification liquid containing an esterification product intermediate.

Further, the specific operation of step two CBS-351 is as follows:

according to the mass ratio of BCMB to sodium o-sulfonate benzaldehyde to sodium methoxide of 1: 0.9-1.1: weighing each substance 0.18-0.24, respectively dissolving esterified liquid containing an esterified substance intermediate, sodium ortho-sulfonate benzaldehyde and sodium methoxide in DMF, adding into a condensation reaction kettle, reacting at 45-55 ℃ for 6-10 h to obtain CBS-351 solution, and feeding the CBS-351 solution into a heat preservation kettle for heat preservation for 20-25 h at the temperature of 45-55 ℃.

Furthermore, the specific operation of the third salting-out step is as follows:

and after the heat preservation of the CBS-351 solution is finished, carrying out reduced pressure distillation, distilling out DMF and methanol, adding refined mother liquor until all materials in the kettle are dissolved, pumping into a salting-out kettle, adding sodium chloride, then cooling to 40 ℃, precipitating CBS-351, then cooling the materials in the cooling kettle to 5 ℃, and carrying out filter pressing to obtain a filter cake, namely a crude CBS-351 product.

Further, the 4, 4' -bischloromethylbiphenyl used in the first step is prepared by the following method:

step (1), synthesizing 4, 4' -dichloromethyl biphenyl: with cyclohexane as a solvent, reacting biphenyl, paraformaldehyde and hydrogen chloride to generate BCMB (4, 4' -bischloromethylbiphenyl) under the action of a composite catalyst;

the composite catalyst is a mixture of a 4A molecular sieve and monochloroacetic acid in a mass ratio of 1: 2-5; stirring and ultrasonic waves are applied simultaneously in the reaction process;

step (2), BCMB washing: filtering the reaction solution obtained in the step one, primarily washing with purified water, distilling to remove cyclohexane, crystallizing at low temperature, and centrifuging to obtain a BCMB crude product;

and (3) refining and drying BCMB: and dissolving the BCMB crude product by using toluene, filtering insoluble impurities, crystallizing at low temperature again, centrifuging, and drying a filter cake to obtain the BCMB finished product.

Furthermore, the specific operation of synthesizing 4, 4' -bischloromethylbiphenyl in the step (1) is as follows: according to the mass ratio of biphenyl to paraformaldehyde to the composite catalyst to the solvent of 1: 0.5-1.5: 0.05-0.15: 3.0-3.5, adding a solvent into a reaction kettle, adding biphenyl into the reaction kettle under the stirring condition, stirring for 15-25 min, continuing to add polyformaldehyde and a composite catalyst into the reaction kettle, controlling the temperature of the materials to be 20-40 ℃, starting ultrasonic waves while stirring, introducing HCl gas to ensure that tail gas is generated, stirring for 5-8 h, stopping ventilation, finishing the reaction, and filtering to obtain a BCMB solution for later use; the composite catalyst is a mixture of a 4A molecular sieve and monochloroacetic acid in a mass ratio of 1: 2-5;

furthermore, the solvent is cyclohexane, and the power of the ultrasonic wave is 800-1200W; the stirring speed is 15-35 r/min when the ultrasonic waves and the stirring are simultaneously applied.

Furthermore, the specific operation steps of the water washing in the step (2) are as follows: adding purified water into a washing kettle according to the mass ratio of a solvent to the purified water of 1: 1.0-1.5, adding a BCMB solution into the washing kettle, stirring for 15-25 min, standing until layering, discharging a water phase, pumping an organic phase into a distillation kettle, distilling at normal pressure to 100 ℃, distilling at negative pressure for 10min, recovering the solvent, after the distillation is finished, sending the material to a washing crystallization kettle, crystallizing at the low temperature of less than or equal to 20 ℃, and centrifuging to obtain a BCMB crude product;

furthermore, according to the mass ratio of BCMB to toluene of 1: 4-6, firstly adding toluene into a refined water washing kettle, then adding a BCMB crude product, heating materials in the kettle to 100 ℃, detecting the pH value of the solution to be neutral after the BCMB is dissolved, and filtering insoluble impurities to obtain a toluene solution of the BCMB; and then, cooling the toluene solution of the BCMB to 40-60 ℃, then sending the solution to a refining crystallization kettle, carrying out low-temperature crystallization at the temperature of less than or equal to 10 ℃, centrifuging, and drying a filter cake to obtain the BCMB finished product.

