CN117866008A - Continuous flow micro-channel reaction method for synthesizing BDP intermediate of phosphorus flame retardant - Google Patents
Continuous flow micro-channel reaction method for synthesizing BDP intermediate of phosphorus flame retardant Download PDFInfo
- Publication number
- CN117866008A CN117866008A CN202311658977.8A CN202311658977A CN117866008A CN 117866008 A CN117866008 A CN 117866008A CN 202311658977 A CN202311658977 A CN 202311658977A CN 117866008 A CN117866008 A CN 117866008A
- Authority
- CN
- China
- Prior art keywords
- reaction
- bdp
- reactor
- bisphenol
- flame retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 15
- 239000011574 phosphorus Substances 0.000 title claims abstract description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000003063 flame retardant Substances 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 230000008878 coupling Effects 0.000 claims abstract description 32
- 238000010168 coupling process Methods 0.000 claims abstract description 32
- 238000005859 coupling reaction Methods 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 18
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 54
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 16
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000005886 esterification reaction Methods 0.000 description 15
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 14
- 230000032050 esterification Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 238000005070 sampling Methods 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 11
- 230000008020 evaporation Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical class COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- -1 and then Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a continuous flow microchannel reaction method for synthesizing a phosphorus flame retardant BDP intermediate. The micro-reaction temperature is controlled at 120-150 ℃, the material flow rate is controlled at 10-30mL/min, and the control pressure is controlled at 0.02-0.1MPa. The catalyst is selected from tetrabutyl titanate; the dosage of the tetrabutyl titanate is 0.01-2 percent of the mass of the bisphenol A serving as the raw material. The microchannel reactor coupling tube reactor used in the method ensures that bisphenol A can not generate crosslinking to generate other impurities in the reaction process in order to facilitate and rapidly feed in the initial stage of reactor feeding and realize good mass and heat transfer. Greatly shortens the reaction time from 5 hours to 5-30 minutes.
Description
Technical Field
The invention belongs to the technical field of continuous synthesis of phosphorus flame retardant BDP in synthesis of phosphorus flame retardant BDP, and particularly relates to a method and a process for continuous synthesis of phosphorus flame retardant BDP intermediates by utilizing a microchannel reactor coupled with a tubular reactor and the like.
Background
Bisphenol A-bis (diphenyl phosphate) (BDP) is a phosphorus-containing organic compound, has the characteristics of high phosphorus content, high relative molecular weight and good thermal stability, and has the advantages of good compatibility with polymer base materials, volatilization resistance, migration resistance, radiation resistance, low toxicity, lasting flame retardant effect and the like.
Many related data such as chinese patent CN101456879A, CN109912646A, CN1414968A and the like have been reported before to synthesize BDP, which comprises the following steps: bisphenol A and excessive phosphorus oxychloride are used as reaction raw materials, esterification reaction is carried out under the action of a catalyst, then excessive phosphorus oxychloride is removed under high-pressure vacuum and reduced pressure, finally, end capping is carried out on the mixture and a little excessive phenol to obtain a BDP crude product, and then, acid washing, alkali washing, water washing and distillation are carried out continuously to obtain a BDP product. In general, the method has the problems of complex process, long reaction time, high temperature and the like, and the synthesized BDP product has the problem of triphenyl phosphate (TPP), which is a harmful substance and has other impurities; the above problems can lead to color problems and flame retardant and other physical properties problems in BDP products. The continuous synthesis method of BDP is reported in Chinese patent D1-CN112409404B, CN116693572A, etc., the residence time of each stage of reaction kettle is more than 3 hours, and the whole time consumption is more than 10 hours.
Therefore, the invention provides a rapid and efficient (BDP esterification reaction time related by the invention can be completed within 1h, so that time cost and personnel cost are saved to a great extent) microchannel reactor coupling tubular reactor continuous synthesis method has the characteristics of high efficiency and intrinsic safety.
Disclosure of Invention
The invention aims at solving the technical problems in the prior art and developing a rapid and efficient continuous esterification synthesis method for a high-purity phosphorus flame retardant BDP intermediate by a microchannel reactor coupling tube reactor. The mass transfer and heat transfer of the reaction are improved, the loss of phosphorus oxychloride is reduced, the time cost and the personnel cost are saved, and meanwhile, the intrinsic safety of the synthesis device is achieved.
