A reaction system and process for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate)

Abstract

The present invention relates to the field of chemical synthesis technology, and in particular to a reaction system and process for preparing resorcinol bis (two 2,6-dimethylphenyl phosphates). The reaction system includes a reaction vessel, and the reaction vessel is sequentially connected with an absorption device, a neutralization device and a tail gas absorption device, and the reaction vessel includes a first reaction vessel and a second reaction vessel, and is connected with an online infrared spectrum detection device, and the gas phase outlet of the first reaction vessel and the second reaction vessel are sequentially connected with the gas phase inlet of the absorption device by a condenser, a flow meter, and a dryer, and the first reaction vessel and the second reaction vessel are both provided with a gas inlet, and the first reaction vessel is also provided with a feed port. The preparation technology of resorcinol bis (two 2,6-dimethylphenyl phosphates) provided by the present invention, green environmental protection, safety and efficiency; product yield is high, purity is good, and by-product high-quality hydrochloric acid.

Description

Technical Field

[0001] The invention relates to the technical field of chemical synthesis, and in particular to a reaction system and process for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate). Background Art

[0002] Resorcinol bis(di-2,6-dimethylphenyl phosphate) is a solid bisphosphate flame retardant with the advantages of symmetrical structure, large steric hindrance, not easy to hydrolyze, volatile resistance, high decomposition temperature, and long-lasting flame retardant effect. It is widely used in the flame retardancy of polycarbonate, acrylonitrile-butadiene-styrene block polymer, polybutylene terephthalate, polyethylene terephthalate and other materials.

[0003] There are two main methods for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate): (1) Excess phosphorus oxychloride reacts with resorcinol, and unreacted phosphorus oxychloride is recovered by reduced pressure distillation to obtain resorcinol bis(phosphorus oxychloride). Then, resorcinol bis(phosphorus oxychloride) reacts with 2,6-dimethylphenol to obtain resorcinol bis(di-2,6-dimethylphenyl phosphate). This method uses a large amount of phosphorus oxychloride and has high energy consumption for recovery; in the second step of esterification, the phenolic hydroxyl group of 2,6-dimethylphenol is affected by the steric hindrance of the methyl group, and the esterification reaction with resorcinol bis(phosphorus oxychloride) is not complete, and the yield is not high. (2) Phosphorus oxychloride reacts with 2,6-dimethylphenol to obtain di-(2,6-dimethylphenyl)phosphorus oxychloride, which is then reacted with resorcinol to obtain resorcinol bis(di-2,6-dimethylphenyl phosphate). This method usually involves adding solid resorcinol or dissolving it in solvents such as xylene and chlorobenzene to a reactor to react with di-(2,6-dimethylphenyl)phosphoryl chloride. Since the reaction system releases a large amount of hydrogen chloride gas, when adding solid resorcinol, hydrogen chloride gas is very easy to leak into the air, and hydrogen chloride gas is very easy to form acid mist with water vapor in the air, which makes it extremely difficult to add materials. In addition, when resorcinol is added at one time, the esterification reaction is very intense, especially the release of hydrogen chloride is very large, and the release rate is difficult to control, which can easily cause safety accidents such as spraying. Resorcinol has a very large polarity and a very low solubility in low-polarity solvents such as xylene and chlorobenzene. If it is dissolved in a solvent and added to the reaction system, the amount of solvent used is very large, and this method cannot be applied to actual production. When determining the reaction endpoint, sampling from the reaction system for testing also has major safety hazards. First, the temperature of the reaction system is high (180°C), and the solvent is very volatile. Second, the reaction system releases a large amount of corrosive hydrogen chloride gas, which can easily cause harm to the sampling personnel and pollute the environment. The currently reported methods for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate) all have some defects, so it is necessary to develop a safer and more efficient device and method for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate). Summary of the invention

[0004] In view of the above deficiencies in the prior art, the object of the present invention is to provide a safe and efficient reaction system and process for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate).

[0005] To achieve the above objectives, the technical solutions adopted are:

[0006] One of the purposes of the present invention is to provide a reaction system for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate), comprising a reaction container, wherein the reaction container is sequentially connected to an absorption device, a neutralization device and a tail gas absorption device, wherein the reaction container comprises a first reaction container and a second reaction container, wherein the first reaction container and the second reaction container are both provided with a top gas phase outlet, a solid feeding port and a bottom liquid phase outlet, wherein the bottom liquid phase outlet of the first reaction container is connected to the top liquid phase inlet of the second reaction container through a pipeline, the first reaction container and the second reaction container are connected to an online infrared spectrum detection device, wherein the gas phase outlets of the first reaction container and the second reaction container are sequentially connected to the gas phase inlet of the absorption device through a condenser, a flow meter and a dryer, wherein the gas phase outlet of the absorption device is connected to the gas phase inlet of the neutralization device through a flow meter, wherein the first reaction container and the second reaction container are both provided with a gas inlet, and the first reaction container is also provided with a feed port.

[0007] On the basis of the above technical solution, the present invention can also make the following improvements:

[0008] Furthermore, the gas phase outlet of the neutralization device is connected to the exhaust port via a flow meter, a tail gas absorption device and the like in sequence.

[0009] The beneficial effect of adopting the above further technical solution is that the flow meter is used to monitor the flow of hydrogen chloride gas, and the tail gas absorption device is connected to the exhaust port to further absorb the residual hydrogen chloride gas and improve environmental protection.

[0010] Furthermore, the absorption device and the neutralization device are both provided with liquid phase outlets, which are respectively a hydrochloric acid outlet and a neutralization liquid outlet, and the absorption device is a packing type spray absorption device.

[0011] The beneficial effect of adopting the above further technical solution is that the absorption device and the neutralization device are provided with liquid phase outlets, which can respectively recover hydrochloric acid and neutralization liquid to achieve resource recycling. The absorption device adopts filler-type spray absorption to improve the absorption efficiency.