The synthetic route of the invention is as follows:

the key step of preparing the CBS-351 fluorescent whitening agent is the synthesis of 4,4 ' -dichloromethyl biphenyl, the problems of long reaction time, low yield and high post-treatment difficulty of the preparation method of the 4,4 ' -dichloromethyl biphenyl generally exist, and the research on how to find the preparation method of the 4,4 ' -dichloromethyl biphenyl with simple process, short reaction time and high yield is always a hotspot researched by the industry, under the trend of the purpose, the inventor of the application considers the limitation of simple stirring on local dispersion, tries to adopt an ultrasonic mode to replace a mechanical stirring mode, and uses CuCl₂、AlCl₃、CoCl₂Formic acid, monochloroacetic acid and phosphoric acid, unfortunately, have not been able to achieve satisfactory results, and it has been unexpectedly found that the addition of a suitable proportion of 4A molecular sieve is advantageous to the reaction when the inventors intend to give up, and therefore, the inventors have conducted intensive studies on the selection of molecular sieves and catalysts and have completed the present invention.

In the search, the inventors found that: when the 4A molecular sieve and monochloroacetic acid are added in the reaction at the same time, the use amount of the catalyst can be obviously reduced, however, when the inventor is happy to find out that whether mechanical stirring and ultrasonic waves are used together, the dependence of the use power of the ultrasonic waves on the reduction of the reaction temperature and the reduction of the reaction time are critically influenced, the use amount of the catalyst can be obviously reduced, the reaction rate can be improved, the reaction time can be shortened, the range of the reaction temperature can be expanded, the sensitivity of the reaction to the temperature can be reduced by adjusting the proportion of the 4A molecular sieve and the monochloroacetic acid and adopting a processing mode of combining mechanical stirring and ultrasonic waves, and the stirring speed and the power of the ultrasonic waves can be adjusted, and the aim of the invention can not be achieved by simply adjusting any one of the components, and finally the mass ratio of the 4A molecular sieve and the monochloroacetic acid is determined to be 1:3.5 through exploration and verification, the treatment mode of mechanical stirring and ultrasonic wave combination is that the power of ultrasonic wave is 800-1200W preferably.

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

the invention provides a novel process for producing a fluorescent brightener CBS-351, which improves the synthesis of 4,4 '-dichloromethyl biphenyl, reduces the synthesis cost of 4, 4' -dichloromethyl biphenyl, improves the yield of 4,4 '-dichloromethyl biphenyl, reduces the reaction temperature sensitivity of 4, 4' -dichloromethyl biphenyl, and simplifies post-treatment, thereby solving the key technology of synthesizing the fluorescent brightener CBS-351 and ensuring that the purity of the prepared CBS-351 can reach more than 99%.

The synthesis method of the fluorescent brightener CBS-351 provided by the invention has the advantages of simple refining process steps, convenience in operation and good refining effect.

Detailed Description

The production process of the present invention is specifically exemplified below.

In the present invention,

biphenyl: shanghai Jing Shanghai chemical industry Co., Ltd., purity of 99%;

paraformaldehyde: hebei aerospace chemical Co., Ltd;

triethyl phosphite: liaoning Tourvey agro chemical industries, Ltd;

sodium o-sulfonate benzaldehyde: hebei Star chemical Co., Ltd;

sodium methoxide: the Schchen Tai Xinda chemical Co., Ltd.

Example 1

A production process of a fluorescent brightener CBS-351 specifically comprises the following steps:

step one, preparing 4, 4' -dichloromethyl biphenyl:

step (1), synthesis: under the action of the composite catalyst, reacting biphenyl, paraformaldehyde and hydrogen chloride to generate BCMB (4, 4' -bischloromethylbiphenyl);

according to the mass ratio of biphenyl, paraformaldehyde, a composite catalyst and a solvent cyclohexane of 1:0.8: 0.10: 3.25, adding 1300Kg of cyclohexane solvent into a reaction kettle, adding 400Kg of biphenyl into the reaction kettle under the stirring condition of 50 revolutions per minute, stirring for 20 minutes, continuously adding 320Kg of paraformaldehyde and 40Kg of composite catalyst into the reaction kettle, controlling the materials to be 20-40 ℃ (the temperature is changed in the reaction process and only needs to be controlled to be 20-40 ℃), simultaneously starting ultrasonic waves under the stirring condition of 25 revolutions per minute, controlling the power of the ultrasonic waves to be 1000W, introducing HCl gas to ensure that tail gas is generated, stirring for reaction for 6.5 hours, stopping ventilation, finishing the reaction, filtering to obtain a BCMB solution for later use; the composite catalyst is a mixture of a 4A molecular sieve and monochloroacetic acid in a mass ratio of 1: 3.5; sampling, detecting the content of BCMB in the BCMB solution, and calculating to obtain 577Kg of total BCMB in the BCMB solution and 88.8 percent of BCMB reaction yield;