The invention provides a process method for producing high-purity phosphorus flame retardant BDP, which uses a microchannel reactor coupled tubular reactor to continuously synthesize the following reaction conditions: characterized by comprising the following procedures
Adding phosphorus oxychloride, a catalyst and bisphenol A into a flask, heating an oil bath to 25-30 ℃, and stirring for 0.5-1.0 h. The raw materials are mixed and pumped into a coupling tubular reactor of a microchannel reactor through a pump body, the reaction temperature is controlled to be 90-150 ℃, the material flow rate is 10-30mL/min, the pressure is 0.02-0.1MPa, and the gas-liquid separator releases hydrogen chloride gas generated by the reaction. And after the reaction is finished, the mixture enters a phosphorus trichloride evaporation kettle, and excessive phosphorus oxychloride is removed, so that a BDP intermediate is obtained.
The microchannel reactor is coupled with the channel form of the tubular reactor, adopts heart shape, linear shape and O shape, and adopts 2-8 modules for micro-reflecting 9mL of each module.
The micro-reaction temperature is controlled to be 120-150 ℃, the material control flow rate is controlled to be 10-30mL/min, and the control pressure is controlled to be 0.02-0.1MPa, so that the residence time of the material in the esterification microchannel reactor coupling tube reactor is controlled.
And a gas-liquid separator is arranged behind the two templates.
Compared with the traditional synthesis technology, the invention has the following beneficial effects:
the microchannel reactor coupling tube reactor used in the method ensures that bisphenol A can not generate crosslinking to generate other impurities in the reaction process in order to facilitate and rapidly feed in the initial stage of reactor feeding and realize good mass and heat transfer. Compared with the traditional gap reaction kettle and kettle type continuous reaction, the reaction time is greatly shortened from 5 hours to 5-30 minutes, continuous, efficient, safe and stable production is realized, the danger of the reaction materials in the use process is greatly reduced by the micro-channel reactor coupling tube type reaction process, and the method has reliable guarantee in the aspects of mass transfer, heat transfer, environmental protection and safety.
Drawings
FIG. 1 is a graph of the results of the end sampling spot plates of the experimental PFA coil.
FIG. 2 is a graph showing the TLC results of bisphenol A as a starting material.
FIG. 3 shows nuclear magnetic resonance spectra of reaction liquids of the tank reaction (A) of comparative example 1 and the microchannel continuous reaction (B) of example 1.
FIG. 4 shows nuclear magnetic resonance spectra of reaction solutions of the tank reaction (A) of comparative example 1 and the microchannel continuous reaction (B) of example 1.
Detailed Description
Example 1
1734g of phosphorus oxychloride, 1.3g of tetrabutyl titanate and 95g of bisphenol A are added into a flask, and the temperature of an oil bath is raised and stirred. The method comprises the steps of mixing raw materials, pumping the raw materials into an esterification microchannel reactor through a diaphragm pump to couple the reactor, configuring a back pressure valve at the tail end of the reactor, controlling the reaction temperature to 120 ℃, enabling the material flow rate to be 17.68mL/min, enabling the pressure to be 0.04MPa, enabling the residence time to be 5min, selecting 5 modules for the microreactor, enabling the channel form of the microchannel reactor to couple the reactor to be heart-shaped, then enabling the microchannel reactor to be connected with a gas-liquid separator to release hydrogen chloride gas generated by the reaction, then enabling the hydrogen chloride gas to be connected with a coil pipe, enabling the hydrogen chloride gas to enter a phosphorus trichloride evaporation bottle after the reaction is finished, and removing excessive phosphorus trichloride to obtain a BDP intermediate. The sampling point plate judges that the bisphenol A as a reaction raw material is completely reacted. The BDP intermediate yield was about 96%.
FIG. 1 is a graph showing the results of the BDP intermediate sample at the end of the PFA coil in example 1, mainly to determine whether bisphenol A remains as a starting material in the experiment, and thus whether the reaction was complete. Wherein the developing agent is 5% (volume fraction) MeOH/DCM, the reaction solution is quenched by methanol, the generated product is continuously reacted with methanol to generate polysubstituted methyl phosphate, three points on TLC are raw material points, mixed points of raw material and reaction solution points in sequence from left to right, and the three points are compared to show that the TLC shows that bisphenol A has disappeared, so that the raw material bisphenol A can be judged to completely react after passing through the micro-channel for 5 minutes.