[0012] Furthermore, the dryer is connected to the absorption device through a buffer.

[0013] The beneficial effect of adopting the above further technical solution is that the dryer is connected to the absorption device through the buffer, which can buffer the pressure fluctuation of the absorption device and improve the stability of the system.

[0014] Furthermore, both the first reaction container and the second reaction container are provided with a stirrer.

[0015] Furthermore, there is a height difference between the first reaction container and the second reaction container, and the first reaction container is higher than the second reaction container, so that the liquid in the first reaction container can enter the second reaction container by gravity.

[0016] Furthermore, the feed port is connected to a feed pump.

[0017] The beneficial effect of adopting the above further technical solution is that: the feed inlet is connected to a feed pump, which can accurately control the feed amount of phosphorus oxychloride to achieve slow dripping.

[0018] Further, the end of the gas phase inlet of the neutralization device is inserted below the liquid level of the neutralization device.

[0019] The beneficial effect of adopting the above further technical solution is that the gas phase inlet end of the neutralization device is inserted below the liquid surface, which can improve the gas-liquid contact efficiency and enhance the neutralization effect.

[0020] The second object of the present invention is to provide a process for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate), comprising the following steps:

[0021] (1) adding deionized water to the absorption device, adding a dilute alkali solution to the neutralization device, passing nitrogen gas through the first reaction container to replace the air in the first reaction container and the pipeline connecting the first reaction container and the absorption device, and in the second reaction container and the pipeline connecting the second reaction container and the absorption device, and then turning off the nitrogen gas;

[0022] (2) adding 2,6-dimethylphenol and catalyst 1 to the first reaction container through the solid feed port of the first reaction container, adding resorcinol and catalyst 2 to the second reaction container through the solid feed port of the second reaction container, turning on the heating function of the first reaction container, and switching the gas phase outlet of the first reaction container and the gas phase inlet of the absorption device to a conducting state; turning on the condenser connected to the first reaction container, and when the temperature reaches the set value, slowly adding phosphorus oxychloride dropwise to the first reaction container, and heating up to carry out a heat preservation reaction, and an online infrared detection device detects that the phenolic hydroxyl group of 2,6-dimethylphenol has reacted completely, and the reaction is completed, and nitrogen is passed through to purge the residual hydrogen chloride gas in the system, and then the gas phase outlet of the first reaction container and the gas phase inlet of the absorption device are switched to a closed state, and the reaction solution is cooled and kept warm for standby use, and nitrogen is kept flowing to maintain the pressure of the system after cooling;

[0023] (3) Turn on the heating function of the second reaction container, turn on the condenser connected thereto, and switch the gas phase outlet of the second reaction container and the gas phase inlet of the absorption device to a conductive state. When the second reaction container reaches the set temperature, slowly add the reaction liquid in the first reaction container dropwise into the second reaction container, and carry out a heat preservation reaction. When the online infrared detection device detects that the phenolic hydroxyl group of resorcinol has reacted completely, cool the reaction liquid and discharge it from the bottom liquid phase outlet.

[0024] Furthermore, in step (2), the molar ratio of 2,6-dimethylphenol to phosphorus oxychloride is 1.95-2.0:1, the catalyst one is at least one of boron trifluoride dibutyl ether and boron trifluoride tetrahydrofuran complex, and the amount of catalyst one is 0.5%-1% of the mass of phosphorus oxychloride.

[0025] Furthermore, in step (2), the molar ratio of resorcinol to phosphorus oxychloride is 1:2.1-2.2, the second catalyst is boron trifluoride tetrahydrofuran complex, and the amount of the second catalyst is 1%-2% of the mass of phosphorus oxychloride.

[0026] The beneficial effect of adopting the above technical solution is that by accurately controlling the molar ratio and the amount of catalyst used, the selectivity and yield of the reaction can be improved and the occurrence of side reactions can be reduced.

[0027] Furthermore, in step (2), the addition temperature of the phosphorus oxychloride is 110°C-120°C, the flow rate of hydrogen chloride gas is controlled to be less than 5L / min, and the phosphorus oxychloride is added. After the addition is completed, the temperature is slowly raised to 130°C-140°C for insulation reaction. After the reaction is completed, the temperature is lowered to 50°C-60°C and insulation is maintained.

[0028] Furthermore, in step (3), the reaction liquid in the first reaction container is added at a temperature of 130°C-140°C, the flow rate of hydrogen chloride gas is controlled to be less than 5L / min, and the reaction liquid in the first reaction container is added. After the addition is completed, the temperature is slowly raised to 150°C-160°C for insulation reaction.

[0029] The beneficial effect of adopting the above technical solution is that by accurately controlling the addition of phosphorus oxychloride, the temperature of the reaction solution and the flow rate of hydrogen chloride gas, the smooth progress of the reaction can be ensured and the danger caused by violent reaction can be avoided.

[0030] Furthermore, the cooling temperature of the condenser is 5° C.-15° C., and the dilute alkali solution is a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution with a mass concentration of 4%-5%.

[0031] The beneficial effect of adopting the above technical solution is that by controlling the cooling temperature of the condenser, the intermediate products can be effectively recovered, and the condenser refluxes the intermediate products such as phosphorus oxychloride and phosphorus oxychloride entrained in the hydrogen chloride gas into the first reaction container and the second reaction container.

[0032] Furthermore, in the step (3), after the reaction liquid is cooled and discharged from the bottom liquid phase outlet, the following steps are also included: transferring to a water washing kettle for water washing, recrystallization and other operations.

[0033] The beneficial effect of adopting the above technical solution is that the product can be further purified and the product quality can be improved through operations such as water washing and recrystallization.

