CN112830867A - Preparation method of energy-saving environment-friendly flame retardant tetrabromo double-part A - Google Patents
Preparation method of energy-saving environment-friendly flame retardant tetrabromo double-part A Download PDFInfo
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- CN112830867A CN112830867A CN202110141242.2A CN202110141242A CN112830867A CN 112830867 A CN112830867 A CN 112830867A CN 202110141242 A CN202110141242 A CN 202110141242A CN 112830867 A CN112830867 A CN 112830867A
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- 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 30
- 239000003063 flame retardant Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000012074 organic phase Substances 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 53
- 239000012071 phase Substances 0.000 claims abstract description 51
- 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 44
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 39
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 17
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 239000012267 brine Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 59
- 239000000706 filtrate Substances 0.000 claims description 35
- 238000004061 bleaching Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 16
- 239000002351 wastewater Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 abstract description 27
- 239000002699 waste material Substances 0.000 abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- 238000004064 recycling Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 239000010413 mother solution Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- WYBOEVJIVYIEJL-UHFFFAOYSA-N 3,3',5-tribromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC=C(O)C(Br)=C1 WYBOEVJIVYIEJL-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of an energy-saving environment-friendly flame retardant tetrabromo double part A, which comprises the following steps: (1) adding a certain amount of bisphenol A into chlorobenzene, stirring until the materials are uniformly mixed, wherein the stirring time is 0.5h, and simultaneously dropwise adding bromine and hydrogen peroxide at a specific temperature to obtain a tetrabromobisphenol A solution. (2) Heating the reaction system to carry out curing reaction, standing and separating out a water phase after curing is finished, collecting an organic phase to carry out standing and layering treatment for four times, cooling the collected organic phase to 8 ℃ by adopting frozen brine after standing and layering for four times, and carrying out suction filtration to obtain a tetrabromo-bis-A product. The preparation method has the advantages that the using frequency of the mother liquor can reach more than 100 times, the generation of waste residues is reduced, and the using amount of sodium sulfite can be saved by 50 percent; the mother liquor is recycled for 100 times, the chroma of the product is 20, the purity is 99.35 percent, and the yield is 99.8 percent; the comprehensive yield of the product is 99.6 percent, and the average purity of the product is 99.54 percent.
Description
Technical Field
The invention relates to tetrabromobisphenol A, in particular to a preparation method of energy-saving and environment-friendly flame retardant tetrabromobisphenol A.
Background
Tetrabromobisphenol A is a reactive flame retardant and an additive flame retardant, is widely used for producing flame retardant plastics, and has good flame retardant effect. As a reactive flame retardant, the flame retardant can be used for producing flame retardant resins such as epoxy resin, polycarbonate and the like; as an additive flame retardant, the flame retardant is used for producing flame retardant resins such as polystyrene resin, ABS resin, phenolic resin and the like.
In the prior art, tetrabromobisphenol A is produced by using chlorobenzene as a solvent, and after the bisphenol A and the chlorobenzene are mixed, metered hydrogen peroxide is added, and then the mixture reacts with bromine to generate the tetrabromobisphenol A. The oxidation reaction is carried out in the reaction process to generate yellow substances, so that the color of the mother liquor is darker and darker in the production process, and the chroma of the product is also bigger and bigger; in order to ensure that the product chromaticity meets the requirement, mother liquor has to be distilled to remove colored substances, and the repeated use times of the chlorobenzene mother liquor are less. Meanwhile, tetrabromobisphenol A has higher solubility in chlorobenzene, so that the product loss is higher, the total yield of the product is lower, and the production cost is higher.
The invention with the application number of CN201710357593.0 discloses a method for producing tetrabromobisphenol A, which prepares a finished product of tetrabromobisphenol A through catalytic reaction, curing reaction, reduction reaction, washing process, crystallization process, centrifugal separation and vacuum drying. According to the technology, the purity of the product is gradually reduced along with the increase of the circulation times of the mother liquor, and meanwhile, the product quality is seriously influenced, so that the chromaticity of the product is higher and higher, and after the mother liquor of the technology is applied for 20 times, the product quality is seriously reduced, and the requirements of customers cannot be met; meanwhile, the patent technology can generate a large amount of waste residues and waste water in practical application, and influences the environment.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method of an energy-saving and environment-friendly flame retardant tetrabromo double A, which achieves the following aims: the circulation times of the mother liquor are increased, and the quality and the yield of the product are ensured; the using amount of sodium sulfite is reduced, and the generation of waste residue is reduced; the washing water is recycled, so that the washing amount is reduced, and the generation of waste water is reduced.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the invention relates to a preparation method of an energy-saving environment-friendly flame retardant tetrabromo double part A, which comprises the following steps:
(1) adding a certain amount of bisphenol A into chlorobenzene, stirring until the materials are uniformly mixed, wherein the stirring time is 0.5h, and simultaneously dropwise adding bromine and hydrogen peroxide at a specific temperature to obtain a tetrabromobisphenol A solution.
(2) Heating the reaction system for curing reaction, standing and separating out a water phase after curing is finished, collecting an organic phase for standing and layering for four times, cooling the collected organic phase after standing and layering for four times to 8 ℃ by using frozen brine, and performing suction filtration to obtain a tetrabromobisphenol A product.
Preferably, the four standing layers are: standing for the first time for layering: adding 20g of 10% sodium sulfite solution into the organic phase for reduction, heating to 90 ℃, standing for 0.5h, separating out the water phase after standing, and collecting the organic phase;
standing and layering for the second time: adding 20g of 10% sodium sulfite solution into the organic phase collected by the first standing and layering for bleaching, heating to 90 ℃, starting standing for 0.5h, separating out the water phase after the standing is finished, and collecting the organic phase;
standing and layering for the third time: adding 50g of water into the organic phase collected by the second standing and layering, heating to 90 ℃, starting standing for 0.5h, separating out the water phase after the standing is finished, and collecting the organic phase;
standing and layering for the fourth time: adding 50g of water into the organic phase collected by the third standing and layering, heating to 90 ℃, starting standing for 0.5h, separating out the water phase after the standing is finished, and collecting the organic phase.
Preferably, the bleaching wastewater generated by the second standing and layering is collected, the polypropionamide is added into the bleaching wastewater, stirred and dissolved, then the polyaluminium chloride is added, the solid is separated out by stirring, the obtained solution is filtered by a sand core funnel of G4, the solid is colored, the filtrate is the treated sodium sulfite, the color is obviously lightened and the sodium sulfite is ready for use, the water obtained by the second washing is also filtered by a sand core funnel of G4, and the filtrate is used for use.
Preferably, the dropping temperature of the bromine and the hydrogen peroxide is 0-30 ℃, preferably 20-30 ℃.
Preferably, the mass ratio of the bisphenol A to the chlorobenzene is 1: 4-6.
Preferably, the bisphenol a: bromine: the molar ratio of hydrogen peroxide is 1: 2.01-2.1: 2.01-2.11.
Preferably, the curing reaction temperature is 0-95 ℃, and preferably 85-95 ℃; the curing time is 0.5-1 h.
Preferably, the dosage of the polypropiocetamide is 0.05% -0.2% of the dosage of the sodium sulfite;
preferably, the dosage of the polyaluminium chloride is 0.05-0.2% of the dosage of sodium sulfite.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method of the energy-saving and environment-friendly flame retardant tetrabromobisphenol A, the yield of the tetrabromobisphenol A product is 80%, the product purity is 99.8%, and the product detection chromaticity is 5.
(2) According to the preparation method of the energy-saving and environment-friendly flame retardant tetrabromo double A, the using frequency of the mother liquor can reach more than 100 times, the generation of waste residues is reduced, and the using amount of sodium sulfite can be saved by 50%.
(3) According to the preparation method of the energy-saving and environment-friendly flame retardant tetrabromo double A, the mother liquor is recycled for 100 times, the product chromaticity is 20, the purity is 99.35%, and the yield is 99.8%; the comprehensive yield of the product is 99.6 percent, and the average purity of the product is 99.54 percent.
(4) According to the preparation method of the energy-saving and environment-friendly flame retardant tetrabromo double part A, waste water obtained by washing twice is filtered by the precision filter and then directly used for washing once, so that the generation of waste water is saved.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
100g of benzene chloride and 22.8g of bisphenol A are added, and stirring is started for 0.5 h. After stirring, dropwise adding 33.2g of bromine and 25.8g of hydrogen peroxide at the same time, controlling the dropwise adding temperature to be 25 ℃, after dropwise adding, heating to 90 ℃, keeping the temperature for reaction for 1h, standing for layering, standing for 0.5h, separating out the water phase, adding 20g of 10% sodium sulfite solution into the organic phase for reduction, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 20g of 10% sodium sulfite solution into the organic phase for bleaching, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of organic phase water, heating to 90 ℃, standing for 0.5h, separating out the water phase, heating to 90 ℃, standing for 0.5h, cooling the organic phase to 8 ℃ by using frozen saline, obtaining a tetrabromobisphenol A product and a filtrate, wherein the filtrate is recycled as a mother liquor.
The mother liquor comprises tetrabromobisphenol A and tribromobisphenol A.
Calculated by bisphenol A, the yield of the tetrabromobisphenol A product is 80%, the purity of the product is 99.8%, and the product detection chromaticity is 5.
And adding 0.02G of polypropylacetamide into the bleaching wastewater obtained by the standing and layering separation in the second step, stirring and dissolving, then adding 0.02G of polyaluminum chloride, stirring to separate out solids, filtering by using a sand core funnel of G4, wherein the solids are colored, the filtrate is the treated sodium sulfite, the color is obviously lightened and the sodium sulfite is ready for use, and the water obtained by secondary washing is also filtered by using a sand core funnel of G4, and the filtrate is used for use.
Example 2
The mother liquor of example 1 was used and 1.5g of fresh chlorobenzene and 22.8g of bisphenol A were added, and stirring was started for 0.5 h. After stirring, dropwise adding 33.2g of bromine and 25.8g of hydrogen peroxide at the same time, controlling the dropwise adding temperature to be 25 ℃, after dropwise adding, heating to 88 ℃, keeping the temperature for reaction for 0.5h, standing for layering, standing for 0.5h, separating out the water phase, reducing 20g of recovered sodium sulfite in an organic phase in a sleeving manner, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 20g of 10% sodium sulfite solution into the organic phase for bleaching, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of water into the organic phase, heating to 90 ℃, standing for 0.5h, separating out the water phase, heating to 90 ℃, standing for 0.5h, cooling the organic phase to 8 ℃ by using frozen saline, obtaining a tetrabromobisphenol A product and filtrate, and recycling the filtrate as mother liquor.
Based on bisphenol A, the yield of the tetrabromobisphenol A product is 99.75%, the purity of the product is 99.78%, and the product detection chromaticity is 5; the overall yield of the product of example 1-2 was 89.875%.
And adding 0.03G of polypropylacetamide into the bleaching wastewater obtained by standing, layering and separating, stirring for dissolving, then adding 0.03G of polyaluminum chloride, stirring to separate out a solid, filtering by using a sand core funnel of G4, wherein the solid is colored, the filtrate is the treated sodium sulfite, the color is obviously lightened for use, and the water obtained by secondary washing is also filtered by using a sand core funnel of G4, and the filtrate is used for use.
Example 3
The mother liquor of example 2 was used and 1.5g of fresh chlorobenzene and 22.8g of bisphenol A were added, and stirring was started for 0.5 h. After stirring, simultaneously dripping 32.6g of bromine and 25.5g of hydrogen peroxide, controlling the dripping temperature to be 30 ℃, after finishing dripping, heating to 88 ℃, keeping the temperature for reaction for 0.5h, standing for layering, standing for 0.5h, separating out a water phase, reducing 20g of recovered sodium sulfite in an organic phase in a sleeving manner, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 20g of 10% sodium sulfite solution into the organic phase for bleaching, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of water into the organic phase, heating to 90 ℃, standing for 0.5h, separating out the water phase, heating to 90 ℃, standing for 0.5h, cooling the organic phase to 8 ℃ by adopting frozen saline, obtaining a tetrabromobisphenol A product and a filtrate, and recycling the filtrate as a mother solution.
Based on bisphenol A, the yield of the tetrabromobisphenol A product is 99.8%, the purity of the product is 99.72%, the product detection chromaticity is 5, and the comprehensive yield of the products of examples 1-3 is 93.18%.
And (3) adding 0.03G of polypropylacetamide into the bleaching wastewater obtained by the standing and layering separation in the second step, stirring and dissolving, then adding 0.03G of polyaluminum chloride, stirring to separate out a solid, filtering by using a sand core funnel of G4, wherein the solid is colored, the filtrate is the treated sodium sulfite, the color is obviously lightened and the sodium sulfite is ready for use, and the water obtained by secondary washing is also filtered by using a sand core funnel of G4, and the filtrate is used for use.
Example 4
The mother liquor from example 3 was used and 1.5g of fresh chlorobenzene and 22.8g of bisphenol A were added, and stirring was started for 0.5 h. After stirring, simultaneously dripping 32.6g of bromine and 25.5g of hydrogen peroxide, controlling the dripping temperature to be 25 ℃, after finishing dripping, heating to 88 ℃, keeping the temperature for reaction for 40min, standing for layering, standing for 0.5h, separating out a water phase, adding 20g of recycled sodium sulfite for reduction in an organic phase, heating to 90 ℃, standing for 0.5h, separating out a water phase, adding 20g of 10% sodium sulfite solution into the organic phase for bleaching, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of organic phase water, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of water into the organic phase, heating to 90 ℃, standing for 0.5h, separating out the water phase, cooling the organic phase to 8 ℃ by adopting frozen saline, and performing suction filtration to obtain a tetrabromobisphenol A product and a filtrate, wherein the filtrate is used as a mother solution for recycling.
Based on bisphenol A, the yield of the tetrabromobisphenol A product is 99.82%, the product purity is 99.75%, the product detection chromaticity is 5, and the comprehensive yield of the products of examples 1-4 is 94.84%.
And (3) adding 0.04G of polypropylacetamide into the bleaching wastewater obtained by the standing and layering separation in the second step, stirring and dissolving, then adding 0.04G of polyaluminum chloride, stirring to separate out solids, filtering by using a sand core funnel of G4, wherein the solids are colored, the filtrate is the treated sodium sulfite, the color is obviously lightened and the sodium sulfite is ready for use, and the water obtained by secondary washing is also filtered by using a sand core funnel of G4, and the filtrate is used for use.
Example 5
The mother liquor of example 4 was used and 1.5g of fresh chlorobenzene and 22.8g of bisphenol A were added, and stirring was started for 0.5 h. After stirring, simultaneously dripping 32.4g of bromine and 25.1g of hydrogen peroxide, controlling the dripping temperature to be 25 ℃, after finishing dripping, heating to 88 ℃, keeping the temperature for reaction for 40min, standing for layering, standing for 0.5h, separating out a water phase, adding 20g of recycled sodium sulfite for reduction in an organic phase, heating to 90 ℃, standing for 0.5h, separating out a water phase, adding 20g of 10% sodium sulfite solution into the organic phase for bleaching, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of organic phase water, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of water into the organic phase, heating to 90 ℃, standing for 0.5h, separating out the water phase, cooling the organic phase to 8 ℃ by adopting frozen saline, and performing suction filtration to obtain a tetrabromobisphenol A product and a filtrate, wherein the filtrate is used as a mother solution for recycling.
Based on bisphenol A, the yield of the tetrabromobisphenol A product is 99.78%, the purity of the product is 99.73%, the product detection chromaticity is 5, and the comprehensive yield of the products in examples 1-5 is 95.83%.
And (3) adding 0.03G of polypropylacetamide into the bleaching wastewater obtained by the standing and layering separation in the second step, stirring and dissolving, then adding 0.03G of polyaluminum chloride, stirring to separate out a solid, filtering by using a sand core funnel of G4, wherein the solid is colored, the filtrate is the treated sodium sulfite, the color is obviously lightened and the sodium sulfite is ready for use, and the water obtained by secondary washing is also filtered by using a sand core funnel of G4, and the filtrate is used for use.
Example 6
The mother liquor from example 5 was used, 1.5g of fresh chlorobenzene and 22.8g of bisphenol A were added, and stirring was started for 0.5 h. After stirring, simultaneously dripping 32.4g of bromine and 25.1g of hydrogen peroxide, controlling the dripping temperature to be 20 ℃, after finishing dripping, heating to 88 ℃, keeping the temperature for reaction for 50min, standing for layering, standing for 0.5h, separating out a water phase, adding 20g of recycled sodium sulfite for reduction in an organic phase, heating to 90 ℃, standing for 0.5h, separating out a water phase, adding 20g of 10% sodium sulfite solution into the organic phase for bleaching, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of organic phase water, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of water into the organic phase, heating to 90 ℃, standing for 0.5h, separating out the water phase, cooling the organic phase to 8 ℃ by adopting frozen saline, and performing suction filtration to obtain a tetrabromobisphenol A product and a filtrate, wherein the filtrate is used as a mother solution for recycling.
Based on bisphenol A, the yield of the tetrabromobisphenol A product is 99.85 percent, the purity of the product is 99.75 percent, the product detection chromaticity is 5, and the comprehensive yield of the products of examples 1 to 6 is 96.5 percent.
And (3) adding 0.03G of polypropylacetamide into the bleaching wastewater obtained by the standing and layering separation in the second step, stirring and dissolving, then adding 0.03G of polyaluminum chloride, stirring to separate out a solid, filtering by using a sand core funnel of G4, wherein the solid is colored, the filtrate is the treated sodium sulfite, the color is obviously lightened and the sodium sulfite is ready for use, and the water obtained by secondary washing is also filtered by using a sand core funnel of G4, and the filtrate is used for use.
Example 7
The mother liquor collected in example 6 was used again 15 times, 1.5g of fresh chlorobenzene and 22.8g of bisphenol A were added each time, and stirring was started for 0.5 h. After stirring, simultaneously dripping 32.6g of bromine and 25.5g of hydrogen peroxide, controlling the dripping temperature to be 25 ℃, after finishing dripping, heating to 88 ℃, keeping the temperature for reaction for 40min, standing for layering, standing for 0.5h, separating out a water phase, adding 20g of recycled sodium sulfite for reduction in an organic phase, heating to 90 ℃, standing for 0.5h, separating out a water phase, adding 20g of 10% sodium sulfite solution into the organic phase for bleaching, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of organic phase water, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of water into the organic phase, heating to 90 ℃, standing for 0.5h, separating out the water phase, cooling the organic phase to 8 ℃ by adopting frozen saline, and performing suction filtration to obtain a tetrabromobisphenol A product and a filtrate, wherein the filtrate is used as a mother solution for recycling.
The 15 th time of mother liquor reuse (namely, the 20 times of mother liquor reuse collected in the example 1), the chroma of the product is 10, the purity is 99.65%, and the yield is 99.8%. The comprehensive yield of the products of examples 1-7 is 98.857%, and the average purity of the products is 99.72%.
Example 8
The mother liquor collected in example 7 was used again for 30 times, 1.5g of fresh chlorobenzene and 22.8g of bisphenol A were added each time, and stirring was started for 0.5 h. After stirring, simultaneously dripping 32.6g of bromine and 25.5g of hydrogen peroxide, controlling the dripping temperature to be 25 ℃, after finishing dripping, heating to 88 ℃, keeping the temperature for reaction for 40min, standing for layering, standing for 0.5h, separating out a water phase, adding 20g of recycled sodium sulfite for reduction in an organic phase, heating to 90 ℃, standing for 0.5h, separating out a water phase, adding 20g of 10% sodium sulfite solution into the organic phase for bleaching, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of organic phase water, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of water into the organic phase, heating to 90 ℃, standing for 0.5h, separating out the water phase, cooling the organic phase to 8 ℃ by adopting frozen saline, and performing suction filtration to obtain a tetrabromobisphenol A product and a filtrate, wherein the filtrate is used as a mother solution for recycling.
The 30 th time of mother liquor reuse (namely, the mother liquor collected in the example 1 is reused for 50 times), the chroma of the product is 15, the purity is 99.55%, and the yield is 99.8%. Examples 1 to 8 the overall yield of the product was 99.41%, and the average purity of the product was 99.63%
EXAMPLE 9
The mother liquor collected in example 8 was used again for 50 times, 1.5g of fresh chlorobenzene and 22.8g of bisphenol A were added each time, and stirring was started for 0.5 h. After stirring, simultaneously dripping 32.6g of bromine and 25.5g of hydrogen peroxide, controlling the dripping temperature to be 25 ℃, after finishing dripping, heating to 88 ℃, keeping the temperature for reaction for 40min, standing for layering, standing for 0.5h, separating out a water phase, adding 20g of recycled sodium sulfite for reduction in an organic phase, heating to 90 ℃, standing for 0.5h, separating out a water phase, adding 20g of 10% sodium sulfite solution into the organic phase for bleaching, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of organic phase water, heating to 90 ℃, standing for 0.5h, separating out the water phase, adding 50g of water into the organic phase, heating to 90 ℃, standing for 0.5h, separating out the water phase, cooling the organic phase to 8 ℃ by adopting frozen saline, and performing suction filtration to obtain a tetrabromobisphenol A product and a filtrate, wherein the filtrate is used as a mother solution for recycling.
The 50 th time of mother liquor reuse (namely the mother liquor collected in the example 1 is reused for 100 times), the chroma of the product is 20, the purity is 99.35%, and the yield is 99.8%. Examples 1 to 9 the overall yield of the product was 99.6%, and the average purity of the product was 99.54%
All percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of an energy-saving environment-friendly flame retardant tetrabromo double A is characterized by comprising the following steps:
(1) adding a certain amount of bisphenol A into chlorobenzene, stirring until the materials are uniformly mixed, wherein the stirring time is 0.5h, and simultaneously dropwise adding bromine and hydrogen peroxide at a specific temperature to obtain a tetrabromobisphenol A solution;
(2) heating the reaction system to carry out curing reaction, standing and separating out a water phase after curing is finished, collecting an organic phase to carry out standing and layering treatment for four times, cooling the collected organic phase to 8 ℃ by adopting frozen brine after standing and layering for four times, and carrying out suction filtration to obtain a tetrabromo-bis-A product.
2. The preparation method of the energy-saving and environment-friendly flame retardant tetrabromo double A as claimed in claim 1, characterized in that the four times of standing layering are as follows: standing for the first time for layering: adding 20g of 10% sodium sulfite solution into the organic phase for reduction, heating to 90 ℃, standing for 0.5h, separating out the water phase after standing, and collecting the organic phase;
standing and layering for the second time: and adding 20g of 10% sodium sulfite solution into the organic phase collected by the first standing and layering for bleaching, raising the temperature to 90 ℃, starting standing for 0.5h, separating out the water phase after the standing is finished, and collecting the organic phase.
3. The preparation method of the energy-saving and environment-friendly flame retardant tetrabromo double A as claimed in claim 2, characterized by further comprising the following steps: and (3) collecting bleaching wastewater generated by the secondary standing and layering, adding polypropionamide into the bleaching wastewater, stirring and dissolving, then adding polyaluminium chloride, stirring to separate out solids, filtering by using a sand core funnel of G4, wherein the solids are colored, the filtrate is treated sodium sulfite, the color is obviously lightened and the filtrate is ready for use, and the water obtained by secondary washing is also filtered by using a sand core funnel of G4, and the filtrate is used for use.
4. The preparation method of the energy-saving and environment-friendly flame retardant tetrabromo double A according to claim 1, characterized in that the dropping temperature of the bromine and the hydrogen peroxide is 0-30 ℃, preferably 20-30 ℃.
5. The preparation method of the energy-saving and environment-friendly flame retardant tetrabromo-bis-A as claimed in claim 1, wherein the mass ratio of the bisphenol A to the chlorobenzene is 1: 4-6.
6. The preparation method of the energy-saving and environment-friendly flame retardant tetrabromo double A as claimed in claim 1, characterized in that the bisphenol A: bromine: the molar ratio of hydrogen peroxide is 1: 2.01-2.1: 2.01-2.11.
7. The preparation method of the energy-saving and environment-friendly flame retardant tetrabromo-bis A as claimed in claim 1, wherein the curing reaction temperature is 0-95 ℃, and the curing time is 0.5-1 h.
8. The preparation method of the energy-saving and environment-friendly flame retardant tetrabromo-bis-A as claimed in claim 7, wherein the curing reaction temperature is 85-95 ℃.
9. The preparation method of the energy-saving and environment-friendly flame retardant tetrabromo-bis-A as claimed in claim 3, wherein the dosage of the polypropionamide is 0.05% -0.2% of the dosage of the sodium sulfite.
10. The preparation method of the energy-saving and environment-friendly flame retardant tetrabromo-bis A as claimed in claim 3, wherein the dosage of the polyaluminium chloride is 0.05% -0.2% of the dosage of sodium sulfite.
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| CN114656335A (en) * | 2022-04-13 | 2022-06-24 | 山东海王化工股份有限公司 | Tetrabromobisphenol A intermediate layer material recycling technology |
| CN114773203A (en) * | 2022-05-25 | 2022-07-22 | 浙江华洲药业有限公司 | Production process of p-nitrobenzyl alcohol |
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