FIG. 2 is a graph showing the TLC results of bisphenol A as a raw material, from left to right, in which SM, a point and a reaction solution are sequentially added, the reaction solution is quenched with methanol, the resultant product is reacted with methanol continuously to produce polysubstituted methyl phosphate, and TLC shows that bisphenol A has disappeared, and again proves that bisphenol A as a raw material can completely react after passing through a microchannel for 5 minutes.
FIG. 3 shows nuclear magnetic resonance hydrogen spectra of a reaction solution of a kettle type reaction and a continuous reaction solution of a micro-channel, and the reaction solution of the micro-channel is compared to obtain the consistency of the reaction solution of the micro-channel for 5 minutes and the reaction solution of the kettle type reaction solution for 4 hours (comparative example 1), so that the success of the experiment is further judged.
FIG. 4 shows nuclear magnetic resonance spectrum of a reaction solution in a kettle reaction and a microchannel continuous reaction, and it can be seen that other phosphorus-containing compounds besides phosphorus trichloride are generated in the reaction solution.
Example 2
1734g of phosphorus oxychloride, 1.3g of tetrabutyl titanate and 95g of bisphenol A are added into a flask, and the temperature of an oil bath is raised and stirred. The raw materials are mixed and then pumped into an esterification microchannel reactor coupling tubular reactor through a diaphragm pump, a back pressure valve is arranged at the tail end of the reactor, wherein the reaction temperature is controlled at 120 ℃, the material flow rate is 10.72mL/min, the pressure is 0.06MPa, the residence time is 8min, 5 modules are selected for the microreactor, the channel shape of the microchannel reactor coupling tubular reactor is heart-shaped, a gas-liquid separator is connected to release hydrogen chloride gas generated by the reaction, then a 100mL1/2PFA coil is connected, and the mixture enters a phosphorus trichloride evaporation bottle after the reaction is finished, so that excessive phosphorus oxychloride is removed, and a BDP intermediate is obtained. The sampling point plate judges that the bisphenol A as a reaction raw material is completely reacted. The BDP intermediate yield was about 98%.
Example 3
1734g of phosphorus oxychloride, 1.3g of tetrabutyl titanate and 95g of bisphenol A are added into a flask, and the temperature of an oil bath is raised and stirred. The raw materials are mixed and then pumped into an esterification microchannel reactor coupling tubular reactor through a diaphragm pump, a back pressure valve is arranged at the tail end of the reactor, wherein the reaction temperature is controlled at 120 ℃, the material flow rate is 15.52mL/min, the pressure is 0.05MPa, the residence time is 5min, 5 modules are selected for the microreactor, the channel shape of the microchannel reactor coupling tubular reactor is heart-shaped, a gas-liquid separator is connected to release hydrogen chloride gas generated by the reaction, then a 100mL1/4PFA coil is connected, and the mixture enters a phosphorus trichloride evaporation bottle after the reaction is finished, so that excessive phosphorus oxychloride is removed, and a BDP intermediate is obtained. The sampling point plate judges that the bisphenol A as a reaction raw material is completely reacted. The BDP intermediate yield was about 96%.
Example 4
1734g of phosphorus oxychloride, 1.3g of tetrabutyl titanate and 95g of bisphenol A are added into a flask, and the temperature of an oil bath is raised and stirred. The raw materials are mixed and then pumped into an esterification microchannel reactor coupling tubular reactor through a diaphragm pump, a back pressure valve is arranged at the tail end of the reactor, wherein the reaction temperature is controlled at 120 ℃, the material flow rate is 20.22mL/min, the pressure is 0.02MPa, the residence time is 5min, 5 modules are selected for the microreactor, the channel shape of the microchannel reactor coupling tubular reactor is heart-shaped, a gas-liquid separator is connected to release hydrogen chloride gas generated by the reaction, then a 100mL1/2PFA coil is connected, and the mixture enters a phosphorus trichloride evaporation bottle after the reaction is finished, so that excessive phosphorus oxychloride is removed, and a BDP intermediate is obtained. The sampling point plate judges that the bisphenol A as a reaction raw material is completely reacted. The BDP intermediate yield was about 92%.