[0034] Furthermore, the method further comprises the following steps: the hydrogen chloride gas generated by the first reaction container and the second reaction container first passes through a condenser, the condenser refluxes intermediate products such as phosphorus oxychloride and phosphorus oxychloride entrained in the hydrogen chloride gas into the first reaction container and the second reaction container, and then passes through a flow meter, a dryer and a buffer into an absorption device, where the hydrogen chloride gas is converted into hydrochloric acid through spray absorption in the absorption device, and the unabsorbed hydrogen chloride gas enters a neutralization device to react with a dilute alkaline solution, and after passing through the neutralization device, the residual hydrogen chloride gas is further adsorbed by a tail gas absorption device and discharged through an exhaust port.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] In the present invention, 2,6-dimethylphenol and phosphorus oxychloride react under the action of catalyst one to generate an intermediate bis(2,6-xylyl)phosphoryl chloride. Then, resorcinol and bis(2,6-xylyl)phosphoryl chloride react under the action of catalyst two to generate resorcinol bis(di-2,6-dimethylphenyl phosphate). The reaction process adopts a solvent-free method, the process is more environmentally friendly, and the drop-feeding method is adopted to effectively control the release rate of hydrogen chloride. By dropping phosphorus oxychloride in the first step and dropping bis(2,6-xylyl)phosphoryl chloride in the second step, the release rate of hydrogen chloride in the two-step esterification reaction process is effectively controlled, and the safety is higher. A gas flowmeter is provided between the absorption device and the reactor to monitor the release rate of hydrogen chloride gas. According to the gas release rate, the feeding rate of the reaction process and the spraying rate of the absorption device are adjusted, thereby solving the feeding problem of resorcinol in the second step esterification reaction; the online infrared spectrum detection equipment can detect the phenol of 2,6-xylenol and resorcinol in the reaction system. The changes of hydroxyl groups can be detected in real time to track the progress of the reaction. There is no need to take samples from the reactor for analysis and detection. The reaction endpoint can be determined more timely, accurately and conveniently, and the overflow of hydrogen chloride gas during the sampling process from the reactor can be avoided. The reaction system uses an absorption device, a neutralization device and a tail gas absorption device to collect, neutralize and adsorb hydrogen chloride gas, avoiding the emission of hydrogen chloride and producing high-quality hydrochloric acid as a by-product. The reaction system is equipped with two reactors, and the reactions of 2,6-dimethylphenol, resorcinol and phosphoryl chloride are carried out in different reactors, which is more efficient. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1The present invention discloses a reaction system and a flow chart for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate).

[0038] The reference numerals are: 100, first reaction vessel; 101, feed pump; 102, first solid feed port; 103, first condenser; 104, first flow meter; 105, first dryer; 106, first buffer; 200, second reaction vessel; 202, second solid feed port; 203, second condenser; 204, second flow meter; 205, second dryer; 206, second buffer; 300, absorption device; 301, circulation pump; 304, third flow meter; 306, third buffer; 400, neutralization device; 404. Fourth flow meter; 500. Tail gas absorption device; 600. Online infrared spectrum detection equipment; 1. First control valve; 2. Second control valve; 3. Third control valve; 4. Fourth control valve; 5. Fifth control valve; 6. Sixth control valve; 7. Seventh control valve; 8. Eighth control valve; 9. Ninth control valve; 10. Tenth control valve; 11. Eleventh control valve; 12. Twelfth control valve; 13. Thirteenth control valve; 14. Fourteenth control valve; 15. Fifteenth control valve; 16. Sixteenth control valve; 17. Seventeenth control valve. DETAILED DESCRIPTION

[0039] The principles and features of the present invention are described below in conjunction with the accompanying drawings. The examples given are only used to explain the present invention and are not used to limit the scope of the present invention.

[0040] like Figure 1As shown, the present invention provides a reaction system for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate), comprising a reaction container, wherein the reaction container is sequentially connected with an absorption device 300, a neutralization device 400 and a tail gas absorption device 500, wherein the reaction container comprises a first reaction container 100 and a second reaction container 200, wherein the first reaction container and the second reaction container 200 are both provided with a top gas phase outlet, a solid feeding port and a bottom liquid phase outlet, wherein the first reaction container 100 is provided with a first solid feeding port 102, the second reaction container 200 is provided with a second solid feeding port 202, the bottom liquid phase outlet of the first reaction container 100 is connected to the top liquid phase inlet of the second reaction container 200 through a pipeline, wherein the bottom liquid phase outlet of the first reaction container 100 is provided with a fourth control valve 4, the top liquid phase inlet of the second reaction container 200 is provided with a fifth control valve 5, the bottom liquid phase outlet of the second reaction container 200 is a material outlet, and is provided with a fourteenth control valve 14, the first The reaction container 100 and the second reaction container 200 are connected to an online infrared spectrum detection device 600. The gas phase outlet of the first reaction container 100 is connected to the gas phase inlet of the absorption device 300 through the third control valve 3, the first condenser 103, the first flowmeter 104, the first dryer 105 and the eighth control valve 8 in sequence. The gas phase outlet of the second reaction container 200 is connected to the gas phase inlet of the absorption device 300 through the seventh control valve 7, the second condenser 203, the second flowmeter 204, the second dryer 205 and the ninth control valve 9 in sequence. The gas phase outlet of the absorption device 300 is connected to the gas phase inlet of the neutralization device 400 through the tenth control valve 10 and the third flowmeter 304 in sequence. The first reaction container 100 and the second reaction container 200 are both provided with a gas inlet, wherein the first reaction container 100 is connected to a nitrogen inlet through the second control valve 2, and the second reaction container 200 is connected to a nitrogen inlet through the sixth control valve 6. The first reaction container 100 is also provided with a feed port.

[0041] In some preferred embodiments, the gas phase outlet of the neutralization device 400 is connected to the exhaust port through the fourth flowmeter 404 and the tail gas absorption device 500. Specifically, a thirteenth control valve 13 is provided between the gas phase outlet of the neutralization device 400 and the fourth flowmeter 404, and a pressure gauge is provided between the fourth flowmeter 404 and the tail gas absorption device 500.

