Preparation method of tert-butylated phenyl phosphate with high purity and low triphenyl phosphate content

Abstract

The invention discloses a preparation method of tert-butylated phenyl phosphate with high purity and low triphenyl phosphate. The preparation method specifically comprises the following steps: carrying out an esterification reaction on phosphorus oxychloride and p-tert-butylphenol in the presence of a Lewis catalyst through gradient heating; and after the reaction is finished, carrying out reduced pressure distillation and molecular distillation to remove phosphorus oxychloride, and adding phenol for blocking to obtain the tert-butylated phenyl phosphate. By adopting gradient heating, the reaction of phosphorus oxychloride is more thorough under mild conditions, the conversion rate of raw materials is improved, the loss of phosphorus oxychloride can be effectively prevented, and the safety and stability of the process are ensured; phosphorus oxychloride is removed through reduced pressure distillation and molecular distillation together, the residual quantity is greatly reduced, so that the content of triphenyl phosphate in tert-butyl phosphate is lower than 0.1%, the product purity is greatly improved, the method is stable in process and simple to operate, special equipment is not needed, consumption is saved, the quality yield of the product in the batch production process is stable, and the method is suitable for industrial production. And subsequent high-end products can be stably generated, and the method is suitable for popularization and application.

Description

TECHNICAL FIELD

[0001] The present application relates to a preparation method of high-purity low-triphenyl phosphate tert-butylated phenyl phosphate ester. BACKGROUND

[0002] Halogen-free phosphate ester flame retardant tert-butylated phenyl phosphate ester (WSFR-HF-4) is widely used in soft polyurethane foam, and the European Chemicals Agency (ECHA) updated the thirty-second list of substances of very high concern (SVHC) on its official website. In this update, triphenyl phosphate (TPP) was officially added to the candidate list of substances of very high concern, so the low-TPP-content phenyl phosphate ester has a large market space.

[0003] Tert-butylated phenyl phosphate ester (WSFR-HF-4) produces triphenyl phosphate during synthesis, and the market requires strict control of the content of triphenyl phosphate (TPP), the lower the better.

[0004] At present, the reported tert-butylated phenyl phosphate ester mainly adopts the reaction of phosphorus oxychloride and tert-butyl phenol in the presence of a Lewis catalyst, and then the excess phosphorus oxychloride is distilled out under reduced pressure, and then end-capped with phenol to obtain tert-butylated phenyl phosphate ester, such as Chinese patents CN104262389A (application number 201410477762.0, invention name tert-butylated triphenyl phosphate preparation method) and CN102268036A (application number 201110136181.7, invention name tert-butylated triphenyl phosphate preparation method). In the above patents, excess phosphorus oxychloride is removed by vacuum distillation, but a large amount of phosphorus oxychloride is produced in the process of mass production, and it is difficult to remove it completely and residual in it. In the process of end-capping with phenol, the activity of phosphorus oxychloride and phenol is very strong, and they can easily react, so impurities such as triphenyl phosphate are produced. Some literatures also report that non-protic solvents are used to remove excess phosphorus oxychloride, but this method will consume a large amount of non-protic solvents and produce a large amount of waste liquid, which is not in line with the requirements of green environmental protection. Therefore, it is particularly important to develop a new preparation method of tert-butylated phenyl phosphate ester with high purity and low triphenyl phosphate content. SUMMARY

[0005] In view of the above deficiencies in the prior art, the purpose of the present application is to provide a preparation method of tert-butylated phenyl phosphate ester with low triphenyl phosphate content, and the quality of the tert-butylated phenyl phosphate ester product prepared by the limited method is higher than that of the same product on the market.