Example 5
1734g of phosphorus oxychloride, 1.3g of tetrabutyl titanate and 95g of bisphenol A are added into a flask, and the temperature of an oil bath is raised and stirred. The raw materials are mixed and then pumped into an esterification microchannel reactor coupling tubular reactor through a diaphragm pump, a back pressure valve is arranged at the tail end of the reactor, wherein the reaction temperature is controlled at 120 ℃, the material flow rate is 18.68mL/min, the pressure is 0.03MPa, the residence time is 6min, 5 modules are selected for the microreactor, the channel shape of the microchannel reactor coupling tubular reactor is heart-shaped, a gas-liquid separator is connected to release hydrogen chloride gas generated by the reaction, then a 100mL1/4PFA coil is connected, and the mixture enters a phosphorus trichloride evaporation bottle after the reaction is finished, so that excessive phosphorus oxychloride is removed, and a BDP intermediate is obtained. The sampling point plate judges that the bisphenol A as a reaction raw material is completely reacted. The BDP intermediate yield was about 97%.
Comparative example 1
1734g of phosphorus oxychloride and 1.3g of anhydrous magnesium chloride are put into a reaction kettle, stirred and heated. After the temperature is raised to 110 ℃, 95g of phosphorus oxychloride is added in batches under the nitrogen atmosphere, and the feeding time is 2 hours. And after the material feeding is finished, heating to 120 ℃ for heat preservation reaction, wherein the heat preservation time is 4 hours. And then removing excessive phosphorus trichloride at 130-140 ℃ under vacuum absolute pressure to obtain an intermediate. The sampling point plate judges that the bisphenol A as a reaction raw material is completely reacted. The BDP intermediate yield was about 98%.
Comparative example 2
1734g of phosphorus oxychloride, 1.3g of anhydrous magnesium chloride and 95g of bisphenol A are added into a flask, and an oil bath is heated and stirred. The raw materials are mixed and then pumped into an esterification microchannel reactor coupling tubular reactor through a diaphragm pump, a back pressure valve is arranged at the tail end of the reactor, wherein the reaction temperature is controlled at 120 ℃, the material flow rate is 10.72mL/min, the pressure is 0.06MPa, the residence time is 8min, 5 modules are selected for the microreactor, the channel shape of the microchannel reactor coupling tubular reactor is heart-shaped, a gas-liquid separator is connected to release hydrogen chloride gas generated by the reaction, then a 100mL1/2PFA coil is connected, and the mixture enters a phosphorus trichloride evaporation bottle after the reaction is finished, so that excessive phosphorus oxychloride is removed, and a BDP intermediate is obtained. The sampling point plate judges that the bisphenol A as a reaction raw material is completely reacted. The BDP intermediate yield was about 99% by calculation. Since anhydrous magnesium chloride is generally soluble and solid in the mixed raw materials, the problem of pipe blockage occurs after the experiment has been carried out for 1 hour.
Comparative example 3
1734g of phosphorus oxychloride, 1.3g of tetrabutyl titanate and 95g of bisphenol A are added into a flask, and the temperature of an oil bath is raised and stirred. The raw materials are mixed and then pumped into an esterification microchannel reactor coupling tubular reactor through a diaphragm pump, wherein a back pressure valve is arranged at the tail end of the reactor, the reaction temperature is controlled to 120 ℃, the material flow rate is 35mL/min, the pressure is 0.08MPa, the residence time is 3min, 5 modules are selected as the microreactor, the channel shape of the microchannel reactor coupling tubular reactor is heart-shaped, a gas-liquid separator is connected to release hydrogen chloride gas generated by the reaction, then the hydrogen chloride gas is connected to a PFA coil, and the PFA coil enters a phosphorus trichloride evaporation bottle after the reaction is finished, so that excessive phosphorus oxychloride is removed, and a BDP intermediate is obtained. The sampling point plate judges that the bisphenol A serving as a reaction raw material is not completely reacted. The BDP intermediate yield was about 77% by calculation.