step (2), washing with water:

adding 1500Kg of purified water into a washing kettle according to the mass ratio of a solvent to the purified water of 1:1.15, then adding a BCMB solution into the washing kettle, stirring for 20min, standing until layering, discharging a water phase, pumping an organic phase into a distillation kettle, distilling at normal pressure to 100 ℃, distilling at negative pressure for 10min, recovering cyclohexane, after the distillation is finished, sending the material to a washing crystallization kettle, crystallizing at the low temperature of less than or equal to 20 ℃, and centrifuging to obtain a BCMB crude product;

and (3) refining and drying:

according to the mass ratio of BCMB to toluene of 1: adding 2885Kg of toluene into a refined water washing kettle, adding a BCMB crude product, heating materials in the kettle to 100 ℃, detecting that the pH of the solution is neutral (if the pH is not neutral, the solution needs to be washed to be neutral by water at 100 ℃) after the BCMB is dissolved, and filtering insoluble impurities to obtain a toluene solution of the BCMB; and then, cooling the toluene solution of the BCMB to 40-60 ℃, then sending the solution to a refining crystallization kettle, carrying out low-temperature crystallization at the temperature of less than or equal to 10 ℃, centrifuging, and drying a filter cake to obtain the BCMB finished product. The purity of the finished BCMB product is detected to be 99.7 percent.

Step two, synthesizing 4-4' -bis (diethoxyphosphonomethyl) biphenyl: 4,4 '-dichloromethyl biphenyl reacts with triethyl phosphite under the heating condition to generate esterified intermediate 4-4' -bis (diethoxyphosphonomethyl) biphenyl;

adding BCMB and triethyl phosphite into an esterification synthesis kettle according to the mass ratio of 1:1.7 of BCMB to triethyl phosphite, heating the materials to 110 ℃ to start reaction, continuously heating to 165 ℃, keeping the temperature for 8 hours, after the reaction is finished, evaporating unreacted triethyl phosphite under reduced pressure to obtain esterification liquid containing an esterified substance intermediate.

Step three, preparing CBS-351: 4-4 '-bis (diethoxyphosphonomethyl) biphenyl, sodium o-sulfonate benzaldehyde and sodium methoxide react to generate CBS-351, namely 4, 4' -bis (2-sulfostyryl) -1, 1-biphenyl;

according to the mass ratio of BCMB to sodium o-sulfonate benzaldehyde to sodium methoxide of 1: 1.01: 0.23, respectively dissolving the esterified liquid containing the esterified intermediate, sodium o-sulfonate benzaldehyde and sodium methoxide in DMF, adding the solution into a condensation reaction kettle, reacting at 45 ℃ for 8 hours to obtain a CBS-351 solution, and feeding the CBS-351 solution into a heat preservation kettle for heat preservation for 22 hours at the temperature of 50 ℃.

Step four, salting out: salting out the CBS-351 solution obtained by the reaction in the step II by sodium chloride, and performing filter pressing to obtain a crude product of the CBS-351;

and after the heat preservation of the CBS-351 solution is finished, carrying out reduced pressure distillation, distilling out DMF and methanol, adding refined mother liquor until all materials in the kettle are dissolved, pumping into a salting-out kettle, adding sodium chloride, then cooling to 40 ℃, precipitating CBS-351, then cooling the materials in the cooling kettle to 5 ℃, and carrying out filter pressing to obtain a filter cake, namely a crude CBS-351 product.