[0006] The present application limits a preparation method of high-purity low-triphenyl phosphate tert-butylated phenyl phosphate ester, which specifically includes the following steps: 1) according to the feeding ratio, add phosphorus oxychloride and Lewis catalyst into an esterification reactor, then slowly add p-tert-butyl phenol, and perform esterification reaction through gradient temperature rising, the gradient temperature rising process is: 80-85℃ for 3 hours, 90-100℃ for 2 hours, 110-120℃ for 2 hours, and 130-140℃ for 2 hours; After the reaction is completed, the temperature of the reaction liquid in step 1) is reduced to 60-100℃, and the phosphorus oxychloride is removed by vacuum distillation under a vacuum degree of 40-100 KPa, and then the phosphorus oxychloride is further removed by two-stage thin film molecular distillation at 60-100℃, the distillation vacuum degree of the first-stage thin film is 200-300 Pa, and the distillation vacuum degree of the second-stage thin film is 30-50 Pa, to obtain a p-tert-butyl phosphinic chloride intermediate; 3) under a nitrogen atmosphere, heat the p-tert-butyl phosphinic chloride intermediate in step 2) to 110-120℃, and add phenol to end-cap, to obtain a crude tert-butylated phenyl phosphonate; 4) after the crude product obtained in step 3) is subjected to alkali washing and water washing, vacuum distillation is performed to obtain a finished product tert-butylated phenyl phosphonate.

[0007] Further, the present application also limits the molar ratio of p-tert-butyl phenol to phosphorus oxychloride in step 1) to 1:3-4.5.

[0008] Further, the present application also limits the Lewis acid catalyst in step 1) to be any one of titanium tetrachloride, butyl titanate, magnesium chloride or aluminum chloride, and the amount is 0.25-0.4% of the mass of phosphorus oxychloride.

[0009] Further, the present application also limits the molar ratio of phenol to p-tert-butyl phenol in step 3) to be 3-4:1.

[0010] Further, the present application also limits the alkali washing to use a 3% sodium hydroxide solution in terms of mass percentage, and the temperature during the alkali washing and water washing is 50-70℃; the vacuum distillation temperature is 90-130℃, and the vacuum degree is 30-100 Pa.

[0011] Further, the present application also limits that a solvent toluene or xylene is added during the alkali washing and water washing, so as to better separate the layers for washing.

[0012] Further, the present application also limits the feeding time of p-tert-butyl phenol in step 1) to be 0.8-1.2 hours.

[0013] Further, the present application also limits that the hydrogen chloride gas generated in step 1) is absorbed by a water injection method.

[0014] By using the above-mentioned technology, compared with the prior art, the present application has the following beneficial effects: 1) The present application directly feeds at room temperature, and adopts gradient heating method when p-tert-butyl phenol and phosphorus oxychloride are esterified, which can keep the reaction under mild conditions, improve the conversion rate of raw materials, and effectively prevent the loss of phosphorus oxychloride, thereby ensuring the safety and stability of the process; 2) In the process of removing phosphorus oxychloride, a large amount of phosphorus oxychloride is removed by vacuum distillation, and then the residual phosphorus oxychloride is further removed by two-stage thin film molecular weight distillation under limited conditions, so that the residual amount of phosphorus oxychloride in the tert-butyl chloroformate is greatly reduced, even to zero, so that the content of triphenyl phosphate in the finally prepared tert-butyl phosphate is less than 0.1%, and even no triphenyl phosphate is detected; 3) In the process of removing phosphorus oxychloride, the temperature is 60-100℃, which avoids the decomposition of the intermediate obtained in the process of high-temperature vacuum distillation, thereby further improving the yield and purity of the product; 4) The method provided by the present application has the advantages of increased yield, improved purity, and greatly reduced content of triphenyl phosphate compared with the prior art method. The method is stable, simple to operate, does not require special equipment, saves consumption, and has stable product quality and yield in batch production, can stably generate subsequent high-end products, and is suitable for popularization and application. DETAILED DESCRIPTION

[0015] The following examples are used to illustrate the present application, but not to limit the scope of the present application.