[0042] In some embodiments, the absorption device 300 and the neutralization device 400 are both provided with liquid phase outlets, which are respectively a hydrochloric acid outlet controlled by a fifteenth control valve 15 and a neutralization liquid outlet controlled by a sixteenth control valve 16. The absorption device 300 is a packed spray absorption device, and the bottom of the absorption device 300 is connected to a seventeenth control valve 17 and a circulation pump 301, and is connected to the top of the absorption device 300 to achieve spraying.

[0043] In an optional embodiment, the dryer is connected to the absorption device 300 through a buffer. A first buffer 106 is provided between the first dryer 105 and the eighth control valve 8, and a second buffer 206 is provided between the second dryer 205 and the ninth control valve 9. A third buffer 306 and an eleventh control valve 11 are provided in sequence between the third flowmeter 304 and the gas phase inlet of the neutralization device 400.

[0044] In an optional embodiment, the neutralization device 400 is provided with a twelfth control valve 12 ， It can be used as a feeding valve to add dilute alkali solution, and as an atmosphere connecting valve during discharge to maintain the system pressure during discharge.

[0045] In some embodiments, both the first reaction container 100 and the second reaction container 200 are provided with a stirrer.

[0046] In an optional embodiment, there is a height difference between the first reaction container 100 and the second reaction container 200, and the first reaction container 100 is higher than the second reaction container 200, so that the liquid in the first reaction container 100 can enter the second reaction container 200 by gravity.

[0047] In some embodiments, the feed port is connected to a feed pump 101 , and a first control valve 1 is provided between the feed pump 101 and the first reaction container 100 .

[0048] In some embodiments, the end of the gas phase inlet of the neutralization device 400 is inserted below the liquid level of the neutralization device 400 .

[0049] In an optional embodiment, the first reaction container 100 and the second reaction container 200 are both reaction kettles.

[0050] The present invention also provides a process for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate), comprising the following steps:

[0051] (1) adding deionized water to the absorption device 300, adding a dilute alkali solution to the neutralization device 400, passing nitrogen gas through the first reaction container 100 to replace the air in the first reaction container 100 and the pipeline connecting it to the absorption device 300, and the second reaction container 200 and the pipeline connecting it to the absorption device 300, and then turning off the nitrogen gas;

[0052] (2) 2,6-dimethylphenol and catalyst 1 are added to the first reaction container 100 through the solid feeding port of the first reaction container 100, and resorcinol and catalyst 2 are added to the second reaction container 200 through the solid feeding port of the second reaction container 200, the heating function of the first reaction container 100 is turned on, and the gas phase outlet of the first reaction container 100 and the gas phase inlet of the absorption device 300 are switched to a conducting state; the condenser connected to the first reaction container 100 is turned on, and when the temperature reaches the set value, phosphorus oxychloride is slowly added dropwise to the first reaction container 100, and the temperature is increased to carry out a heat preservation reaction, and the online infrared spectrum detection device 600 detects that the phenolic hydroxyl group of 2,6-dimethylphenol has reacted completely, and the reaction is completed, and nitrogen is passed through the system to purge the residual hydrogen chloride gas, and then the gas phase outlet of the first reaction container 100 and the gas phase inlet of the absorption device 300 are switched to a closed state, and the reaction solution is cooled and kept warm for standby use, and nitrogen is kept flowing to maintain the pressure of the system after cooling;

[0053] (3) Turn on the heating function of the second reaction vessel 200, and turn on the condenser connected thereto, and at the same time switch the gas phase outlet of the second reaction vessel 200 and the gas phase inlet of the absorption device 300 to a conducting state, wait until the second reaction vessel 200 reaches the set temperature, slowly drop the reaction liquid in the first reaction vessel 100 into the second reaction vessel 200, close the connecting valve between the first reaction vessel 100 and the second reaction vessel 200 after the dropwise addition is completed, and carry out a heat preservation reaction, the online infrared spectrum detection device 600 detects that the phenolic hydroxyl group of resorcinol has reacted completely, pass nitrogen to purge the residual hydrogen chloride gas in the system, and then switch the gas phase outlet of the second reaction vessel 200 and the gas phase inlet of the absorption device 300 to a closed state, cool the reaction liquid, and discharge it from the bottom liquid phase outlet.

[0054] In an optional embodiment, the molar ratio of 2,6-dimethylphenol to phosphorus oxychloride in step (2) is 1.95-2.0:1, the catalyst one is at least one of boron trifluoride dibutyl ether and boron trifluoride tetrahydrofuran complex, and the amount of catalyst one is 0.5%-1% of the mass of phosphorus oxychloride.

[0055] In some embodiments, the molar ratio of resorcinol to phosphorus oxychloride in step (2) is 1:2.1-2.2, the catalyst 2 is boron trifluoride tetrahydrofuran complex, and the amount of catalyst 2 is 1%-2% of the mass of phosphorus oxychloride.

[0056] In some embodiments, the addition temperature of the phosphorus oxychloride in step (2) is 110°C-120°C, and the flow rate of hydrogen chloride gas is controlled to be less than 5L / min. After the phosphorus oxychloride is added, the temperature is slowly raised to 130°C-140°C for insulation reaction. After the reaction is completed, the temperature is lowered to 50°C-60°C and insulation is maintained.

[0057] In some embodiments, in step (3), the reaction liquid in the first reaction container 100 is added at a temperature of 130°C-140°C, the flow rate of hydrogen chloride gas is controlled to be less than 5L / min, the reaction liquid in the first reaction container 100 is added, and after the addition is completed, the temperature is slowly raised to 150°C-160°C for insulation reaction.

[0058] In an optional embodiment, the cooling temperature of the condenser is 5° C.-15° C., and the dilute alkali solution is a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution with a mass concentration of 4%-5%.

[0059] In some embodiments, in step (3), after the reaction liquid is cooled and discharged from the bottom liquid phase outlet, the following steps are further included: transferring to a water washing kettle for water washing, recrystallization and other operations.