Step five, refining: adding water into a dissolving kettle, sequentially adding the CBS-351 crude product and active carbon, heating the materials to 90 ℃, filtering the active carbon, cooling the clear filtrate to 40 ℃, transferring the clear filtrate into a crystallization kettle, cooling to 5 ℃, separating out CBS-351 crystals, performing filter pressing, and drying filter cakes to obtain the CBS-351 finished product. The purity of the obtained CBS-351 finished product is 99.5 percent

Example 2

A production process of a fluorescent brightener CBS-351 specifically comprises the following steps:

step one, preparing 4, 4' -dichloromethyl biphenyl:

step (1), reaction: under the action of the composite catalyst, reacting biphenyl, paraformaldehyde and hydrogen chloride to generate BCMB (4, 4' -bischloromethylbiphenyl);

according to the mass ratio of biphenyl to paraformaldehyde to a composite catalyst to a solvent cyclohexane of 1:1.2: 0.13: 3.0, firstly adding 1200Kg of cyclohexane solvent into a reaction kettle, adding 400Kg of biphenyl into the reaction kettle under the stirring condition of 60 revolutions per minute, stirring for 25 minutes, then continuously adding 480Kg of paraformaldehyde and 52Kg of composite catalyst (the mass ratio of 4A molecular sieve to monochloroacetic acid is 1:4.5, namely 9.5Kg of 4A molecular sieve and 42.5Kg of monochloroacetic chloride) into the reaction kettle, then controlling the materials to be 20-40 ℃ (the temperature is changed in the reaction process, as long as the temperature is controlled to be 20-40 ℃), simultaneously starting ultrasonic waves under the stirring condition of 20 revolutions per minute, wherein the power of the ultrasonic waves is 1200W, introducing HCl gas to ensure that tail gas is generated, stirring for 5 hours, stopping ventilation, finishing the reaction, and filtering to obtain a BCMB solution for later use; sampling, detecting the content of BCMB in the BCMB solution, and calculating to obtain the total amount of the BCMB in the BCMB solution to be 570Kg, wherein the reaction yield is 87.7%;

step (2), washing with water:

adding 1560Kg of purified water into a washing kettle according to the mass ratio of the solvent to the purified water of 1:1.3, then adding the BCMB solution into the washing kettle, stirring for 25min, standing for layering, discharging a water phase, pumping an organic phase into a distillation kettle, distilling at normal pressure to 100 ℃, distilling at negative pressure for 10min, recovering the solvent, after the distillation is finished, sending the material to a washing crystallization kettle, crystallizing at the low temperature of less than or equal to 20 ℃, and centrifuging to obtain a BCMB crude product;

and (3) refining and drying:

according to the mass ratio of BCMB to toluene of 1: 5.5, firstly adding 3135Kg of toluene into a refined water washing kettle, then adding a BCMB crude product, heating the materials in the kettle to 100 ℃, detecting the pH value of the solution to be neutral (if the pH value is not neutral, washing the solution to be neutral by using water at 100 ℃) after the BCMB is dissolved, and filtering insoluble impurities to obtain a toluene solution of the BCMB; and then, cooling the toluene solution of the BCMB to 40-60 ℃, then sending the solution to a refining crystallization kettle, carrying out low-temperature crystallization at the temperature of less than or equal to 10 ℃, centrifuging, and drying a filter cake to obtain the BCMB finished product. Detecting the purity of the BCMB finished product to be 99.4%;

step two, synthesizing 4-4' -bis (diethoxyphosphonomethyl) biphenyl: 4,4 '-dichloromethyl biphenyl reacts with triethyl phosphite under the heating condition to generate esterified intermediate 4-4' -bis (diethoxyphosphonomethyl) biphenyl;

adding BCMB and triethyl phosphite into an esterification synthesis kettle according to the mass ratio of 1:1.7 of BCMB to triethyl phosphite, heating the materials to 110 ℃ to start reaction, continuously heating to 175 ℃, preserving heat for 6 hours, and after the reaction is finished, evaporating unreacted triethyl phosphite under reduced pressure to obtain esterification liquid containing an esterified substance intermediate.

Step three, preparing CBS-351: 4-4 '-bis (diethoxyphosphonomethyl) biphenyl, sodium o-sulfonate benzaldehyde and sodium methoxide react to generate CBS-351, namely 4, 4' -bis (2-sulfostyryl) -1, 1-biphenyl;

according to the mass ratio of BCMB to sodium o-sulfonate benzaldehyde to sodium methoxide of 1: 1.01: 0.23, respectively dissolving the esterified liquid containing the esterified intermediate, sodium o-sulfonate benzaldehyde and sodium methoxide in DMF, adding the solution into a condensation reaction kettle, reacting at 55 ℃ for 6 hours to obtain a CBS-351 solution, and feeding the CBS-351 solution into a heat preservation kettle for heat preservation for 25 hours at the temperature of 45 ℃.