[0016] Example 1: A method for preparing high-purity low-triphenyl phosphate tert-butyl phenyl phosphate, comprising the following steps: 1) Put 2000 kg of phosphorus oxychloride and 4 kg of aluminum chloride catalyst (0.2% of the mass of phosphorus oxychloride) into the esterification reactor, and add 1000 kg of p-tert-butyl phenol using a double-screw feeder, which takes about 1 hour to complete. After completion, perform esterification by gradient heating: slowly heat to 80-85℃ for 3 hours, heat to 90-100℃ for 2 hours, heat to 110-120℃ for 2 hours, heat to 130-140℃ for 2 hours, and absorb the generated hydrogen chloride gas by water injection; 2) After the reaction is completed, recover the phosphorus oxychloride by vacuum distillation at a temperature of 60-100℃ and a vacuum degree of 40-100 KPa, and then further remove the phosphorus oxychloride by two-stage thin film molecular distillation: the first-stage thin film distillation is performed at 200-250 Pa, and the second-stage thin film distillation is performed at a vacuum degree of 30-50 Pa and a temperature of 60-100℃, to obtain a p-tert-butyl phospho-chloroformate intermediate; 3) The p-tert-butyl phenyl phosphonate crude product of step 2) is transferred into the next reactor under nitrogen protection, and then phenol 1300 kg is introduced at a temperature of 110-120°C. The introduction is completed in about 3 hours, and then the temperature is kept for 2 hours. Then, the vacuum degree is 60-100 Pa, and the temperature is 130-140°C. The vacuum is kept for 1 hour to obtain the crude p-tert-butyl phenyl phosphonate; 4) The p-tert-butyl phenyl phosphonate crude product is added into toluene, and then washed with 3% sodium hydroxide solution (the concentration is mass percentage, and the same below). Then, the product is washed with water at a temperature of 55-60°C, and the water layer PH is 7-8. The water-washed p-tert-butyl phenyl phosphonate is dehydrated by vacuum distillation at a temperature of 90-130°C and a vacuum degree of 60-100 Pa. The distilled product 2643 kg is input into the product storage tank, and the yield is 95.8%, and the TPP content is 0.01%.

[0017] Example 2: A preparation method of high-purity low-phosphorus triphenyl phosphate tert-butyl phenyl phosphate, comprising the following steps: 1) Phosphorus oxychloride 2100 kg and catalyst titanium tetrachloride 6.3 kg (0.3% of the mass of titanium tetrachloride) are introduced into an esterification reactor, and then p-tert-butyl phenol 1000 kg is added by a double helix feeder. The addition is completed in about 1 hour, and then the temperature is slowly increased to 80-85°C and kept for 3 hours. The temperature is increased to 90-100°C and kept for 2 hours. The temperature is increased to 110-120°C and kept for 2 hours. The temperature is increased to 130-140°C and kept for 2 hours. The generated hydrogen chloride gas is absorbed by water spraying; 2) After the reaction is completed, the phosphorus oxychloride is recovered by vacuum distillation at a temperature of 60-100°C and a vacuum degree of 40-100 KPa. Then, the phosphorus oxychloride is further removed by two-stage thin film molecular distillation: the first-stage thin film distillation is at a vacuum degree of 200-250 Pa, and the second-stage thin film distillation is at a vacuum degree of 30-50 Pa, and the temperature is 60-100°C. The p-tert-butyl phosphonate intermediate is obtained. 3) The p-tert-butyl phosphonate intermediate of step 2) is transferred into the next reactor under nitrogen protection, and then phenol 1300 kg is introduced at a temperature of 110-120°C. The introduction is completed in about 3 hours, and then the temperature is kept for 2 hours. Then, the vacuum degree is 60-100 Pa, and the temperature is 130-140°C. The vacuum is kept for 1 hour to obtain the crude p-tert-butyl phenyl phosphonate; 4) The p-tert-butyl phenyl phosphonate crude product is added into toluene, and then washed with 3% sodium hydroxide solution. Then, the product is washed with water at a temperature of 55-60°C, and the water layer PH is 7-8. The water-washed p-tert-butyl phenyl phosphonate is dehydrated by vacuum distillation at a temperature of 90-130°C and a vacuum degree of 60-100 Pa. The distilled product 2643 kg is input into the product storage tank, and the yield is 95.3%, and the TPP content is 0.06%.

[0018] Example 3: A method for preparing high-purity low-phosphorus triphenyl phosphate tert-butylated phenyl phosphate ester, comprising the following steps: 1) Control the passage of phosphorus oxychloride 1500 kg and catalyst aluminum trichloride 4.3 kg (0.29% of the mass of phosphorus oxychloride) into the esterification reactor, add p-tert-butyl phenol 1000 kg using a double helical screw feeder, and complete the addition in about 1 hour. After completion, slowly warm to 80-85°C for 3 hours, warm to 90-100°C for 2 hours, warm to 110-120°C for 2 hours, warm to 130-140°C for 2 hours, and absorb the hydrogen chloride gas generated during the reaction using a water injection method; 2) After the reaction is complete, recover and distill the phosphorus oxychloride under a vacuum of 40-100 KPa at a temperature of 60-100°C, and then perform vacuum distillation by two-stage thin film molecular distillation. The first-stage thin film distillation is performed at a vacuum of 200-250 Pa, and the second-stage thin film distillation is performed at a vacuum of 30-50 Pa and a temperature of 60-100°C, to obtain the p-tert-butyl phosphorus oxychloride intermediate; 3) Under nitrogen, transfer the p-tert-butyl phosphorus oxychloride intermediate of step 2) to the next reaction kettle, warm, control the temperature at 110-120°C, and then pass in phenol 1300 kg, which takes about 3 hours to complete. After completion, warm for 2 hours and then vacuum, at a vacuum of 60-100 Pa and a temperature of 130-140°C, for 1 hour to obtain the crude tert-butyl phenyl phosphate ester; 4) Add the crude tert-butyl phenyl phosphate ester to toluene, perform alkaline washing with 3% sodium hydroxide solution, and water washing at a temperature of 55-60°C, with the water layer having a pH of 7-8. The water-washed tert-butyl phenyl phosphate ester is subjected to vacuum distillation at a temperature of 90-130°C and a vacuum of 60-100 Pa. The product after distillation, 2643 kg, is input into the finished product storage tank, with a yield of 95.2% and a TPP of 0.06%.

[0019] Example 4: A method for preparing high-purity low-phosphorus triphenyl phosphate tert-butylated phenyl phosphate ester, comprising the following steps: 1) Control the passage of phosphorus oxychloride 2000 kg and catalyst aluminum trichloride 6 kg (0.3% of the mass of phosphorus oxychloride) into the esterification reactor, add p-tert-butyl phenol 1000 kg using a double helical screw feeder, and complete the addition in about 1 hour. After completion, slowly warm to 80-85°C for 3 hours, warm to 90-100°C for 2 hours, warm to 110-120°C for 2 hours, warm to 130-140°C for 2 hours, and absorb the hydrogen chloride gas generated during the reaction using a water injection method; 2) After the reaction, the temperature is 60-100°C, the vacuum degree is 40-100 KPa, and the distillation of phosphorus oxychloride is recovered under reduced pressure, and then two-stage thin film molecular distillation is carried out, the first-stage thin film distillation is 200-250 Pa, the second-stage thin film distillation is 30-50 Pa, and the temperature is 60-100°C, to obtain the p-tert-butyl phosphorus oxychloride intermediate; 3) The p-tert-butyl phosphorus oxychloride intermediate of step 2) is transferred to the next reaction kettle under nitrogen, heated, and the temperature is controlled at 110-120°C, then phenol 1300 kg is introduced, about 3 hours are introduced, after the introduction is completed, 2 hours of heat preservation are carried out, then vacuum is extracted, the vacuum degree is 60-100 Pa, the temperature is 130-140°C, and the acid is extracted for 1 hour, to obtain the crude tert-butyl phenyl phosphonate; 4) The crude tert-butyl phenyl phosphonate is added to toluene, washed with 3% sodium hydroxide solution, washed with water, the washing temperature is 55-60°C, the water layer PH=7-8; the washed tert-butyl phenyl phosphonate is distilled under reduced pressure, the temperature is 90-130°C, the vacuum degree is 60-100 Pa, the product 2643 kg after distillation is input into the product storage tank, the yield is 93.7%, and the TPP is 0.1%.

[0020] Example 5: A preparation method of high-purity low-phosphorus triphenyl phosphate tert-butyl phenyl phosphonate, comprising the following steps: 1) Control the introduction of phosphorus oxychloride 2100 kg and catalyst titanium tetrachloride 6.3 kg (0.3% of the mass of titanium tetrachloride) into the esterification reaction kettle, add p-tert-butyl phenol 1000 kg through a double-screw feeder, about 1 hour is added, after the addition is completed, slowly heat to 80-85°C, heat for 3 hours, heat to 90-100°C, heat for 2 hours, heat to 110-120°C, heat for 2 hours, heat to 130-140°C, heat for 2 hours, and the hydrogen chloride gas generated in the reaction is absorbed by water spraying; 2) After the reaction, the distillation of phosphorus oxychloride is recovered under reduced pressure, the vacuum degree is 40-100 KPa, and the temperature is 100-140°C, to obtain the tert-butyl phosphorus oxychloride intermediate; 3) The p-tert-butyl phosphorus oxychloride intermediate of step 2) is transferred to the next reaction kettle under nitrogen, heated, and the temperature is controlled at 110-120°C, then phenol 1300 kg is introduced, about 3 hours are introduced, after the introduction is completed, 2 hours of heat preservation are carried out, then vacuum is extracted, the vacuum degree is 60-100 Pa, the temperature is 130-140°C, and the acid is extracted for 1 hour, to obtain the crude tert-butyl phenyl phosphonate; 4) The crude tert-butyl phenyl phosphate is added to toluene, washed with 3% sodium hydroxide solution, washed with water, washing temperature 55-60°C, water layer PH = 7-8; the water-washed tert-butyl phenyl phosphate is distilled under reduced pressure at a temperature of 90-130°C and a vacuum degree of 60-100 Pa, and the distilled product 2643 kg is input into a product storage tank, with a yield of 91% and TPP of 0.82%.

[0021] Example 6: A preparation method of tert-butylated phenyl phosphate of high-purity low-phosphorus triphenyl phosphate, comprising the following steps: 1) Control the passage of phosphorus oxychloride 2000 kg and catalyst aluminum trichloride 5.8 kg (0.29% of the mass of phosphorus oxychloride) into an esterification reaction kettle, and add p-tert-butyl phenol 1000 kg using a double helical screw feeder, which is completed in about 1 hour, and then slowly heat to 80-85°C for 3 hours, heat to 90-100°C for 2 hours, heat to 110-120°C for 2 hours, heat to 130-140°C for 2 hours, and absorb the generated hydrogen chloride gas using a water spraying method; 2) After the reaction, distill the phosphorus oxychloride under reduced pressure at a temperature of 60-100°C and a vacuum degree of 40-100 KPa, and then perform two-stage thin film molecular distillation under reduced pressure, with the first-stage thin film distillation being performed at 200-250 Pa and a temperature of 60-100°C to obtain a p-tert-butyl phosphorus oxychloride intermediate; 3) Under nitrogen, transfer the p-tert-butyl phosphorus oxychloride intermediate of step 2) to a next-stage reaction kettle, heat, control the temperature at 110-120°C, then pass in phenol 1300 kg, which is completed in about 3 hours, and then heat for 2 hours, then vacuumize, with a vacuum degree of 60-100 Pa and a temperature of 130-140°C, and acidize for 1 hour to obtain crude tert-butyl phenyl phosphate; 4) The crude tert-butyl phenyl phosphate is added to toluene, washed with 3% sodium hydroxide solution, washed with water, washing temperature 55-60°C, water layer PH = 7-8; the water-washed tert-butyl phenyl phosphate is distilled under reduced pressure at a temperature of 90-130°C and a vacuum degree of 60-100 Pa, and the distilled product 2643 kg is input into a product storage tank, with a yield of 94% and TPP of 0.56%.

[0022] Example 7: A preparation method of tert-butylated phenyl phosphate of high-purity low-phosphorus triphenyl phosphate, comprising the following steps: 1) Control the passage of phosphorus oxychloride 2000 kg and catalyst aluminum trichloride 5.8 kg (0.29% of the mass of phosphorus oxychloride) into an esterification reaction kettle, and add p-tert-butyl phenol 1000 kg using a double helical screw feeder, which is completed in about 1 hour, and then slowly heat to 80-85°C for 3 hours, heat to 90-100°C for 2 hours, heat to 110-120°C for 2 hours, heat to 130-140°C for 2 hours, and absorb the generated hydrogen chloride gas using a water spraying method; 2) After the reaction, the temperature is 60-100℃, the vacuum degree is 40-100KPa, and the phosphorus oxychloride is recovered by vacuum distillation, and then two-stage thin film molecular distillation is carried out, the first-stage thin film distillation is 200-250Pa, the second-stage thin film distillation is 30-50Pa, and the temperature is 60-100℃, to obtain the p-tert-butyl phosphorus oxychloride intermediate; 3) The p-tert-butyl phosphorus oxychloride intermediate of step 2) is transferred to the next reaction kettle under nitrogen, heated, and the temperature is controlled at 110-120℃, then phenol 1300kg is introduced, about 3 hours are needed for the introduction, after the introduction, 2 hours of heat preservation are needed, then vacuum is extracted, the vacuum degree is 60-100Pa, and the temperature is 130-140℃, and the acid is extracted for 1 hour, to obtain the crude tert-butyl phenyl phosphonate; 4) The crude tert-butyl phenyl phosphonate is added to toluene, washed with 3% sodium hydroxide solution, washed with water, the washing temperature is 55-60℃, the water layer PH=7-8; the washed tert-butyl phenyl phosphonate is subjected to vacuum distillation at a temperature of 90-130℃ and a vacuum degree of 60-100Pa, and the product 2643kg after distillation is input into the product storage tank, with a yield of 85%, TPP: 0.18%.

[0023] Example 8: A method for preparing high-purity low-phosphorus triphenyl phosphate tert-butyl phenyl phosphonate, comprising the following steps: 1) Control the introduction of phosphorus oxychloride 2000kg and catalyst aluminum chloride 5.8kg (0.29% of the mass of phosphorus oxychloride) into the esterification reaction kettle, add p-tert-butyl phenol 1000kg with a double helix feeder, about 1 hour is needed for the addition, after the addition, slowly heat to 80-85℃ for 3 hours, heat to 90-100℃ for 4 hours, heat to 130-140℃ for 2 hours, and the hydrogen chloride gas generated in the reaction is absorbed by water injection; 2) After the reaction, the temperature is 60-100℃, the vacuum degree is 40-100KPa, and the phosphorus oxychloride is recovered by vacuum distillation, and then two-stage thin film molecular distillation is carried out, the first-stage thin film distillation is 200-250Pa, the second-stage thin film distillation is 30-50Pa, and the temperature is 60-100℃, to obtain the p-tert-butyl phosphorus oxychloride intermediate; 3) The p-tert-butyl phosphorus oxychloride intermediate of step 2) is transferred to the next reaction kettle under nitrogen, heated, and the temperature is controlled at 110-120℃, then phenol 1300kg is introduced, about 3 hours are needed for the introduction, after the introduction, 2 hours of heat preservation are needed, then vacuum is extracted, the vacuum degree is 60-100Pa, and the temperature is 130-140℃, and the acid is extracted for 1 hour, to obtain the crude tert-butyl phenyl phosphonate; 4) The crude tert-butyl phenyl phosphate is added to toluene, washed with 3% sodium hydroxide solution, washed with water, washing temperature 55-60°C, water layer PH = 7-8; the water-washed tert-butyl phenyl phosphate is distilled under reduced pressure at a temperature of 90-130°C and a vacuum degree of 60-100 Pa, and the distilled product 2643 kg is input into a product storage tank, with a yield of 94.7% and TPP of 0.12%.

[0024] Example 9: A preparation method of tert-butylated phenyl phosphate of high-purity low-phosphorus triphenyl phosphate, comprising the following steps: 1) Control the passage of phosphorus oxychloride 2000 kg and catalyst aluminum chloride 5.8 kg (0.29% of the mass of phosphorus oxychloride) into an esterification reactor, add p-tert-butyl phenol 1000 kg through a double-screw feeder, complete the addition in about 1 hour, slowly warm to 80-85°C for 3 hours, warm to 110-120°C for 4 hours, warm to 130-140°C for 2 hours, and absorb the generated hydrogen chloride gas by water injection; 2) After the reaction is completed, recover and distill the phosphorus oxychloride under reduced pressure at a temperature of 60-100°C and a vacuum degree of 40-100 KPa, and then perform reduced pressure distillation through two-stage thin film molecular distillation, with a first-stage thin film distillation vacuum degree of 200-250 Pa and a second-stage thin film distillation vacuum degree of 30-50 Pa, and a temperature of 60-100°C, to obtain a p-tert-butyl phosphorus oxychloride intermediate; 3) Under nitrogen, transfer the p-tert-butyl phosphorus oxychloride intermediate of step 2) to a next-stage reactor, warm, control the temperature at 110-120°C, then pass in phenol 1300 kg, complete the passage in about 3 hours, after the passage, warm for 2 hours, then vacuumize, vacuum degree 60-100 Pa, temperature 130-140°C, and acidize for 1 hour, to obtain a crude tert-butyl phenyl phosphate; 4) The crude tert-butyl phenyl phosphate is added to toluene, washed with 3% sodium hydroxide solution, washed with water, washing temperature 55-60°C, water layer PH = 7-8; the water-washed tert-butyl phenyl phosphate is distilled under reduced pressure at a temperature of 90-130°C and a vacuum degree of 60-100 Pa, and the distilled product 2643 kg is input into a product storage tank, with a yield of 94.7% and TPP of 0.12%.

[0025] Example 10: A preparation method of tert-butylated phenyl phosphate of high-purity low-phosphorus triphenyl phosphate, comprising the following steps: 1) Control the phosphorus oxychloride 2000 kg, catalyst aluminum chloride 5.8 kg (0.29% of the mass of phosphorus oxychloride) into the esterification reactor, using a double screw feeder to add p-tert-butyl phenol 1000 kg, about 1 hour to add, after adding slowly to warm to 90-100 ℃ for 5 hours, to warm to 130-140 ℃ for 4 hours, the reaction of hydrogen chloride gas generated by the method of water injection for absorption; 2) After the reaction, the temperature is 60-100 ℃, the vacuum degree is 40-100 KPa, the distillation of phosphorus oxychloride is recovered under reduced pressure, and then two-stage thin film molecular distillation is carried out under reduced pressure, the first-stage thin film distillation is 200-250 Pa, the second-stage thin film distillation is 30-50 Pa, and the temperature is 60-100 ℃, to obtain the p-tert-butyl phosphorus oxychloride intermediate; 3) The p-tert-butyl phosphorus oxychloride intermediate of step 2) is transferred to the next reaction kettle under nitrogen, the temperature is controlled at 110-120 ℃, then phenol 1300 kg is introduced, about 3 hours to complete, after the completion of the introduction, the temperature is kept for 2 hours, then the vacuum degree is 60-100 Pa, the temperature is 130-140 ℃, and the acid is extracted for 1 hour, to obtain the crude p-tert-butyl phenyl phosphonate; 4) The crude p-tert-butyl phenyl phosphonate is added to toluene, washed with 3% sodium hydroxide solution, washed with water, the washing temperature is 55-60 ℃, the water layer PH=7-8; the p-tert-butyl phenyl phosphonate washed with water is distilled under reduced pressure, the temperature is 90-130 ℃, the vacuum degree is 60-100 Pa, the product after distillation 2643 kg is input into the product storage tank, the yield is 93.9%, and the TPP is 0.14%.

[0026] Example 11: A method for preparing high-purity low-phosphorus triphenyl phosphate tert-butyl phenyl phosphonate, comprising the following steps: 1) Control the phosphorus oxychloride 2000 kg, catalyst aluminum chloride 5.8 kg (0.29% of the mass of phosphorus oxychloride) into the esterification reactor, using a double screw feeder to add p-tert-butyl phenol 1000 kg, about 1 hour to add, after adding slowly to warm to 80-85 ℃ for 5 hours, to warm to 130-140 ℃ for 4 hours, the reaction of hydrogen chloride gas generated by the method of water injection for absorption; 2) After the reaction, the temperature is 60-100 ℃, the vacuum degree is 40-100 KPa, the distillation of phosphorus oxychloride is recovered under reduced pressure, and then two-stage thin film molecular distillation is carried out under reduced pressure, the first-stage thin film distillation is 200-250 Pa, the temperature is 60-100 ℃, to obtain the p-tert-butyl phosphorus oxychloride intermediate; 3) The p-tert-butyl phosphinic chloride intermediate of step 2) is transferred to the next reactor under nitrogen, heated and the temperature is controlled at 110-120°C, then phenol 1300 kg is introduced, which is completed in about 3 hours, after which the temperature is maintained for 2 hours, then vacuum is applied, the vacuum degree is 60-100 Pa, the temperature is 130-140°C, and the acid is extracted for 1 hour to obtain the crude p-tert-butyl phenyl phosphinate; 4) The crude p-tert-butyl phenyl phosphinate is added to toluene, washed with 3% sodium hydroxide solution, washed with water, the washing temperature is 55-60°C, the water layer PH=7-8; the p-tert-butyl phenyl phosphinate washed with water is distilled under reduced pressure, the distillation temperature is 90-130°C, the vacuum degree is 60-100 Pa, the product 2643 kg after distillation is input into the product storage tank, the yield is 94.8%, and TPP is 0.14%.

Claims

1. A process for the preparation of high purity tertiary butylated phenyl phosphates of triphenyl phosphate phosphates of low phosphorus, characterized in that The method comprises the following steps: 1) according to the feeding ratio, phosphorus oxychloride and Lewis catalyst are added into an esterification reactor, then p-tert-butyl phenol is slowly added, and esterification is carried out through gradient temperature rising, wherein the gradient temperature rising process is as follows: 80-85°C for 3 hours, 90-100°C for 2 hours, 110-120°C for 2 hours, and 130-140°C for 2 hours; after the reaction is completed, the temperature of the reaction liquid in step 1) is reduced to 60-100°C, and phosphorus oxychloride is removed by vacuum distillation under a vacuum degree of 40-100 KPa, then phosphorus oxychloride is further removed by two-stage thin film molecular distillation at 60-100°C, the vacuum degree of the first-stage thin film distillation is 200-300 Pa, and the vacuum degree of the second-stage thin film distillation is 30-50 Pa, so that a p-tert-butyl phosphinic chloride intermediate is obtained; 3) under a nitrogen atmosphere, the p-tert-butyl phosphinic chloride intermediate in step 2) is heated to 110-120°C, phenol is added for capping, and a crude tert-butyl phenyl phosphinate is obtained; 4) after the crude product obtained in step 3) is washed with alkali and water, vacuum distillation is carried out to obtain a finished product tert-butyl phenyl phosphinate.

2. A process for the preparation of high purity tertiary butylated phenyl phosphonate of triphenyl phosphonate of low phosphorus according to claim 1, characterized by The molar ratio of p-tert-butyl phenol to phosphorus oxychloride in step 1) is 1:3-4.

5.

3. A process for the preparation of high purity tertiary butylated phenyl phosphonate of triphenyl phosphonate of low phosphorus according to claim 1, characterized by The Lewis acid catalyst in step 1) is any one of titanium tetrachloride, butyl titanate, magnesium chloride or aluminum chloride, and the amount is 0.25-0.4% of the mass of phosphorus oxychloride.

4. The process for the preparation of high purity tertiary butylated phenyl phosphonate of triphenyl phosphonate of low phosphorus according to claim 1, characterized in that The molar ratio of phenol to p-tert-butyl phenol in step 3) is 3-4:

1.

5. The process for the preparation of high purity tertiary butylated phenyl phosphonate of triphenyl phosphonate of low phosphorus according to claim 1, characterized by In step 4), 3% sodium hydroxide solution is used for alkali washing, the temperature during alkali washing and water washing is 50-70°C, the vacuum distillation temperature is 90-130°C, and the vacuum degree is 30-100 Pa.

6. A process for the preparation of high purity tertiary butylated phenyl phosphates of triphenyl phosphate phosphates of low phosphorus according to claim 5, characterized by During alkali washing and water washing, a solvent such as toluene or xylene is added to better separate the layers for washing.

7. A process for the preparation of high purity tertiary butylated phenyl phosphates of triphenyl phosphate of low phosphorus acid according to any one of claims 1 to 6, characterized in that The feeding time of p-tert-butyl phenol in step 1) is 0.8-1.2 hours.

8. A process for the preparation of high purity tertiary butylated phenyl phosphates of triphenyl phosphate of low phosphorus acid according to any one of claims 1 to 6, characterized in that The hydrogen chloride gas generated in step 1) is absorbed by water spraying.