[0060] As a preferred embodiment, the following steps are also included: the hydrogen chloride gas generated by the first reaction vessel 100 and the second reaction vessel 200 first passes through a condenser, and the condenser refluxes intermediate products such as phosphorus oxychloride and phosphorus oxychloride entrained in the hydrogen chloride gas into the first reaction vessel 100 and the second reaction vessel 200, and then passes through a flow meter, a dryer and a buffer into an absorption device 300, and is converted into hydrochloric acid through spray absorption in the absorption device 300, and the unabsorbed hydrogen chloride gas enters a neutralization device 400 to react with a dilute alkaline solution, and after passing through the neutralization device 400, the residual hydrogen chloride gas is further adsorbed by a tail gas absorption device 500 and discharged through an exhaust port.

[0061] Example 1

[0062] Check all components and connecting valves of the reaction equipment to ensure that all components are working properly. Add 8L of deionized water to the absorption device 300, and add 10L of 4% sodium hydroxide solution to the neutralization device 400. Open the second control valve 2 to pass nitrogen to the first reaction container 100 to replace the air in the first reaction container 100 and the pipeline connecting it to the absorption device 300. At the same time, open the fourth control valve 4 and the fifth control valve 5 to replace the air in the second reaction container 200 and the pipeline connecting it to the absorption device 300. Then close the eighth control valve 8, the ninth control valve 9, the fourth control valve 4, and the fifth control valve 5, and turn off the nitrogen at the same time. 7.697 kg (63.0 mol) of 2,6-dimethylphenol and 48.3 g of boron trifluoride dibutyl ether were added to the first reaction vessel 100 through the first solid feed port 102; 1.652 kg (15.0 mol) of resorcinol and 48.3 g of boron trifluoride tetrahydrofuran complex were added to the second reaction vessel 200 through the second solid feed port 202. The heating function of the first reaction vessel 100 was turned on, and the eighth control valve 8 and the third control valve 3 of the gas phase injection connecting the absorption device 300 and the first reaction vessel 100 were opened at the same time, and the first condenser 103 connected to the first reaction vessel 100 was turned on. When the refrigeration temperature was 5°C and the temperature of the first reaction vessel 100 was 110°C, the spray absorption system of the absorption device 300 was started. 4.83 kg (31.5 mol) of phosphorus oxychloride is added dropwise to the first reaction vessel 100 through the feed pump 101, and the flow rate of hydrogen chloride gas is controlled to be less than 5 L / min. After the addition is completed, the temperature is slowly raised to 130°C for heat preservation and reaction. The online infrared spectrum detection device 600 detects that the phenolic hydroxyl group of 2,6-dimethylphenol has reacted completely, and the reaction is over. The residual hydrogen chloride gas in the system is purged with nitrogen, and then the eighth control valve 8 and the third control valve 3 of the gas phase inlet connecting the absorption device 300 to the first reaction vessel 100 are closed. The reaction liquid is cooled to 50°C for standby use, and nitrogen is kept flowing to maintain the pressure of the system after cooling. The heating function of the second reaction vessel 200 is turned on, and the second condenser 203 connected thereto is turned on, and the ninth control valve 9 and the seventh control valve 7 of the gas phase inlet connecting the absorption device 300 to the second reaction vessel 200 are opened. When the refrigeration temperature reaches 10°C and the temperature of the second reaction container 200 is 130°C, slowly drop the reaction liquid in the first reaction container 100 into the second reaction container 200, and control the flow rate of hydrogen chloride gas to be less than 5L / min to add the reaction liquid in the first reaction container 100. After the addition is completed, close the fourth control valve 4 and the fifth control valve 5. Slowly raise the temperature to 160°C for reaction. The online infrared spectrum detection equipment 600 detects that the phenolic hydroxyl group of resorcinol has reacted completely, open the sixth control valve 6, pass nitrogen to purge the residual hydrogen chloride gas in the system, and then close the ninth control valve 9 and the seventh control valve 7 of the gas phase inlet connecting the absorption device 300 and the second reaction container 200.The reaction liquid was cooled and discharged from the fourteenth control valve 14. During the cooling and discharging process, nitrogen was kept flowing to maintain the pressure of the system. The material was transferred to a water washing kettle for water washing and recrystallization to obtain a product with a yield of 95% and a purity of 99.1%.

[0063] Example 2

[0064] Check all components and connecting valves of the reaction equipment to ensure that all components are working properly. Add 8L of deionized water to the absorption device 300, and add 10L of potassium hydroxide solution with a mass concentration of 5% to the neutralization device 400. Open the second control valve 2 to pass nitrogen to the first reaction container 100 to replace the air in the first reaction container 100 and the pipeline connecting it to the absorption device 300. At the same time, open the fourth control valve 4 and the fifth control valve 5 to replace the air in the second reaction container 200 and the pipeline connecting it to the absorption device 300. Then close the eighth control valve 8, the ninth control valve 9, the fourth control valve 4, and the fifth control valve 5, and turn off the nitrogen at the same time. 7.682 kg (62.89 mol) of 2,6-dimethylphenol and 24.8 g of boron trifluoride tetrahydrofuran complex were added to the first reaction vessel 100 through the first solid feed port 102; 1.652 kg (15.0 mol) of resorcinol and 89.0 g of boron trifluoride tetrahydrofuran complex were added to the second reaction vessel 200 through the second solid feed port 202. The heating function of the first reaction vessel 100 was turned on, and the eighth control valve 8 and the third control valve 3 of the gas phase injection connecting the absorption device 300 and the first reaction vessel 100 were opened at the same time, and the first condenser 103 connected to the first reaction vessel 100 was turned on. When the refrigeration temperature was 10°C and the temperature of the first reaction vessel 100 was 115°C, the spray absorption system of the absorption device 300 was started. 4.945 kg (32.25 mol) of phosphorus oxychloride is added to the first reaction vessel 100 through the feed pump 101, and the flow rate of hydrogen chloride gas is controlled to be less than 5 L / min before adding phosphorus oxychloride. After the addition is completed, the temperature is slowly raised to 140°C for heat preservation and reaction. The online infrared spectrum detection equipment 600 detects that the phenolic hydroxyl group of 2,6-dimethylphenol has reacted completely, and the reaction is over. The residual hydrogen chloride gas in the system is purged with nitrogen, and then the eighth control valve 8 and the third control valve 3 of the gas phase inlet connecting the absorption device 300 to the first reaction vessel 100 are closed. The reaction liquid is cooled to 55°C for standby use, and nitrogen is kept flowing to maintain the pressure of the system after cooling. The heating function of the second reaction vessel 200 is turned on, and the second condenser 203 connected thereto is turned on, and the ninth control valve 9 and the seventh control valve 7 of the gas phase inlet connecting the absorption device 300 to the second reaction vessel 200 are opened. When the refrigeration temperature reaches 15°C and the temperature of the second reaction container 200 is 135°C, slowly add the reaction liquid in the first reaction container 100 to the second reaction container 200, and control the flow rate of hydrogen chloride gas to be less than 5L / min to add the reaction liquid in the first reaction container 100. After the addition is completed, close the fourth control valve 4 and the fifth control valve 5. Slowly raise the temperature to 155°C for reaction. The online infrared spectrum detection equipment 600 detects that the phenolic hydroxyl group of resorcinol has reacted completely, open the sixth control valve 6, pass nitrogen to purge the residual hydrogen chloride gas in the system, and then close the ninth control valve 9 and the seventh control valve 7 of the gas phase inlet connecting the absorption device 300 and the second reaction container 200.The reaction liquid was cooled and discharged from the fourteenth control valve 14. During the cooling and discharging process, nitrogen was kept flowing to maintain the pressure of the system. The material was transferred to a water washing kettle for water washing and recrystallization, with a yield of 94% and a purity of 99.2%.

[0065] Example 3

[0066] Check all components and connecting valves of the reaction equipment to ensure that all components are working properly. Add 8L of deionized water to the absorption device 300, and add 10L of 5% sodium hydroxide solution to the neutralization device 400. Open the second control valve 2 to pass nitrogen to the first reaction container 100 to replace the air in the first reaction container 100 and the pipeline connecting it to the absorption device 300. At the same time, open the fourth control valve 4 and the fifth control valve 5 to replace the air in the second reaction container 200 and the pipeline connecting it to the absorption device 300. Then close the eighth control valve 8, the ninth control valve 9, the fourth control valve 4, and the fifth control valve 5, and turn off the nitrogen at the same time. 7.942 kg (65.01 mol) of 2,6-dimethylphenol and 25.3 g of boron trifluoride dibutyl ether were added to the first reaction vessel 100 through the first solid feed port 102; 1.652 kg (15.0 mol) of resorcinol and 75.9 g of boron trifluoride tetrahydrofuran complex were added to the second reaction vessel 200 through the second solid feed port 202. The heating function of the first reaction vessel 100 was turned on, and the eighth control valve 8 and the third control valve 3 of the gas phase injection connecting the absorption device 300 and the first reaction vessel 100 were opened at the same time, and the first condenser 103 connected to the first reaction vessel 100 was turned on. When the refrigeration temperature was 15°C and the temperature of the first reaction vessel 100 was 120°C, the spray absorption system of the absorption device 300 was started. 5.06 kg (33.0 mol) of phosphorus oxychloride is added to the first reaction vessel 100 through the feed pump 101, and the flow rate of hydrogen chloride gas is controlled to be less than 5 L / min. After the addition is completed, the temperature is slowly raised to 135°C for heat preservation and reaction. The online infrared spectrum detection device 600 detects that the phenolic hydroxyl group of 2,6-dimethylphenol has reacted completely, and the reaction is over. The residual hydrogen chloride gas in the system is purged with nitrogen, and then the eighth control valve 8 and the third control valve 3 of the gas phase inlet connecting the absorption device 300 to the first reaction vessel 100 are closed. The reaction liquid is cooled to 60°C for standby use, and nitrogen is kept flowing to maintain the pressure of the system after cooling. The heating function of the second reaction vessel 200 is turned on, and the second condenser 203 connected thereto is turned on, and the ninth control valve 9 and the seventh control valve 7 of the gas phase inlet connecting the absorption device 300 to the second reaction vessel 200 are opened. When the refrigeration temperature reaches 5°C and the temperature of the second reaction container 200 is 140°C, slowly add the reaction liquid in the first reaction container 100 to the second reaction container 200, and control the flow rate of hydrogen chloride gas to be less than 5L / min to add the reaction liquid in the first reaction container 100. After the addition is completed, close the fourth control valve 4 and the fifth control valve 5. Slowly raise the temperature to 150°C for reaction. The online infrared spectrum detection equipment 600 detects that the phenolic hydroxyl group of resorcinol has reacted completely, open the sixth control valve 6, pass nitrogen to purge the residual hydrogen chloride gas in the system, and then close the ninth control valve 9 and the seventh control valve 7 of the gas phase inlet connecting the absorption device 300 and the second reaction container 200.The reaction liquid was cooled and discharged from the fourteenth control valve 14. During the cooling and discharging process, nitrogen was kept flowing to maintain the pressure of the system. The material was transferred to a water washing kettle for water washing and recrystallization, with a yield of 96% and a purity of 99.1%.

[0067] Example 4

[0068] Check all components and connecting valves of the reaction equipment to ensure that all components are working properly. Add 8L of deionized water to the absorption device 300, and add 10L of potassium hydroxide solution with a mass concentration of 4.5% to the neutralization device 400. Open the second control valve 2 to pass nitrogen to the first reaction container 100 to replace the air in the first reaction container 100 and the pipeline connecting it to the absorption device 300. At the same time, open the fourth control valve 4 and the fifth control valve 5 to replace the air in the second reaction container 200 and the pipeline connecting it to the absorption device 300. Then close the eighth control valve 8, the ninth control valve 9, the fourth control valve 4, and the fifth control valve 5, and turn off the nitrogen at the same time. 7.99 kg (65.4 mol) of 2,6-dimethylphenol and 35.1 g of boron trifluoride dibutyl ether were added to the first reaction vessel 100 through the first solid feed port 102; 1.652 kg (15.0 mol) of resorcinol and 100.3 g of boron trifluoride tetrahydrofuran complex were added to the second reaction vessel 200 through the second solid feed port 202. The heating function of the first reaction vessel 100 was turned on, and the eighth control valve 8 and the third control valve 3 of the gas phase injection connecting the absorption device 300 and the first reaction vessel 100 were opened at the same time, and the first condenser 103 connected to the first reaction vessel 100 was turned on. When the refrigeration temperature was 7°C and the temperature of the first reaction vessel 100 was 113°C, the spray absorption system of the absorption device 300 was started. 5.014 kg (32.7 mol) of phosphorus oxychloride is added to the first reaction vessel 100 through the feed pump 101, and the flow rate of hydrogen chloride gas is controlled to be less than 5 L / min. After the addition is completed, the temperature is slowly raised to 137°C for heat preservation and reaction. The online infrared spectrum detection device 600 detects that the phenolic hydroxyl group of 2,6-dimethylphenol has reacted completely, and the reaction is over. The residual hydrogen chloride gas in the system is purged with nitrogen, and then the eighth control valve 8 and the third control valve 3 of the gas phase inlet connecting the absorption device 300 to the first reaction vessel 100 are closed. The reaction liquid is cooled to 53°C for standby use, and nitrogen is kept flowing to maintain the pressure of the system after cooling. The heating function of the second reaction vessel 200 is turned on, and the second condenser 203 connected thereto is turned on, and the ninth control valve 9 and the seventh control valve 7 of the gas phase inlet connecting the absorption device 300 to the second reaction vessel 200 are opened. When the refrigeration temperature reaches 12°C and the temperature of the second reaction container 200 is 136°C, slowly add the reaction liquid in the first reaction container 100 to the second reaction container 200, and control the flow rate of hydrogen chloride gas to be less than 5L / min to add the reaction liquid in the first reaction container 100. After the addition is completed, close the fourth control valve 4 and the fifth control valve 5. Slowly raise the temperature to 158°C for reaction. The online infrared spectrum detection equipment 600 detects that the phenolic hydroxyl group of resorcinol has reacted completely, open the sixth control valve 6, pass nitrogen to purge the residual hydrogen chloride gas in the system, and then close the ninth control valve 9 and the seventh control valve 7 of the gas phase inlet connecting the absorption device 300 and the second reaction container 200.The reaction liquid is cooled and discharged from the fourteenth control valve 14. During the cooling and discharging process, nitrogen is kept flowing to maintain the pressure of the system. The material is transferred to a water washing kettle for water washing and recrystallization, with a yield of 95% and a purity of 99.3%.

[0069] Example 5

[0070] Check all components and connecting valves of the reaction equipment to ensure that all components are working properly. Add 8L of deionized water to the absorption device 300, and add 10L of sodium hydroxide solution with a mass concentration of 4.5% to the neutralization device 400. Open the second control valve 2 to pass nitrogen to the first reaction container 100 to replace the air in the first reaction container 100 and the pipeline connecting it to the absorption device 300. At the same time, open the fourth control valve 4 and the fifth control valve 5 to replace the air in the second reaction container 200 and the pipeline connecting it to the absorption device 300. Then close the eighth control valve 8, the ninth control valve 9, the fourth control valve 4, and the fifth control valve 5, and turn off the nitrogen at the same time. 7.917 kg (64.8 mol) of 2,6-dimethylphenol and 49.6 g of boron trifluoride tetrahydrofuran complex were added to the first reaction vessel 100 through the first solid feed port 102; 1.652 kg (15.0 mol) of resorcinol and 64.6 g of boron trifluoride tetrahydrofuran complex were added to the second reaction vessel 200 through the second solid feed port 202. The heating function of the first reaction vessel 100 was turned on, and the eighth control valve 8 and the third control valve 3 of the gas phase injection connecting the absorption device 300 and the first reaction vessel 100 were opened at the same time, and the first condenser 103 connected to the first reaction vessel 100 was turned on. When the refrigeration temperature was 12°C and the temperature of the first reaction vessel 100 was 118°C, the spray absorption system of the absorption device 300 was started. 4.968 kg (32.4 mol) of phosphorus oxychloride is added to the first reaction vessel 100 through the feed pump 101, and the flow rate of hydrogen chloride gas is controlled to be less than 5 L / min before adding phosphorus oxychloride. After the addition is completed, the temperature is slowly raised to 140°C for heat preservation and reaction. The online infrared spectrum detection equipment 600 detects that the phenolic hydroxyl group of 2,6-dimethylphenol has reacted completely, and the reaction is over. The residual hydrogen chloride gas in the system is purged with nitrogen, and then the eighth control valve 8 and the third control valve 3 of the gas phase inlet connecting the absorption device 300 to the first reaction vessel 100 are closed. The reaction liquid is cooled to 58°C for standby use, and nitrogen is kept flowing to maintain the pressure of the system after cooling. The heating function of the second reaction vessel 200 is turned on, and the second condenser 203 connected thereto is turned on, and the ninth control valve 9 and the seventh control valve 7 of the gas phase inlet connecting the absorption device 300 to the second reaction vessel 200 are opened. When the refrigeration temperature reaches 14°C and the temperature of the second reaction container 200 is 138°C, slowly add the reaction liquid in the first reaction container 100 to the second reaction container 200, and control the flow rate of hydrogen chloride gas to be less than 5L / min to add the reaction liquid in the first reaction container 100. After the addition is completed, close the fourth control valve 4 and the fifth control valve 5. Slowly raise the temperature to 156°C for reaction. The online infrared spectrum detection equipment 600 detects that the phenolic hydroxyl group of resorcinol has reacted completely, open the sixth control valve 6, pass nitrogen to purge the residual hydrogen chloride gas in the system, and then close the ninth control valve 9 and the seventh control valve 7 of the gas phase inlet connecting the absorption device 300 and the second reaction container 200.The reaction liquid was cooled and discharged from the fourteenth control valve 14. During the cooling and discharging process, nitrogen was kept flowing to maintain the pressure of the system. The material was transferred to a water washing kettle for water washing and recrystallization, with a yield of 94% and a purity of 99.2%.

[0071] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A reaction system for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate), comprising a reaction container, characterized in that: The reaction container is connected with an absorption device, a neutralization device and a tail gas absorption device in sequence, and the reaction container includes a first reaction container and a second reaction container. The first reaction container and the second reaction container are both provided with a top gas phase outlet, a solid feeding port and a bottom liquid phase outlet. The bottom liquid phase outlet of the first reaction container is connected with the top liquid phase inlet of the second reaction container through a pipeline. The first reaction container and the second reaction container are connected with an online infrared spectrum detection device. The gas phase outlets of the first reaction container and the second reaction container are both connected with the gas phase inlet of the absorption device through a condenser, a flow meter and a dryer in sequence. The gas phase outlet of the absorption device is connected with the gas phase inlet of the neutralization device through a flow meter. The first reaction container and the second reaction container are both provided with a gas inlet, and the first reaction container is also provided with a feed port.

2. The reaction system for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate) according to claim 1, characterized in that: The gas phase outlet of the neutralization device is connected to the exhaust port through a flow meter and a tail gas absorption device in sequence.

3. The reaction system for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate) according to claim 1, characterized in that: The absorption device and the neutralization device are both provided with liquid phase outlets, and the absorption device is a filler-type spray absorption device.

4. The reaction system for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate) according to claim 1, characterized in that: The dryer is connected to the absorption device through a buffer.

5. A process for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate), characterized in that: The following steps are involved: (1) adding deionized water to the absorption device, adding a dilute alkali solution to the neutralization device, passing nitrogen gas through the first reaction container to replace the air in the first reaction container and the pipeline connecting the first reaction container and the absorption device, and in the second reaction container and the pipeline connecting the second reaction container and the absorption device, and then turning off the nitrogen gas; (2) adding 2,6-dimethylphenol and catalyst 1 to the first reaction container through the solid feed port of the first reaction container, adding resorcinol and catalyst 2 to the second reaction container through the solid feed port of the second reaction container, turning on the heating function of the first reaction container, and switching the gas phase outlet of the first reaction container and the gas phase inlet of the absorption device to a conducting state; turning on the condenser connected to the first reaction container, and when the temperature reaches the set value, slowly adding phosphorus oxychloride dropwise to the first reaction container, and heating up to carry out a heat preservation reaction, and an online infrared detection device detects that the phenolic hydroxyl group of 2,6-dimethylphenol has reacted completely, and the reaction is completed, and nitrogen is passed through to purge the residual hydrogen chloride gas in the system, and then the gas phase outlet of the first reaction container and the gas phase inlet of the absorption device are switched to a closed state, and the reaction solution is cooled and kept warm for standby use, and nitrogen is kept flowing to maintain the pressure of the system after cooling; (3) Turn on the heating function of the second reaction container, turn on the condenser connected thereto, and switch the gas phase outlet of the second reaction container and the gas phase inlet of the absorption device to a conducting state. When the second reaction container reaches the set temperature, slowly drop the reaction liquid in the first reaction container into the second reaction container. After the dropwise addition is completed, close the connecting valve between the first reaction container and the second reaction container, and carry out a heat preservation reaction. The online infrared detection device detects that the phenolic hydroxyl group of resorcinol has reacted completely. Nitrogen is passed to purge the residual hydrogen chloride gas in the system. Then, the gas phase outlet of the second reaction container and the gas phase inlet of the absorption device are switched to a closed state, the reaction liquid is cooled, and discharged from the bottom liquid phase outlet.

6. The process for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate) according to claim 5, characterized in that: The molar ratio of 2,6-dimethylphenol to phosphorus oxychloride in step (2) is 1.95-2.0:1, the catalyst one is at least one of boron trifluoride dibutyl ether and boron trifluoride tetrahydrofuran complex, and the amount of catalyst one is 0.5% to 1% of the mass of phosphorus oxychloride.

7. The process for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate) according to claim 5, characterized in that: The molar ratio of resorcinol to phosphorus oxychloride in step (2) is 1:2.1-2.2, the second catalyst is boron trifluoride tetrahydrofuran complex, and the amount of the second catalyst is 1% to 2% of the mass of phosphorus oxychloride.

8. The process for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate) according to claim 5, characterized in that: The addition temperature of the phosphorus oxychloride in step (2) is 110°C-120°C, and the flow rate of hydrogen chloride gas is controlled to be less than 5L / min. After the addition of phosphorus oxychloride is completed, the temperature is slowly raised to 130°C-140°C for insulation reaction. After the reaction is completed, the temperature is lowered to 50°C-60°C and insulation is maintained.

9. The process for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate) according to claim 5, characterized in that: Step (3) The reaction liquid in the first reaction container is added at a temperature of 130°C-140°C, and the flow rate of hydrogen chloride gas is controlled to be less than 5L / min. The reaction liquid in the first reaction container is added, and after the addition is completed, the temperature is slowly raised to 150°C-160°C for insulation reaction.

10. The process for preparing resorcinol bis(di-2,6-dimethylphenyl phosphate) according to claim 5, characterized in that: The cooling temperature of the condenser is 5° C.-15° C., and the dilute alkali solution is a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution with a mass concentration of 4%-5%.

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