Comparative example 4
1734g of phosphorus oxychloride, 1.3g of tetrabutyl titanate and 95g of bisphenol A are added into a flask, and the temperature of an oil bath is raised and stirred. The method comprises the steps of mixing raw materials, pumping the raw materials into an esterification microchannel reactor coupling tubular reactor through a diaphragm pump, configuring a back pressure valve at the tail end of the reactor, controlling the reaction temperature to 120 ℃, enabling the material flow rate to be 5mL/min, enabling the pressure to be 0.01MPa, enabling the residence time to be 18min, enabling a microreactor to select 5 modules, enabling the channel shape of the microchannel reactor coupling tubular reactor to be heart-shaped, enabling a gas-liquid separator to release hydrogen chloride gas generated by the reaction, and then enabling the hydrogen chloride gas to enter a PFA coil, enabling the PFA coil to enter a phosphorus trichloride evaporation bottle after the reaction is finished, and removing excessive phosphorus oxychloride to obtain a BDP intermediate. The sampling point plate judges that the bisphenol A as a reaction raw material is completely reacted. The BDP intermediate yield was about 96% by calculation. The experiment controls the flow rate by adjusting the back pressure valve, and the pressure limit explosion risk of the pipe blockage and the pipeline exists due to the increase of the internal pressure.
Comparative example 5
1734g of phosphorus oxychloride, 1.3g of tetrabutyl titanate and 95g of bisphenol A are added into a flask, and the temperature of an oil bath is raised and stirred. The raw materials are pumped into an esterification microchannel reactor coupling tubular reactor through a diaphragm pump after being mixed, a back pressure valve is arranged at the tail end of the reactor, wherein the reaction temperature is controlled at 120 ℃, the material flow rate is 17.68mL/min, the pressure is 0.04MPa, the residence time is 5min, 5 modules are selected for the microreactor, the channel shape of the microchannel reactor coupling tubular reactor is linear, a gas-liquid separator is connected after the microchannel reactor coupling tubular reactor is used for releasing hydrogen chloride gas generated by the reaction, then the hydrogen chloride gas is connected into a PFA coil, and the PFA coil enters a phosphorus trichloride evaporation bottle after the reaction is finished, so that excessive phosphorus oxychloride is removed, and a BDP intermediate is obtained. The sampling spot plate judges that the bisphenol A serving as the reaction raw material has partial residues. The BDP intermediate yield was about 88% by calculation.
Comparative example 6
1734g of phosphorus oxychloride, 1.3g of tetrabutyl titanate and 95g of bisphenol A are added into a flask, and the temperature of an oil bath is raised and stirred. The raw materials are pumped into an esterification microchannel reactor coupling tubular reactor through a diaphragm pump after being mixed, a back pressure valve is arranged at the tail end of the reactor, wherein the reaction temperature is controlled at 120 ℃, the material flow rate is 17.68mL/min, the pressure is 0.04MPa, the residence time is 5min, 5 modules are selected for the microreactor, the channel shape of the microchannel reactor coupling tubular reactor is O-shaped, a gas-liquid separator is connected after the microchannel reactor coupling tubular reactor coupling is used for releasing hydrogen chloride gas generated by the reaction, the reaction is connected with a PFA coil, and the PFA coil enters a phosphorus trichloride evaporation bottle after the reaction is finished, so that excessive phosphorus oxychloride is removed, and a BDP intermediate is obtained. The sampling point plate judges that the bisphenol A as a reaction raw material is completely reacted. The BDP intermediate yield was about 90% by calculation.
The result of the continuous experiments of the coupling tube type reactor of the micro-channel reactor for multiple times and the product yield verification shows that the yield of the BDP intermediate can reach about 90-99 percent, the BDP intermediate is stable, the esterification reaction of the BDP can be completed, and in conclusion, the BDP can be judged to be carried out by the continuous process of the coupling tube type reactor of the micro-channel reactor.
The multistage micro-channel reactor coupling tube reactor series-parallel connection mode can be used for design, one feed is used for premixing reaction raw materials in a batching bottle in advance, then the feed is carried out at a certain temperature, and the viscosity of the system is lower. The micro-channel reactor is coupled with the channel form of the tubular reactor during the reaction, adopts heart shape, linear shape and O shape, and adopts 2-8 modules for micro-reaction of 9mL of each module.
Claims (4)
1. A continuous flow micro-channel reaction method for synthesizing a BDP intermediate of a phosphorus flame retardant is characterized by comprising the following steps:
mixing phosphorus oxychloride, a catalyst and bisphenol A, stirring uniformly, mixing raw materials, pumping the raw materials into a microchannel reactor coupling tubular reactor through a pump body, and reacting through a continuous flow microchannel to obtain the BDP intermediate.