Step four, salting out: salting out the CBS-351 solution obtained by the reaction in the step II by sodium chloride, and performing filter pressing to obtain a crude product of the CBS-351;

and after the heat preservation of the CBS-351 solution is finished, carrying out reduced pressure distillation, distilling out DMF and methanol, adding refined mother liquor until all materials in the kettle are dissolved, pumping into a salting-out kettle, adding sodium chloride, then cooling to 40 ℃, precipitating CBS-351, then cooling the materials in the cooling kettle to 5 ℃, and carrying out filter pressing to obtain a filter cake, namely a crude CBS-351 product.

Step five, refining: adding water into a dissolving kettle, sequentially adding the CBS-351 crude product and active carbon, heating the materials to 95 ℃, filtering the active carbon, cooling the clear filtrate to 40 ℃, transferring the clear filtrate into a crystallization kettle, cooling to 5 ℃, separating out CBS-351 crystals, performing filter pressing, and drying filter cakes to obtain the CBS-351 finished product. The purity of the obtained CBS-351 finished product is 99.3 percent.

Example 3

A production process of a fluorescent brightener CBS-351 specifically comprises the following steps:

step one, preparing 4, 4' -dichloromethyl biphenyl:

step (1), reaction: under the action of the composite catalyst, reacting biphenyl, paraformaldehyde and hydrogen chloride to generate BCMB (4, 4' -bischloromethylbiphenyl);

according to the mass ratio of biphenyl, paraformaldehyde, a composite catalyst and a solvent cyclohexane of 1:0.7: 0.08: 3.5, adding 1400Kg of cyclohexane solvent into a reaction kettle, adding 400Kg of biphenyl into the reaction kettle under the stirring condition of 50 revolutions per minute, stirring for 20 minutes, continuously adding 280Kg of paraformaldehyde and 32Kg of composite catalyst (the mass ratio of the 4A molecular sieve to monochloroacetic acid is 1:2.5, namely 9.1Kg of the 4A molecular sieve and 22.9Kg of monochloroacetic chloride) into the reaction kettle, then controlling the materials to be 20-40 ℃ (the temperature is changed in the reaction process, as long as the temperature is controlled to be 20-40 ℃), simultaneously starting ultrasonic waves under the stirring condition of 30 revolutions per minute, wherein the power of the ultrasonic waves is 800W, introducing HCl gas to ensure that tail gas is generated, stirring and reacting for 8 hours, stopping ventilation, finishing the reaction, and filtering to obtain a BCMB solution for later use; the composite catalyst is a mixture of a 4A molecular sieve and monochloroacetic acid in a mass ratio of 1: 2.5; sampling, detecting the content of BCMB in the BCMB solution, and calculating to obtain the total amount of the BCMB in the BCMB solution to be 562Kg and the reaction yield to be 86.5%;

step (2), washing with water:

according to the mass ratio of the solvent to the purified water of 1:1.0, firstly adding 1400Kg of purified water into a washing kettle, then adding the BCMB solution into the washing kettle, stirring for 20min, standing until layering, discharging a water phase, pumping an organic phase into a distillation kettle, distilling at normal pressure to 100 ℃, distilling at negative pressure for 10min, recovering the solvent, after the distillation is finished, sending the material into a washing crystallization kettle, crystallizing at the low temperature of less than or equal to 20 ℃, and centrifuging to obtain a BCMB crude product;

and (3) refining and drying:

according to the mass ratio of BCMB to toluene of 1:4.5, firstly adding 2529Kg of methylbenzene into a refined water washing kettle, then adding a BCMB crude product, heating materials in the kettle to 100 ℃, detecting the pH value of the solution to be neutral (if the pH value is not neutral, washing the solution to be neutral by using water at 100 ℃) after the BCMB is dissolved, and filtering insoluble impurities to obtain a methylbenzene solution of the BCMB; and then, cooling the toluene solution of the BCMB to 40-60 ℃, then sending the solution to a refining crystallization kettle, carrying out low-temperature crystallization at the temperature of less than or equal to 10 ℃, centrifuging, and drying a filter cake to obtain the BCMB finished product. The purity of the finished BCMB product is detected to be 99.5 percent.

Step two, synthesizing 4-4' -bis (diethoxyphosphonomethyl) biphenyl: 4,4 '-dichloromethyl biphenyl reacts with triethyl phosphite under the heating condition to generate esterified intermediate 4-4' -bis (diethoxyphosphonomethyl) biphenyl;

adding BCMB and triethyl phosphite into an esterification synthesis kettle according to the mass ratio of 1:1.7 of BCMB to triethyl phosphite, heating the materials to 110 ℃ to start reaction, continuously heating to 155 ℃, preserving heat for 10 hours, and after the reaction is finished, evaporating unreacted triethyl phosphite under reduced pressure to obtain esterification liquid containing an esterified substance intermediate.

Step three, preparing CBS-351: 4-4 '-bis (diethoxyphosphonomethyl) biphenyl, sodium o-sulfonate benzaldehyde and sodium methoxide react to generate CBS-351, namely 4, 4' -bis (2-sulfostyryl) -1, 1-biphenyl;

according to the mass ratio of BCMB to sodium o-sulfonate benzaldehyde to sodium methoxide of 1: 1.01: 0.23, respectively dissolving the esterified liquid containing the esterified intermediate, sodium o-sulfonate benzaldehyde and sodium methoxide in DMF, adding the solution into a condensation reaction kettle, reacting at 40 ℃ for 10 hours to obtain a CBS-351 solution, and feeding the CBS-351 solution into a heat preservation kettle for heat preservation for 20 hours at the temperature of 55 ℃.

Step four, salting out: salting out the CBS-351 solution obtained by the reaction in the step II by sodium chloride, and performing filter pressing to obtain a crude product of the CBS-351;

and after the heat preservation of the CBS-351 solution is finished, carrying out reduced pressure distillation, distilling out DMF and methanol, adding refined mother liquor until all materials in the kettle are dissolved, pumping into a salting-out kettle, adding sodium chloride, then cooling to 40 ℃, precipitating CBS-351, then cooling the materials in the cooling kettle to 5 ℃, and carrying out filter pressing to obtain a filter cake, namely a crude CBS-351 product.

Step five, refining: adding water into a dissolving kettle, sequentially adding a CBS-351 crude product and active carbon, heating the materials to 85 ℃, filtering the active carbon, cooling the clear filtrate to 40 ℃, transferring the clear filtrate into a crystallization kettle, cooling to 5 ℃, separating out CBS-351 crystals, performing filter pressing, and drying a filter cake to obtain a CBS-351 finished product; the purity of the obtained CBS-351 finished product is 99.3 percent.

Comparative example 1

The same as example 1, except that in the step (1) of the first step, the mass of the 4A molecular sieve added was 15.2Kg (the amount of the composite catalyst added was 46.3, the mass ratio of the 4A molecular sieve to monochloroacetic acid was 1:2, the mass ratio of biphenyl to the composite catalyst was 0.12), and the yield of BCMB was 0;

and the second to fifth steps can not be continued.

Comparative example 2

The same as example 1, except that in the step (1) of the first step, the mass of the 4A molecular sieve added is 4.5Kg (the addition amount of the composite catalyst is 35.6, the mass ratio of the 4A molecular sieve to monochloroacetic acid is 1:6.9, the mass ratio of biphenyl to the composite catalyst is 0.09), and the yield of BCMB is 0;

and the second to fifth steps can not be continued.

Comparative example 3

The same as example 1, except that in the step (1) of the first step, the mass of the added monochloroethane is 50.2Kg (the adding amount of the composite catalyst is 59.1, the mass ratio of the 4A molecular sieve to the monochloroacetic acid is 1:5.6, the mass ratio of the biphenyl to the composite catalyst is 0.15), and the yield of BCMB is 0;

and the second to fifth steps can not be continued.

Comparative example 4

The same as example 1, except that in the step (1) of the first step, the mass of the added monochloroethane was 18.5Kg (the added amount of the composite catalyst was 27.4, the mass ratio of the 4A molecular sieve to the monochloroacetic acid was 1:2.1, the mass ratio of the biphenyl to the composite catalyst was 0.07), and the yield of BCMB was 0;

and the second to fifth steps can not be continued.

Comparative example 5

The same as example 1, except that in the step (1) of the first step, only mechanical stirring is adopted, ultrasonic waves are not applied, the reaction time is 12 hours, and the yield of BCMB is 11%; the purity of the BCMB finished product is 99.3 percent;

the purity of the obtained CBS-351 finished product is 99.1%.

Comparative example 6

The method is the same as the example 1, except that in the step (1) of the step one, only ultrasonic waves are adopted, mechanical stirring is not adopted, the power of the ultrasonic waves is 1000W, the reaction time is 15 hours, and the yield of the BCMB is 8 percent; the purity of the BCMB finished product is 99.5 percent;

the purity of the obtained CBS-351 finished product is 99.1%.

Comparative example 7

The same as example 1, except that in the step (1) of the first step, the power of ultrasonic waves is 400W, the reaction time is 10 hours, and the yield of BCMB is 40%; the purity of the BCMB finished product is 99.5 percent; the purity of the obtained CBS-351 finished product is 99.2 percent.

Comparative example 8

The same as example 1, except that in the step (1) of the first step, the power of ultrasonic wave is 1700W, the reaction time is 4 hours, and the yield of BCMB is 49%; the purity of the BCMB finished product is 99.4 percent; the purity of the obtained CBS-351 finished product is 99.1%.

Comparative example 9

The method is the same as the example 1, except that in the step (1) of the first step, when ultrasonic waves and stirring are simultaneously applied, the stirring rotating speed is 40 r/min, the reaction time is 5 hours, and the BCMB yield is 60 percent; the purity of the BCMB finished product is 99.5 percent; the purity of the obtained CBS-351 finished product is 99.2 percent.

Comparative example 10

The method is the same as the example 1, except that in the step (1) of the first step, when ultrasonic waves and stirring are simultaneously applied, the stirring rotating speed is 10 r/min, the reaction time is 9 hours, and the BCMB yield is 20 percent; the purity of the BCMB finished product is 99.5 percent; the purity of the obtained CBS-351 finished product is 99.1%.

Comparative example 11:

a production process of a fluorescent brightener CBS-351 specifically comprises the following steps:

step one, preparing 4, 4' -dichloromethyl biphenyl:

step (1), reaction: under the action of the composite catalyst, reacting biphenyl, paraformaldehyde and hydrogen chloride to generate BCMB (4, 4' -bischloromethylbiphenyl);

according to the mass ratio of biphenyl, paraformaldehyde, a composite catalyst and a solvent cyclohexane of 1:0.8: 0.90: 3.25, adding 1300Kg of cyclohexane solvent into the reaction kettle, adding 400Kg of biphenyl into the reaction kettle under the stirring condition of 50 revolutions per minute, stirring for 20 minutes, and continuously adding 320Kg of paraformaldehyde and 360Kg of zinc chloride catalyst into the reaction kettle; then controlling the temperature of the material to be 18-22 ℃, introducing HCl gas to ensure that tail gas is generated, stirring for reacting for 25 hours, stopping introducing the gas, finishing the reaction, and filtering to obtain BCMB solution for later use; sampling, detecting the content of BCMB in the BCMB solution, and calculating to obtain 392Kg of total BCMB in the BCMB solution, wherein the reaction yield is 60.2%;

step (2), washing with water:

adding 1500Kg of purified water into a washing kettle according to the mass ratio of the solvent to the purified water of 1:1.15, then adding the BCMB solution into the washing kettle, stirring for 20min, standing until layering, discharging a water phase, pumping an organic phase into a distillation kettle, distilling at normal pressure to 100 ℃, distilling at negative pressure for 10min, recovering the solvent, after the distillation is finished, sending the material to a washing crystallization kettle, crystallizing at the low temperature of less than or equal to 20 ℃, and centrifuging to obtain a BCMB crude product;

and (3) refining and drying:

according to the mass ratio of BCMB to toluene of 1: adding 1960Kg of toluene into a refined water washing kettle, adding a crude product of BCMB, heating the materials in the kettle to 100 ℃, detecting the pH value of the solution to be neutral (if the pH value is not neutral, washing the solution to be neutral by water at 100 ℃) after the BCMB is dissolved, and filtering insoluble impurities to obtain a toluene solution of the BCMB; and then, cooling the toluene solution of the BCMB to 40-60 ℃, then sending the solution to a refining crystallization kettle, carrying out low-temperature crystallization at the temperature of less than or equal to 10 ℃, centrifuging, and drying a filter cake to obtain the BCMB finished product. The purity of the BCMB finished product is detected to be 99.1 percent.

The second to fifth steps are the same as example 1; the purity of the obtained CBS-351 finished product is 99.3 percent.

The embodiments described above are only preferred embodiments of the invention and are not exhaustive of the possible implementations of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.