CONTINUOUS INDUSTRIAL PRODUCTION METHOD OF HIGH-PURITY BISPHENOL A-BIS(DIPHENYL PHOSPHATE)

Abstract

Disclosed is a continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate). The method includes: dividing bisphenol A into two parts, mixing a part of the bisphenol A with phosphorus oxychloride and a Lewis acid catalyst, adding the mixture into a continuous multistage crosslinked reactor, removing excessive phosphorus oxychloride through distillation, adding an organic base acid binding agent and the rest of the bisphenol A to react for 1.5 to 3 h at a temperature of 115° C. to 120° C. to obtain an intermediate product reaction liquid, mixing the intermediate product reaction liquid with phenol, adding the mixture into a multistage esterification reactor for esterification reaction, continuously supplying the consumed phenol in the esterification process, obtaining a crude product after the reaction is completed, sequentially performing continuous acid washing, continuous alkali washing and continuous water washing, and performing continuous solvent recovery and filtration to obtain a bisphenol A-bis(diphenyl phosphate) finished product.

Claims

1. A continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate), comprising the following processes: 1) dividing bisphenol A into two parts, firstly premixing a part of the bisphenol A with phosphorus oxychloride and a Lewis acid catalyst to form a reaction liquid; adding the reaction liquid into a continuous multistage crosslinked reactor in a continuous feeding manner, and taking a reaction by controlling a reaction temperature at 80° C. to 120° C. and a reaction pressure at −0.015 to −0.02 MPa; after the reaction is completed, removing excessive phosphorus oxychloride by using a film evaporator through reduced pressure distillation, adding an organic base acid binding agent and the rest of the bisphenol A into a distillation remaining liquid, and taking a reaction for 1.5 to 3 h at a temperature of 115° C. to 120° C. to obtain an intermediate product reaction liquid; 2) premixing the intermediate product reaction liquid obtained in the step 1) with a phenol initial raw material, then, adding the mixture into a multistage esterification reactor in a continuous feeding manner, and taking an esterification reaction by controlling a reaction temperature at 90 to 150° C. and a reaction pressure at −0.015 to 0.02 MPa; continuously supplying consumed phenol in the multistage esterification reaction process so that a reaction progress is accelerated, obtaining a bisphenol A-bis(diphenyl phosphate) crude product after the reaction is completed, and dissolving the crude product into an organic solvent to form a crude product solution; and 3) sequentially performing continuous acid washing, continuous alkali washing and continuous water washing on the crude product solution obtained in the step 2), and performing continuous solvent recovery and filtration to obtain a bisphenol A-bis(diphenyl phosphate) finished product.

2. The continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate) according to claim 1, wherein in the step 1), a first part of the bisphenol A firstly participating in the reaction accounts for 70% to 80% of the total amount of the bisphenol A, and the rest of the bisphenol A finally participating in the reaction accounts for 30% to 20% of the total amount of bisphenol A.

3. The continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate) according to claim 1, wherein in the step 1), the Lewis acid catalyst is at least one of anhydrous magnesium chloride, anhydrous aluminum chloride, zinc chloride and titanium tetrachloride; and a weight of the added Lewis acid catalyst is 0.1% to 2% of a total weight of two parts of the bisphenol A.

4. The continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate) according to claim 1, wherein in the step 1), a ratio of a weight of the added phosphorus oxychloride to a total weight of the two parts of the added bisphenol A is 2.5-3.5:1.

5. The continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate) according to claim 1, wherein in the step 1), the organic base acid binding agent is organic amine, and a ratio of a weight of the added organic base acid binding agent to the total weight of the two parts of the added bisphenol A is 1:7-8.

6. The continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate) according to claim 5, wherein the organic amine is triethylamine, ammonia gas or N-methylmorpholine.

7. The continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate) according to claim 1, wherein in the step 1), the continuous multistage crosslinked reactor comprises four stages of reactors, a reaction temperature of a first-stage reactor is 80° C. to 85° C., a reaction temperature of a second-stage reactor is 90° C. to 100° C., a reaction temperature of a third-stage reactor is 100° C. to 110° C., a reaction temperature of a fourth-stage reactor is 110° C. to 120° C., and a dwell time of materials in each reactor is 2 to 2.5 h.

8. The continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate) according to claim 1, wherein in the step 2), the multistage esterification reactor comprises four stages of reactors connected in series, a reaction temperature of a first-stage reactor is 90° C. to 105° C., a reaction temperature of a second-stage reactor is 110° C. to 115° C., a reaction temperature of a third-stage reactor is 130° C. to 135° C., a reaction temperature of a fourth-stage reactor is 140° C. to 145° C., and a dwell time of materials in each reactor is 1.5 to 2 h.

9. The continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate) according to claim 1, wherein in the step 2), the multistage esterification reactor comprises four stages of reactors connected in series, consumed phenol is additionally supplied into a second-stage reactor, a third-stage reactor and a fourth-stage reactor, and an amount of the phenol supplied to each stage is 1% to 5% of a weight of the phenol initial raw material.

10. The continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate) according to claim 1, wherein a ratio of a total weight of the two parts of the bisphenol A in the step 1) to a weight of the phenol initial raw material in the step 2) is 2-2.5:1.

Description

DESCRIPTION OF THE EMBODIMENTS

[0028] The present invention will be further illustrated hereafter in combination with specific embodiments, but the protection scope of the present invention is not limited thereto.

Embodiment 1

[0029] A continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate) specifically included the following steps:

[0030] 1. Multistage crosslinked reaction:

[0031] Phosphorus oxychloride (4500 Kg/h), magnesium chloride (20 Kg/h) and bisphenol A (1200 Kg/h) were proportionally and continuously added into a premixing kettle, and were premixed in the premixing kettle in a heated manner, then, a reaction liquid in the premixing kettle flew into a fourth-stage reactor from a first-stage reactor in a continuous feeding manner, a reaction temperature of the first-stage reactor was 80° C. to 85° C., a reaction temperature of a second-stage reactor was 90° C. to 100° C., a reaction temperature of a third-stage reactor was 100° C. to 110° C., a reaction temperature of the fourth-stage reactor was 110° C. to 120° C., a dwell time of materials in each reactor was 2 h, and a reaction pressure was respectively controlled at −0.015 mpa to −0.02 mpa.

[0032] For the reaction liquid flowing out from the fourth-stage reactor, excessive phosphorus oxychloride was removed by using a film evaporator through reduced pressure distillation, a vacuum degree was 50 pa, a distillation temperature was 120° C. to 130° C., and a distillation remaining liquid was continuously supplied into a fifth-stage reactor at a flow rate of 2500 kg/h. At the same time, bisphenol A (300 Kg/h) and triethylamine (220 Kg/h) were input into the fifth-stage reactor for esterification reaction, a reaction temperature of the fifth-stage reactor was 115° C. to 120° C., a material dwell time was 2 h, and an intermediate product reaction liquid was obtained after the reaction was completed.

[0033] 2. Multistage Esterification Reaction:

[0034] The intermediate product reaction liquid obtained in the step 1 was added into a static mixer at a flow rate of 3000 kg/h. At the same time, the phenol was added into the static mixer at a flow rate of 2100 kg/h to be mixed. The obtained mixed liquid flew to the fourth-stage reactor from the first-stage reactor in a continuous feeding manner, a reaction temperature of the first-stage reactor was 100° C. to 105° C., a reaction temperature of a second-stage reactor was 120° C. to 130° C., phenol at a flow rate of 100 kg/h was introduced and supplied at the same time of the second-stage reaction, a reaction temperature of the third-stage reactor was 130° C. to 135° C., phenol at a flow rate of 100 kg/h was introduced and supplied at the same time of the third-stage reaction, a reaction temperature of the fourth-stage reactor was 140° C. to 145° C., phenol at a flow rate of 100 kg/h was introduced and supplied at the same time of the fourth-stage reaction, a dwell time of materials of each reactor was 2 h, each reaction pressure was controlled to be −0.015 mpa to −0.02 mpa, and a crude product was finally obtained. The obtained crude product was dissolved into toluene at a mass ratio of 1:1 to form a crude product solution.

[0035] 3. Crude Product Refining

[0036] The crude product solution (4800 Kg/h) and 10% hydrochloric acid (800 Kg/h) were introduced into an acid washing tower, and a circulating pump was started for forced circulation. After materials rise to a half of the volume of an acid washing tank, an acid washing feeding pump was started, at the same time, a mixed solvent (8000 Kg/h) was introduced for extraction in a washing tower, a mixed liquid enters an acid washing layering tower for layering, and a temperature was controlled at 60° C. to 70° C. in an acid washing process.

[0037] After the acid washing was completed, an organic layer (12800 Kg/h) obtained after acid washing layering and a 5% alkali liquid (2000 Kg/h) were introduced into an alkali washing tower for alkali washing, the mixed liquid entered an alkali washing layering tower for layering, and a temperature was controlled to be 60° C. to 70° C. in the alkali washing process.

[0038] After the alkali washing was completed, the organic layer (12800 Kg/h) obtained after the alkali washing layering and process water (1500 Kg/h) were introduced into a water washing tower for water washing, the mixed liquid entered a water washing layering tower for layering, and a temperature was controlled to be 60° C. to 70° C. in the water washing process.

[0039] For the crude product after water washing, a residual solvent was removed through film distillation, a film distillation temperature was 120° C. to 130° C., a vacuum degree was 40 to 70 pa, 4319 kg of a bisphenol A-bis(diphenyl phosphate) finished product was obtained, and a product yield was 98%.

Comparative Example 1

[0040] A continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate) had the same experiment steps as Embodiment 1. The difference was only that in Comparative example 1, in the multistage crosslinked reaction work procedure in step 1, the bisphenol A was added in one step, and no triethylamine was added, and the rest steps were identical to those of Embodiment 1.

[0041] Specifically, a process of the multistage crosslinked reaction work procedure in Comparative example 1 was as follows:

[0042] 1. Multistage Crosslinked Reaction:

[0043] Phosphorus oxychloride (4500 Kg/h), magnesium chloride (20 Kg/h) and bisphenol A (1500 Kg/h) were proportionally and continuously added into a premixing kettle, and were premixed in the premixing kettle in a heated manner, then, a reaction liquid in the premixing kettle flew into a fourth-stage reactor from a first-stage reactor in a continuous feeding manner, a reaction temperature of the first-stage reactor was 80° C. to 85° C., a reaction temperature of a second-stage reactor was 90° C. to 100° C., a reaction temperature of a third-stage reactor was 100° C. to 110° C., a reaction temperature of the fourth-stage reactor was 110° C. to 120° C., a dwell time of materials in each reactor was 2 h, and a reaction pressure was respectively controlled at −0.015 mpa to −0.02 mpa.

[0044] For the reaction liquid flowing out from the fourth-stage reactor, excessive phosphorus oxychloride was removed by using a film evaporator through reduced pressure distillation, a vacuum degree was 50 pa, a distillation temperature was 120° C. to 130° C., and an intermediate product reaction liquid obtained after the complete reaction took a multistage esterification reaction for a next step.

Comparative Example 2

[0045] A continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate) had the same experiment steps as Embodiment 1. The difference was only that in Comparative example 2, in the multistage crosslinked reaction work procedure in step 1, the bisphenol A was added in two times, and no triethylamine was added, and the rest steps were identical to those of Embodiment 1.

[0046] Specifically, a process of the multistage crosslinked reaction work procedure in Comparative example 2 was as follows:

[0047] 1. Multistage Crosslinked Reaction:

[0048] Phosphorus oxychloride (4500 Kg/h), magnesium chloride (20 Kg/h) and bisphenol A (1200 Kg/h) were proportionally and continuously added into a premixing kettle, and were premixed in the premixing kettle in a heated manner, then, a reaction liquid in the premixing kettle flew into a fourth-stage reactor from a first-stage reactor in a continuous feeding manner, a reaction temperature of the first-stage reactor was 80° C. to 85° C., a reaction temperature of a second-stage reactor was 90° C. to 100° C., a reaction temperature of a third-stage reactor was 100° C. to 110° C., a reaction temperature of the fourth-stage reactor was 110° C. to 120° C., a dwell time of materials in each reactor was 2 h, and a reaction pressure was respectively controlled at −0.015 mpa to −0.02 mpa.

[0049] For the reaction liquid flowing out from the fourth-stage reactor, excessive phosphorus oxychloride was removed by using a film evaporator through reduced pressure distillation, a vacuum degree was 50 pa, a distillation temperature was 120° C. to 130° C., and a distillation remaining liquid was continuously supplied into a fifth-stage reactor at a flow rate of 2500 kg/h. At the same time, bisphenol A (500 Kg/h) was input into the fifth-stage reactor for esterification reaction, a reaction temperature of the fifth-stage reactor was 115° C. to 120° C., a material dwell time was 2 h, and an intermediate product reaction liquid obtained after the reaction was completed took a multistage esterification reaction for a next step.

Comparative Example 3

[0050] A continuous industrial production method of high-purity bisphenol A-bis(diphenyl phosphate) had the same experiment steps as Embodiment 1. The difference was only that in Comparative example 3, in the multistage crosslinked reaction work procedure in step 1, the bisphenol A was added in one step, and triethylamine was added, and the rest steps were identical to those of Embodiment 1.

[0051] Specifically, a process of the multistage crosslinked reaction work procedure in Comparative example 3 was as follows:

[0052] 1. Multistage Crosslinked Reaction:

[0053] Phosphorus oxychloride (4500 Kg/h), magnesium chloride (20 Kg/h) and bisphenol A (1500 Kg/h) were proportionally and continuously added into a premixing kettle, and were premixed in the premixing kettle in a heated manner, then, a reaction liquid in the premixing kettle flew into a fourth-stage reactor from a first-stage reactor in a continuous feeding manner, a reaction temperature of the first-stage reactor was 80° C. to 85° C., a reaction temperature of a second-stage reactor was 90° C. to 100° C., a reaction temperature of a third-stage reactor was 100° C. to 110° C., a reaction temperature of the fourth-stage reactor was 110° C. to 120° C., a dwell time of materials in each reactor was 2 h, and a reaction pressure was respectively controlled at −0.015 mpa to −0.02 mpa.

[0054] For the reaction liquid flowing out from the fourth-stage reactor, excessive phosphorus oxychloride was removed by using a film evaporator through reduced pressure distillation, a vacuum degree was 50 pa, a distillation temperature was 120° C. to 130° C., and a distillation remaining liquid was continuously supplied into a fifth-stage reactor at a flow rate of 2800 kg/h. At the same time, triethylamine (220 Kg/h) was input into the fifth-stage reactor for esterification reaction, a reaction temperature of the fifth-stage reactor was 115° C. to 120° C., a material dwell time was 2 h, and an intermediate product reaction liquid was obtained after the reaction was completed.

Embodiment 2

[0055] Embodiment 2 was basically identical to Embodiment 1, the amount of phosphorus oxychloride was changed into 5500 Kg/h, and other reaction conditions were unchanged.

Embodiment 3

[0056] Embodiment 3 was basically identical to Embodiment 1, the adding proportions of the bisphenol A in two times were changed, the amount of the added bisphenol A in the first time was changed into 70% of the total amount (that is, a flow rate of the bisphenol A firstly participating in the reaction was 1050 kg/h), the rest 30% of the bisphenol A was added in the second time (that is, a flow rate of the rest of the bisphenol A participating in the reaction in the later stage was 450 kg/h), other reaction conditions were unchanged, and the experiment was performed.

Embodiment 4: Experiment Performed by Traditional Method

[0057] 1. 4500 kg of phosphorus oxychloride and 20 kg of magnesium chloride were sequentially added into a glass-lined reaction kettle. Stirring was performed, and the temperature was slowly raised. When the temperature was raised to 90° C. to 100° C., 1500 kg of bisphenol A was started to be added, and the adding time was 4 h. After the bisphenol A was added, the temperature was raised to 115 to 120° C., and was then preserved for 8 h. After the temperature preservation was completed, the reactor was changed to remove phosphorus oxychloride. A vacuum pump was started, the phosphorus oxychloride was removed through distillation. Most phosphorus oxychloride was firstly removed at a low temperature, then, the vacuum was adjusted to −0.98 mpa, the temperature was continuously raised to 130 to 140° C. and was preserved until no phosphorus oxychloride was distilled, the distillation time was totally about 5 to 8 h, and an intermediate product was obtained.

[0058] 2. The above intermediate product was transferred into a reaction kettle, the temperature was raised to 110° C. to 120° C., 2400 kg of phenol was added dropwise, and the adding time was about 4 h. After the dropwise addition was completed, the temperature was raised to 140° to 150° C., the heat preservation was performed for 4 h, sampling and analysis were performed, and a crude product was obtained.