2. The continuous flow micro-channel reaction method for synthesizing the BDP intermediate of the phosphorus flame retardant according to claim 1, wherein the micro-reaction temperature is controlled to be 120-150 ℃, the material flow rate is controlled to be 10-30mL/min, and the control pressure is controlled to be 0.02-0.1MPa.
3. The continuous flow microchannel reaction process for synthesizing a phosphorus flame retardant BDP intermediate according to claim 1, characterized in that the catalyst is selected from tetrabutyl titanate; the dosage of the tetrabutyl titanate is 0.01-2 percent of the mass of the bisphenol A serving as the raw material.
4. The continuous flow micro-channel reaction method for synthesizing a phosphorus flame retardant BDP intermediate according to claim 1, wherein the reaction time is 5-30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311658977.8A CN117866008A (en) | 2023-12-04 | 2023-12-04 | Continuous flow micro-channel reaction method for synthesizing BDP intermediate of phosphorus flame retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311658977.8A CN117866008A (en) | 2023-12-04 | 2023-12-04 | Continuous flow micro-channel reaction method for synthesizing BDP intermediate of phosphorus flame retardant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117866008A true CN117866008A (en) | 2024-04-12 |
Family
ID=90593653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311658977.8A Pending CN117866008A (en) | 2023-12-04 | 2023-12-04 | Continuous flow micro-channel reaction method for synthesizing BDP intermediate of phosphorus flame retardant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117866008A (en) |
-
2023
- 2023-12-04 CN CN202311658977.8A patent/CN117866008A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112409404B (en) | Continuous industrial production method of high-purity bisphenol A-bis (diphenyl phosphate) | |
| CN109096328A (en) | A kind of method of the continuous synthesizing phosphorous acid diethylester of micro passage reaction | |
| CN112225642B (en) | Method for preparing resorcinol by micro-channel reaction | |
| CN108558941B (en) | Method for preparing 2-chloroethyl phosphoric acid di (2-chloroethyl) ester through rearrangement reaction | |
| CN110294675B (en) | Method and system for preparing methyl acetoacetate by adopting tubular continuous flow reactor | |
| CN108864178B (en) | Micro-reaction method and device for synthesizing tris (2-chloropropyl) phosphate | |
| CN117866008A (en) | Continuous flow micro-channel reaction method for synthesizing BDP intermediate of phosphorus flame retardant | |
| CN102516051B (en) | Method for preparing isophorone by acetone liquid condensation with alkali catalyst | |
| US20070161823A1 (en) | Process for the preparation of methylheptenone | |
| CN111072515B (en) | Method for continuously synthesizing thiaminoximic acid intermediate | |
| CN112961035A (en) | Process and device for continuously synthesizing tribromophenol by microreactor | |
| CN113999098A (en) | Method for synthesizing 2,3, 5-trimethylbenzoquinone | |
| CN114539030A (en) | Method for preparing 2,2 ' -dihydroxy-3, 3 ', 5,5 ' -tetra-tert-butyl biphenyl by using microchannel reactor | |
| CN109232213A (en) | The method of hydroxy pivalin aldehyde is prepared under a kind of super critical condition | |
| CN113336696B (en) | Preparation method of meta-allyl aromatic compound | |
| CN114195617B (en) | Synthesis method of 4-bromodiphenyl | |
| KR890004134B1 (en) | Process for the preparation of phenyldichloro phosphine | |
| CN118026851A (en) | Micro-channel preparation method of o-nitrobenzaldehyde | |
| CN112694417B (en) | Preparation method and device of 1-cyano-2-propenyl acetate | |
| CN106631690A (en) | Preparation method of 1-adamantanol | |
| CN100408584C (en) | Preparation process of diethyl zinc | |
| CN117736130A (en) | Method for preparing 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane by utilizing microchannel reactor | |
| CN117866005A (en) | Preparation method of halogen-free phosphorus-containing ionic liquid | |
| CN113201004A (en) | Method for rapidly preparing cyclopropane derivative based on microchannel reaction technology | |
| CN115650851A (en) | Preparation method of 2-fluoro-4-bromo-6-methyl benzoate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |