Continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate)
阅读说明：本技术 一种高纯双酚a-双（二苯基磷酸酯）的连续工业化生产方法 (Continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate) ) 是由 李旭锋 吕云兴 王秋伟 吴宪水 于 2020-12-07 设计创作，主要内容包括：本发明公开了一种高纯双酚A-双(二苯基磷酸酯)的连续工业化生产方法,将双酚A分为两部分,部分双酚A与三氯氧磷和路易斯酸催化剂混合,加料到连续多级交联反应器中反应,反应结束后蒸除过量的三氯氧磷,蒸馏剩余液中加入有机碱缚酸剂与剩余的双酚A在115-120℃温度下反应1.5-3h,获得中间产物反应液,再与苯酚混合后加料到多级酯化反应器中进行酯化反应,酯化的过程中连续补给消耗的苯酚,反应结束后得到粗品,依次经连续酸洗、连续碱洗、连续水洗,连续溶剂回收、过滤得到双酚A-双(二苯基磷酸酯)成品。本发明的方法降低生产成本,其产品收率提高到97%以上,产品色号提升至50以下、TPP控制0.1%,异丙烯基苯基二苯基磷酸酯小于50 ppm,各产品质量指标波动小。(The invention discloses a continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate), which comprises the steps of dividing bisphenol A into two parts, mixing part of bisphenol A with phosphorus oxychloride and a Lewis acid catalyst, feeding the mixture into a continuous multistage cross-linking reactor for reaction, evaporating excessive phosphorus oxychloride after the reaction is finished, adding an organic alkali acid-binding agent into the distillation residual liquid for reaction with the rest of bisphenol A at the temperature of 115 ℃ and 120 ℃ for 1.5-3 hours to obtain an intermediate product reaction liquid, mixing the intermediate product reaction liquid with phenol, feeding the mixture into a multistage esterification reactor for esterification reaction, continuously supplying consumed phenol during the esterification process, obtaining a crude product after the reaction is finished, and sequentially carrying out continuous acid washing, continuous alkali washing, continuous water washing, continuous solvent recovery and filtration to obtain a bisphenol A-bis (diphenyl phosphate) finished product. The method of the invention reduces the production cost, improves the product yield to more than 97 percent, improves the product color number to less than 50, controls the TPP to be 0.1 percent, controls the isopropenyl phenyl diphenyl phosphate to be less than 50 ppm, and has small fluctuation of the quality indexes of the products.)
1. A continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate) is characterized by comprising the following steps:
1) dividing bisphenol A into two parts, and firstly, premixing part of bisphenol A, phosphorus oxychloride and a Lewis acid catalyst to form a reaction solution; the reaction liquid is fed into a continuous multistage crosslinking reactor in a continuous feeding mode, the reaction temperature is controlled to be 80-120 ℃, and the reaction pressure is controlled to be-0.015 to-0.02 MPa for reaction; after the reaction is finished, removing excessive phosphorus oxychloride by reduced pressure distillation through a film evaporator, adding an organic alkali acid-binding agent and the rest bisphenol A into the distillation residual liquid, and reacting at the temperature of 115-120 ℃ for 1.5-3h 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, and then adding the mixture into a multistage esterification reactor in a continuous feeding mode, wherein the reaction temperature is controlled at 90-150 ℃, and the reaction pressure is-0.015-0.02 MPa to perform esterification reaction; continuously supplying consumed phenol in the process of multi-stage esterification reaction to accelerate the reaction process, obtaining a bisphenol A-bis (diphenyl phosphate) crude product after the reaction is finished, and dissolving the crude product in an organic solvent to form a crude product solution;
3) and (3) sequentially carrying out continuous acid washing, continuous alkali washing and continuous water washing on the crude product solution obtained in the step 2), and continuously recovering and filtering the solvent to obtain a finished product of the bisphenol A-bis (diphenyl phosphate).
2. The continuous industrial production process of high purity bisphenol A-bis (diphenylphosphate) according to claim 1, wherein in step 1), the first portion of bisphenol A to be reacted first is 70 to 80% of the total amount of bisphenol A, and the remaining portion of bisphenol A to be reacted last is 30 to 20% of the total amount of bisphenol A.
3. The continuous industrial production process of high purity bisphenol A-bis (diphenylphosphate) according to claim 1, wherein in step 1), the Lewis acid catalyst is at least one of anhydrous magnesium chloride, anhydrous aluminum chloride, zinc chloride and titanium tetrachloride, preferably anhydrous magnesium chloride; the weight of the Lewis acid catalyst is 0.1-2% of the total weight of the two parts of bisphenol A.
4. The continuous industrial process for producing highly pure bisphenol A-bis (diphenylphosphate) according to claim 1, wherein the ratio of the charged weight of phosphorus oxychloride to the total charged weight of two-part bisphenol A in step 1) is 2.5 to 3.5: 1.
5. The continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate) as claimed in claim 1, wherein in step 1), said organic base acid-binding agent is organic amine, and the ratio of the feeding weight of the organic base acid-binding agent to the total feeding weight of the two-part bisphenol A is 1: 7-8.
6. The continuous industrial process for producing high-purity bisphenol A-bis (diphenylphosphate) according to claim 5, wherein said organic amine is triethylamine, ammonia gas or N-methylmorpholine, preferably triethylamine.
7. The continuous industrial production method of high purity bisphenol A-bis (diphenyl phosphate) as claimed in claim 1, wherein in step 1), the continuous multi-stage crosslinking reactor comprises four-stage reactors, the reaction temperature of the first-stage reactor is 80-85 ℃, the reaction temperature of the second-stage reactor is 90-100 ℃, the reaction temperature of the third-stage reactor is 100-110 ℃, the reaction temperature of the fourth-stage reactor is 110-120 ℃, and the residence time of the materials in each reactor is 2-2.5 hours.
8. The continuous industrial production method of high purity bisphenol A-bis (diphenyl phosphate) as claimed in claim 1, wherein in step 2), the multi-stage esterification reactor comprises serially connected four-stage reactors, the temperature of the first stage reactor is 90-105 ℃, the reaction temperature of the second stage reactor is 110-.
9. The continuous industrial process for producing high purity bisphenol A-bis (diphenylphosphate) according to claim 1, wherein in step 2), the multi-stage esterification reactor comprises four-stage reactors connected in series, the second, third and fourth stage reactors are each additionally supplemented with the consumed phenol, and the amount of the phenol supplemented in each stage is 1-5% by weight of the starting phenol material.
10. The continuous industrial process for producing high purity bisphenol A bis (diphenylphosphate) according to claim 1, wherein the ratio of the total weight of the two-part bisphenol A of the step 1) to the weight of the phenol starting material of the step 2) is 2 to 2.5: 1.
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate).
Background
Bisphenol A-bis (diphenyl phosphate) (BDP for short) has a molecular formula of C39H34O8P2Molecular weight 692, its structural formula is as follows:
，
bisphenol A-bis (diphenyl phosphate) is an oligomeric non-halogen flame retardant and is a good plasticizer at the same time, is mainly applied to thermoplastic engineering plastics such as epoxy resin and polymers thereof for PC, ABS, PC/ABS and PPO/HIPS hard circuit boards, and has flame retardant property greatly superior to that of traditional flame retardants such as alkyl phenyl phosphate. In recent years, new energy automobiles have been widely popularized, and the demand for bisphenol a-bis (diphenyl phosphate) has been remarkably increased, and the market demand is low.
At present, the preparation method of bisphenol a-bis (diphenyl phosphate) flame retardant is mainly chinese patent CN101456879A (application No. 200710179279.4, entitled preparation method of flame retardant bisphenol a bis (diphenyl phosphate)), which adopts phosphorus oxychloride to react with bisphenol a, after the reaction, the phosphorus oxychloride is distilled out under reduced pressure, and then phenol is used for end capping treatment to obtain bisphenol a-bis (diphenyl phosphate).
For example, chinese patent CN101348500A, chinese patent CN1414968A, chinese patent CN1367788A and the like all disclose a production method of bisphenol a-bis (diphenyl phosphate), the production process is: reacting bisphenol A with excessive phosphorus oxychloride in the presence of a Lewis catalyst, then removing the excessive phosphorus oxychloride by high vacuum reduced pressure distillation, reacting with phenol to prepare a BDP crude product, further carrying out acid washing, alkali washing and water washing on the BDP crude product in the presence of a solvent, distilling to remove the solvent and water, and filtering to obtain the BDP product. Generally, BDP produced by the industrial method usually contains about 1 to 3 percent of triphenyl phosphate TPP and about 1 percent of isopropenyl diphenyl benzoate, which are harmful substances, and the instability phenomenon of isopropyl group, wherein the existence of isopropenyl causes the color of the product to change dark in illumination, and the existence of TPP causes the defects, pollution and corrosion of a molded product, and the problems of volatilization, exudation and the like easily occur after the product enters materials, thus affecting the flame retardance and other physical properties of the product.
The existing production method of bisphenol A-bis (diphenyl phosphate) is mainly intermittent synthesis reaction, intermittent reaction has long time period, needs a large amount of workers, has serious phenomena of bubble leakage and leakage in a chemical plant, has poor operating environment of the workers, can harm the health of human bodies, can generate danger of life sometimes, and has high energy consumption and low production yield. In addition, due to the existence of air and water vapor in the surrounding environment, the reaction process and the result of the intermittent process are greatly influenced, the prepared bisphenol A phenyl condensed phosphate BDP product contains more triphenyl phosphine oxide (TPP), the TPP has certain toxicity to aquatic organisms, and the TPP content of the product is strictly controlled in the international market.
Therefore, the method for continuously preparing the bisphenol A-bis (diphenyl phosphate) with high purity has important significance.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate).
The continuous industrial production method of the high-purity bisphenol A-bis (diphenyl phosphate) is characterized by comprising the following steps of:
1) dividing bisphenol A into two parts, and firstly, premixing part of bisphenol A, phosphorus oxychloride and a Lewis acid catalyst to form a reaction solution; the reaction liquid is fed into a continuous multistage crosslinking reactor in a continuous feeding mode, the reaction temperature is controlled to be 80-120 ℃, and the reaction pressure is controlled to be-0.015 to-0.02 MPa for reaction; after the reaction is finished, removing excessive phosphorus oxychloride by reduced pressure distillation through a film evaporator, adding an organic alkali acid-binding agent and the rest bisphenol A into the distillation residual liquid, and reacting at the temperature of 115-120 ℃ for 1.5-3h 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, and then adding the mixture into a multistage esterification reactor in a continuous feeding mode, wherein the reaction temperature is controlled at 90-150 ℃, and the reaction pressure is-0.015-0.02 MPa to perform esterification reaction; continuously supplying consumed phenol in the process of multi-stage esterification reaction to accelerate the reaction process, obtaining a bisphenol A-bis (diphenyl phosphate) crude product after the reaction is finished, and dissolving the crude product in an organic solvent to form a crude product solution;
3) and (3) sequentially carrying out continuous acid washing, continuous alkali washing and continuous water washing on the crude product solution obtained in the step 2), and continuously recovering and filtering the solvent to obtain a finished product of the bisphenol A-bis (diphenyl phosphate).
The continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate) is characterized in that in the step 1), the first part of bisphenol A which firstly participates in the reaction accounts for 70-80% of the total amount of bisphenol A, and the rest part of bisphenol A which finally participates in the reaction accounts for 30-20% of the total amount of bisphenol A.
The continuous industrial production method of the high-purity bisphenol A-bis (diphenyl phosphate) is characterized in that 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 is preferably anhydrous magnesium chloride; the weight of the Lewis acid catalyst is 0.1-2% of the total weight of the two parts of bisphenol A.
The continuous industrial production method of the high-purity bisphenol A-bis (diphenyl phosphate) is characterized in that in the step 1), the ratio of the feeding weight of the phosphorus oxychloride to the total feeding weight of the two parts of bisphenol A is 2.5-3.5: 1.
The continuous industrial production method of the high-purity bisphenol A-bis (diphenyl phosphate) is characterized in that in the step 1), the organic alkali acid-binding agent is organic amine, and the ratio of the feeding weight of the organic alkali acid-binding agent to the total feeding weight of the two parts of bisphenol A is 1: 7-8.
The continuous industrial production method of the high-purity bisphenol A-bis (diphenyl phosphate) is characterized in that the organic amine is triethylamine, ammonia gas or N-methylmorpholine, and triethylamine is preferred.
The continuous industrial production method of the high-purity bisphenol A-bis (diphenyl phosphate) is characterized in that in the step 1), the continuous multi-stage crosslinking reactor comprises a four-stage reactor, the reaction temperature of the first-stage reactor is 80-85 ℃, the reaction temperature of the second-stage reactor is 90-100 ℃, the reaction temperature of the third-stage reactor is 100-.
The continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate) is characterized in that in the step 2), the multistage esterification reactor comprises four-stage reactors connected in series, the temperature of the first-stage reactor is 90-105 ℃, the reaction temperature of the second-stage reactor is 110-.
The continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate) is characterized in that in the step 2), the multistage esterification reactor comprises four-stage reactors connected in series, the second, third and fourth stage reactors are additionally supplemented with consumed phenol, and the supplement amount of each stage of phenol is 1-5% of the weight of the initial raw material of phenol.
The continuous industrial production method of the high-purity bisphenol A-bis (diphenyl phosphate) is characterized in that the weight ratio of the total weight of the two parts of bisphenol A in the step 1) to the initial raw material of phenol in the step 2) is 2-2.5: 1.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1) according to the invention, part of bisphenol A is reacted firstly, the state of bisphenol A in the reaction process is solid, and if a large amount of bisphenol A is fed once in the reaction process, a large amount of bisphenol A solid exists in phosphorus oxychloride, so that the reaction of bisphenol A is slow, and thus under the condition of high temperature and long-time retention, bisphenol A is easy to generate decomposition side reaction at this time, and allyl phenol and phenol are decomposed. The two substances are easy to react with phosphorus oxychloride, allylphenol and phosphorus oxychloride are easy to react to generate isopropenylphenyl diphenyl phosphate as an impurity, phenol and phosphorus oxychloride are easy to react to generate triphenyl phosphate as an impurity, the two substances are harmful, and the content of the two substances is required to be strictly controlled in the production process of the product.
In the production process, bisphenol A is fed in two parts, excessive phosphorus oxychloride is removed after the first-stage reaction is finished, the produced intermediate contains a plurality of acyl chloride groups, the intermediate and the hydroxyl in the rest bisphenol are further subjected to crosslinking reaction, and the crosslinking reaction is performed by adding organic base to neutralize hydrogen chloride gas released in the reaction process, so that the reaction is performed in the positive direction, the reaction process is accelerated, and the purposes of shortening the reaction time and reducing impurities are achieved.
2) In the multi-stage esterification reaction process, a large amount of hydrogen chloride gas is released in the esterification reaction process, the hydrogen chloride gas is removed through negative pressure operation, phenol is easily taken out in the reaction removal process, and the reaction is carried out in the positive direction by a method of continuously introducing phenol for replenishment in the reaction process in each reactor, so that the esterification reaction is complete, and the low yield is avoided.
3) The production process disclosed by the invention has the advantages that the production cost is reduced, the labor intensity of operators is greatly reduced, the labor efficiency is improved, the product yield is greatly improved, the batch production quality is stable, the safe and environment-friendly production is achieved, the product yield is improved to more than 97%, the product color number is improved to less than 50, the TPP (thermoplastic vulcanizate) is controlled to 0.1%, the isopropenyl phenyl diphenyl phosphate is less than 50 ppm, and the quality index fluctuation of each product is small.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
a continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate) specifically comprises the following steps:
1. multi-stage crosslinking reaction:
4500Kg/h of phosphorus oxychloride, 20Kg/h of magnesium chloride and 1200Kg/h of bisphenol A are continuously fed into a premixing kettle in proportion, reaction liquid in the premixing kettle flows from a first-stage reactor to a fourth-stage reactor in a continuous feeding mode after being heated and premixed in the premixing kettle, the reaction temperature of the first-stage reactor is 80-85 ℃, the reaction temperature of the second-stage reactor is 90-100 ℃, the reaction temperature of the third-stage reactor is 100 plus materials, the reaction temperature of the fourth-stage reactor is 110 plus materials, the retention time of the materials in each reactor is 2 hours, and the reaction pressure is controlled to be carried out under-0.015 mpa to-0.02 mpa.
And distilling the excessive phosphorus oxychloride from the reaction liquid flowing out of the fourth-stage reactor through a thin film evaporator under reduced pressure, wherein the vacuum degree is 50pa, the distillation temperature is 120-130 ℃, the distillation residual liquid is continuously fed into the fifth-stage reactor at the flow rate of 2500kg/h, simultaneously, 300kg/h of bisphenol A and 220kg/h of triethylamine are fed into the fifth-stage reactor for esterification reaction, the reaction temperature of the fifth-stage reactor is 115-120 ℃, the materials stay for 2 hours, and the intermediate product reaction liquid is obtained after the reaction is completed.
2. Multistage esterification reaction
The intermediate product reaction liquid obtained in the step 1 is sent into a static mixer at the flow rate of 3000kg/h, phenol is sent into the static mixer at the flow rate of 2100kg/h for mixing, the obtained mixed liquid flows from a first-stage reactor to a fourth-stage reactor in a continuous feeding mode, the reaction temperature of the first-stage reactor is 105 ℃ plus the temperature of the second-stage reactor is 130 ℃ plus the temperature of the second-stage reactor, 100kg/h of flow rate phenol is introduced for replenishment while the second-stage reaction is carried out, the reaction temperature of the third-stage reactor is 130 plus the temperature of the third-stage reactor is 135 ℃, 100kg/h of flow rate phenol is introduced for replenishment while the third-stage reaction is carried out, the reaction temperature of the fourth-stage reactor is 140 plus the temperature of the fourth-stage reactor 145 ℃, 100kg/h of flow rate phenol is introduced for replenishment while the fourth-stage reaction is carried out, the material residence time of each reactor is 2 hours, and the reaction pressure is controlled to be carried out under, and finally obtaining a crude product. The resulting crude product was dissolved in toluene in a mass ratio of 1:1 to form a crude solution.
3. Refining of crude product
Introducing 4800kg/h of crude product solution and 800kg/h of 10% hydrochloric acid into the pickling tower, starting a circulating pump for forced circulation, starting a pickling feeding pump when the material rises to a half of the volume of a pickling tank, introducing 8000kg/h of mixed solvent into the pickling tower for extraction, allowing the mixed liquid to enter a pickling layering tower for layering, and controlling the temperature to be 60-70 ℃ in the pickling process;
after acid washing is finished, introducing an acid-washed layered organic layer of 12800kg/h and 5% alkali liquor of 2000 kg/h into an alkali washing tower for alkali washing, allowing mixed liquid to enter the alkali washing layered tower for layering, and controlling the temperature to be 60-70 ℃ in the alkali washing process;
after the alkaline washing is finished, introducing 12800kg/h of an organic layer subjected to alkaline washing layering and 1500kg/h of process water into a washing tower for washing, layering the mixed liquid in the washing layering tower, and controlling the temperature to be 60-70 ℃ in the washing process;
the residual solvent of the crude product after washing is removed by thin film distillation, the thin film distillation temperature is 120-130 ℃, and the vacuum is 40-70pa, thus obtaining 4319kg of finished product of bisphenol A-bis (diphenyl phosphate) with the product yield of 98 percent.
Comparative example 1:
a continuous industrial production method of high purity bisphenol A-bis (diphenyl phosphate) was carried out in the same manner as in example 1 except that "comparative example 1 was carried out in the step 1 multi-stage crosslinking reaction procedure, bisphenol A was added at one time without adding triethylamine", and the remaining steps were the same as in example 1.
Specifically, the procedure of the multistage crosslinking reaction procedure of the comparative document 1 is as follows:
1. multi-stage crosslinking reaction:
4500Kg/h of phosphorus oxychloride, 20Kg/h of magnesium chloride and 1500Kg/h of bisphenol A are continuously fed into a premixing kettle in proportion, reaction liquid in the premixing kettle flows from a first-stage reactor to a fourth-stage reactor in a continuous feeding mode after being heated and premixed in the premixing kettle, the reaction temperature of the first-stage reactor is 80-85 ℃, the reaction temperature of the second-stage reactor is 90-100 ℃, the reaction temperature of the third-stage reactor is 100 plus materials, the reaction temperature of the fourth-stage reactor is 110 plus materials, the retention time of the materials in each reactor is 2 hours, and the reaction pressure is controlled to be within-0.015 mpa to-0.02 mpa.
And (3) distilling the excessive phosphorus oxychloride from the reaction liquid flowing out of the fourth-stage reactor through a thin-film evaporator under reduced pressure, wherein the vacuum degree is 50pa, the distillation temperature is 120-130 ℃, and after the reaction is completed, obtaining an intermediate product reaction liquid for the next multi-stage esterification reaction.
Comparative example 2:
a continuous industrial production method of high purity bisphenol A-bis (diphenyl phosphate) was carried out in the same manner as in example 1 except that "comparative example 2, in the step 1 of multi-stage crosslinking reaction, bisphenol A was added in two portions without adding triethylamine" and the remaining steps were the same as in example 1.
Specifically, the procedure of the multistage crosslinking reaction procedure of the comparison document 2 is as follows:
1. multi-stage crosslinking reaction:
4500Kg/h of phosphorus oxychloride, 20Kg/h of magnesium chloride and 1200Kg/h of bisphenol A are continuously fed into a premixing kettle in proportion, reaction liquid in the premixing kettle flows from a first-stage reactor to a fourth-stage reactor in a continuous feeding mode after being heated and premixed in the premixing kettle, the reaction temperature of the first-stage reactor is 80-85 ℃, the reaction temperature of the second-stage reactor is 90-100 ℃, the reaction temperature of the third-stage reactor is 100 plus materials, the reaction temperature of the fourth-stage reactor is 110 plus materials, the retention time of the materials in each reactor is 2 hours, and the reaction pressure is controlled to be carried out under-0.015 mpa to-0.02 mpa.
And distilling the excessive phosphorus oxychloride from the reaction liquid flowing out of the fourth-stage reactor through a film evaporator under reduced pressure, wherein the vacuum degree is 50pa, the distillation temperature is 120-130 ℃, the flow rate of the distillation residual liquid is 2500kg/h, continuously feeding the excessive phosphorus oxychloride into the fifth-stage reactor, simultaneously feeding 500kg/h of bisphenol A into the fifth-stage reactor for esterification, the reaction temperature of the fifth-stage reactor is 115-120 ℃, keeping the materials for 2 hours, and obtaining an intermediate product reaction liquid after the reaction is completed for next multi-stage esterification.
Comparative example 3:
a continuous industrial production method of high purity bisphenol A-bis (diphenyl phosphate) was conducted in the same manner as in example 1 except that "comparative example 3, in the step 1 of multi-stage crosslinking reaction, bisphenol A was added at one time and triethylamine was added", and the remaining steps were the same as in example 1.
Specifically, the procedure of the multistage crosslinking reaction procedure of the comparison document 3 is as follows:
1. multi-stage crosslinking reaction:
4500Kg/h of phosphorus oxychloride, 20Kg/h of magnesium chloride and 1500Kg/h of bisphenol A are continuously fed into a premixing kettle in proportion, reaction liquid in the premixing kettle flows from a first-stage reactor to a fourth-stage reactor in a continuous feeding mode after being heated and premixed in the premixing kettle, the reaction temperature of the first-stage reactor is 80-85 ℃, the reaction temperature of the second-stage reactor is 90-100 ℃, the reaction temperature of the third-stage reactor is 100 plus materials, the reaction temperature of the fourth-stage reactor is 110 plus materials, the retention time of the materials in each reactor is 2 hours, and the reaction pressure is controlled to be within-0.015 mpa to-0.02 mpa.
And distilling the excessive phosphorus oxychloride from the reaction liquid flowing out of the fourth-stage reactor through a thin-film evaporator under reduced pressure, wherein the vacuum degree is 50pa, the distillation temperature is 120-130 ℃, 2800kg/h of distillation residual liquid is continuously fed into the fifth-stage reactor, 220kg/h of triethylamine is simultaneously input into the fifth-stage reactor for esterification, the reaction temperature of the fifth-stage reactor is 115-120 ℃, the material stays for 2 hours, and the intermediate product reaction liquid is obtained after the reaction is completed.
Example 2:
the amount of phosphorus oxychloride was changed to 5500kg/h in substantially the same manner as in example 1, and the other reaction conditions were unchanged.
Example 3:
basically the same as example 1, the two-time feeding ratio of bisphenol A was changed to 70% of the total amount of bisphenol A added for the first time (i.e., 1050kg/h for the first portion of bisphenol A to be reacted first) and to the remaining 30% of the total amount of bisphenol A added for the second time (i.e., 450kg/h for the second portion of bisphenol A to be reacted later), and the other reaction conditions were not changed.
Example 4: the conventional method is used for testing
1. 4500kg of phosphorus oxychloride and 20kg of magnesium chloride are sequentially added into the glass lining reaction kettle. Stirring and slowly heating. Heating to 90-100 deg.c, and feeding bisphenol A in 1500kg for 4 hr. After the feeding is finished, the temperature is raised to 115-plus-120 ℃ for heat preservation for 8 hours. After the heat preservation is finished, the kettle is rotated to remove phosphorus oxychloride. And starting a vacuum pump, distilling to remove phosphorus oxychloride, removing most of the phosphorus oxychloride at low temperature, adjusting the vacuum to-0.98 mpa, continuously heating to 130-140 ℃, keeping the temperature until no phosphorus oxychloride is evaporated, and distilling for about 5-8 hours to obtain an intermediate.
2. Transferring the intermediate into a reaction kettle, heating to 110-120 ℃, dropwise adding 2400kg of phenol for about 4 hours, heating to 140-150 ℃ after dropwise adding, preserving heat for 4 hours, sampling and analyzing to obtain a crude product.
3. Completely transferring the crude product into a washing kettle, adding a solvent, heating to 65-70 ℃, slowly adding 800kg of quantitative water, adding 1000kg of 30% hydrochloric acid, heating to 65-70 ℃, stirring for 1 hour, and standing for half a hour to obtain a water layer; then 1000kg of water is added, 400kg of liquid caustic soda 30% is added, the temperature is raised to 65-70 ℃, the mixture is stirred for 1 hour, and the mixture is kept still for half a hour to form a water layer. Adding 1500kg of water slowly into the material layer, heating to 65-70 ℃, preserving the heat for 1 hour, standing for half a hour to form a water layer, and washing with water to test the pH = 6-7 for the second time. And after washing, feeding the materials to a distillation kettle to remove the solvent, raising the temperature of reduced pressure distillation to 140-150 ℃, and obtaining a sample after the solvent is removed.
Performance testing of the prepared bisphenol a-bis (diphenyl phosphate) product:
1. the detection method comprises the following steps:
1) the color number determination method comprises the following steps: GB-3143;
2) the acid value measurement method comprises the following steps: GB-264-1983;
3) the method for detecting the content of triphenyl phosphate adopts a liquid chromatography method, and specifically comprises the following steps:
chromatographic conditions are as follows: mobile phase: methanol: water = 90:10, column: Diamonsil (150mm × 4.6mm,5um) detection wavelength: 254 nm. Column temperature: 25 ℃, injection volume: 20 ul;
triphenyl phosphate standard (content 99.8%) is weighed and prepared into 0.1%, 0.2%, 0.4%, 0.6%, 1.0%, 1.5% and 2.0% solution, and diluted with methanol to make a standard curve.
Sample preparation: weighing 0.2g sample, diluting to 10ml with mobile phase, dissolving, injecting sample, and injecting sample 20 ul. The triphenyl phosphate content in the sample is calculated according to the standard curve.
4) The method for detecting the content of isopropenyl phenyl diphenyl phosphate adopts a liquid chromatography method, and specifically comprises the following steps:
chromatographic conditions are as follows: mobile phase: methanol: water = 90:10, column: Diamonsil (150mm × 4.6mm,5um) detection wavelength: 254 nm. Column temperature: 25 ℃, injection volume: 20 ul;
an isopropenylphenyl diphenyl phosphate standard substance (the content is 99.8%) is weighed to prepare a solution of 10ppm, 20 ppm, 40 ppm, 60 ppm, 80 ppm and 100 ppm, and the solution is diluted by methanol to prepare a standard curve.
Sample preparation: weighing 0.2g sample, diluting to 10ml with mobile phase, dissolving, injecting sample, and injecting sample 20 ul. The isopropenylphenyl diphenyl phosphate content of the sample is calculated according to a standard curve.
2. Sample preparation: the products prepared in examples 1-4 and comparative examples 1 and 3.
3. The experimental results are as follows: see table 1.
Table 1 the results show that: compared with the comparative examples 1-2 and 4, the products prepared by the method disclosed by the invention have the advantages that the isopropenyl phenyl diphenyl phosphate and triphenyl phosphate content is greatly reduced, the triphenyl phosphate content is reduced from more than 2% to below 0.1% of triphenyl phosphate, the isopropenyl phenyl diphenyl phosphate content is reduced to below 40 ppm, and the product yield is improved to above 97%.
The consumption can be saved in the intelligent production process, the operating environment of workers is greatly improved, the labor cost is reduced, the quality of products in the batch production process is stable, the yield is stable, and high-end products can be stably generated. In a word, compared with the prior art, the method provided by the invention has the advantages of increased yield, increased purity, reduced impurity content and stability.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.