[0059] 3. The crude product was completely transferred into a washing kettle, a solvent was added, the temperature was raised to 65 to 70° C., then, 800 kg of quantity fixing water was slowly added, 1000 kg of 30% hydrochloric acid was added, the temperature was raised to 65° C. to 70° C., stirring was performed for 1 h, and still standing was performed for half an hour to separate out a water layer. Then, 1000 kg of water was added, 400 kg of 30% sodium hydroxide was added, the temperature was raised to 65° C. to 70° C., stirring was performed for 1 h, and 1 standing was performed for half an hour to separate a water layer. 1500 kg of water was slowly added into a material layer, the temperature was raised to 65° C. to 70° C., and was preserved for 1 h. Still standing was performed for half an hour to separate out a water layer, water washing was performed twice, and a pH value was tested to be 6 to 7. After the washing was completed, the materials were conveyed into a distillation still to remove the solvent, a reduced pressure distillation temperature was finally raised to 140° C. to 150° C., and a sample was obtained after the solvent was removed.

[0060] Performance Test on Prepared Bisphenol A-Bis(Diphenyl Phosphate) Product

[0061] 1. Detection method:

[0062] 1) Color number determination method: GB-3143;

[0063] 2) Acid value determination method: GB-264-1983;

[0064] 3) Liquid chromatography method for triphenyl phosphate content detection, specifically characterized in that:

[0065] Chromatographic condition: mobile phase:methanol:water=90:10, chromatographic column: Diamonsil (150 mm×4.6 mm, 5 um), detection wavelength: 254 nm, column temperature: 25° C., and sample volume: 20 ul.

[0066] A triphenyl phosphate standard product (content 99.8%) was weighed to prepare 0.1%, 0.2%, 0.4%, 0.6%, 1.0%, 1.5% and 2.0% solutions, the solutions were diluted by methanol, and a standard curve was made.

[0067] Sample preparation: 0.2 g of the sample was weighed, and was diluted by the mobile phase to 10 ml, dissolution and sample feeding were performed, and the sample volume was 20 ul. The content of triphenyl phosphate in the sample was calculated according to the standard curve.

[0068] 4) Liquid chromatography method for isopropylphenyl diphenyl phosphate content detection, specifically characterized in that:

[0069] Chromatographic condition: mobile phase:methanol:water=90:10, chromatographic column: Diamonsil (150 mm×4.6 mm, 5 um), detection wavelength: 254 nm, column temperature: 25° C., and sample volume: 20 ul.

[0070] An isopropylphenyl diphenyl phosphate standard product (content 99.8%) was weighed to prepare 10 ppm, 20 ppm, 40 ppm, 60 ppm, 80 ppm and 100 ppm solutions, the solutions were diluted by methanol, and a standard curve was made.

[0071] Sample preparation: 0.2 g of the sample was weighed, and was diluted by the mobile phase to 10 ml, dissolution and sample feeding were performed, and the sample volume was 20 ul. The content of isopropylphenyl diphenyl phosphate in the sample was calculated according to the standard curve.

[0072] 2. Sample: products prepared according to Embodiments 1 to 4 and Comparative examples 1 and 3.

[0073] 3. Experiment results: see Table 1.

TABLE-US-00001 TABLE 1 Experiment results Comparative Comparative Comparative Item Embodiment 1 example 1 example 2 example 3 Embodiment 2 Embodiment 3 Embodiment 4 Color 20 50 40 50 30 30 60 number Yield   98%   94%   95% 95.2% 97.5% 98.5% 85% Content of 0.10% 0.85% 0.56% 0.41% 0.12% 0.08% 2.1% triphenyl phosphate Content of 31 5608 6101 4202 42 23 11008 isopropylphenyl diphenyl phosphate (ppm)

[0074] The results in Table 1 show that: through comparison of Embodiments 1 to 3 with Comparative examples 1 to 2 and Embodiment 4, the contents of isopropylphenyl diphenyl phosphate and triphenyl phosphate in the product prepared by the method of the present invention were greatly reduced, the content of the triphenyl phosphate was reduced from 2% or higher to 0.1% or lower of the triphenyl phosphate, the content of isopropylphenyl diphenyl phosphate was reduced to 40 ppm or lower, and a product yield was improved to 97% or higher.

[0075] In the intelligent production process, the consumption can be reduced, the operation environment of workers is greatly improved, the labor cost is reduced, in the batch production process, the product quality and yield are stable, and high-end product can be stably produced. In a word, compared with a method in the prior art, the method provided by the present invention has the advantages that the yield is increased, the purity is increased, the impurity content is reduced, and the method is stable.