CN114230444A - Preparation method of tribromophenol - Google Patents
Preparation method of tribromophenol Download PDFInfo
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- CN114230444A CN114230444A CN202111539727.3A CN202111539727A CN114230444A CN 114230444 A CN114230444 A CN 114230444A CN 202111539727 A CN202111539727 A CN 202111539727A CN 114230444 A CN114230444 A CN 114230444A
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- tribromophenol
- bromine
- halogenated alkane
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- chloride
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- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title abstract description 13
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims abstract description 66
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 60
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000000047 product Substances 0.000 claims abstract description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 20
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 12
- 239000006227 byproduct Substances 0.000 claims abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 37
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 36
- 229910052794 bromium Inorganic materials 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 21
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 14
- VPGDQIZKDYWQPS-UHFFFAOYSA-N sodium;2,3,4-tribromophenol Chemical compound [Na].OC1=CC=C(Br)C(Br)=C1Br VPGDQIZKDYWQPS-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 51
- 239000000543 intermediate Substances 0.000 description 20
- 239000012071 phase Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000005893 bromination reaction Methods 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 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 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 239000012450 pharmaceutical intermediate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
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- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/24—Inter-halogen compounds
-
- 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
Abstract
The invention relates to a preparation method of tribromophenol, belonging to the field of chemical synthesis. A preparation method of tribromophenol comprises the steps of dropwise adding halogenated alkane solution of bromine chloride into halogenated alkane solution of phenol, controlling the temperature of a reaction system to be not higher than 30 ℃ for reaction, separating by-product hydrogen chloride to obtain reaction liquid containing tribromophenol, and separating tribromophenol from the reaction liquid, wherein the mass concentration of bromine chloride in the halogenated alkane solution of bromine chloride is 25-60%; the mass concentration of phenol in the halogenated alkane solution of phenol is 5-10%. The method is easy for industrial production, environment-friendly, small in three-waste yield, high in production efficiency, good in product quality, high in product yield of more than 96% and high in purity of tribromophenol product of 99%.
Description
Technical Field
The invention relates to a preparation method of tribromophenol, belonging to the field of chemical synthesis.
Background
Tribromophenol (TBP) is an important fine chemical intermediate, is mainly used for reactive or additive flame retardants, and can also be used for pharmaceutical intermediates and mildew-proof preservatives. With the rapid development of the synthetic material industry, the demand of flame retardant synthesized by tribromophenol as raw material is rapidly increased, the market at home and abroad is very good, and the flame retardant is one of fine chemical intermediates with development potential and prospect at home.
The industrial synthesis of tribromophenol generally adopts water as a reaction medium, and bromine and phenol directly carry out substitution reaction. The direct bromination method produces hydrogen bromide as a byproduct, so that the atom utilization rate of bromine is only 50 percent at most. In order to improve the utilization rate of bromine, an oxidizing agent can be added into a reaction system to convert the generated hydrogen bromide into bromine, and the bromination reaction is continued, wherein the commonly used oxidizing agent is hydrogen peroxide, and related patents comprise CN101219935, CN10671236, CN101219935 and the like. The hydrogen peroxide is high in price and short in product transportation radius, and in addition, industrial products are generally 27.5% aqueous solution, more water is introduced into a tribromophenol reaction system, so that the waste water amount is increased, and the waste water treatment difficulty is high.
Bromine chloride (BrCl) is a interhalogen compound, and can be used in the fields of bactericides, oxidants, bleaches, industrial disinfectants, industrial water treatment agents and the like, and can also be used for coal-fired flue gas demercuration. The most important application of bromine chloride is as a brominating agent for bromination of flame retardants, dye intermediates and pharmaceutical intermediates. Compared with bromine, bromine chloride has two orders of magnitude faster bromination reaction speed, 1-2 times less metal corrosion rate, lower solidifying point (no heat preservation is needed in cold regions), 40% of effective bromine content per unit mass and high bromine atom utilization rate.
The bromine chloride substituted bromine is used as a brominating agent for synthesizing tribromophenol, so that the theoretical value of the utilization rate of bromine atoms is 100%, no oxidant is needed to be added, and the bromination reaction rate is high. There are reports in the literature (the development and application of Yanfan tribromophenol [ J ] journal of chemical industry, 1991, 000(002): 22-24.; research on the synthesis of 2,4, 6-tribromophenol by Liehu, Liu Han Hu. bromine chloride method [ J ] Anhui chemical industry, 1996(4): 16-18.) the synthesis of TBP by bromine chloride, high product yield, 50% bromine saving, reaction temperature of the process being 40 ℃, and a large amount of hydrochloric acid solution being added in the system to avoid the decomposition of bromine chloride and absorption of byproduct hydrogen chloride, the process has the problems of: firstly, 2-5% of chloride is generated in the product (bromination reaction is carried out in an organic phase, hydrochloric acid in a two-phase state does not completely play a protection role, and bromine chloride in the organic phase can be gasified and decomposed under the reaction condition of 40 ℃); the dihydrochloride phase can absorb bromine chloride in the organic phase while absorbing hydrogen chloride, so that the bromination reaction in the organic phase is not facilitated, and in addition, the added hydrochloric acid solution has the problem of treatment of phenol-containing acidic solution after the reaction; thirdly, the process does not address the removal of the reaction solvent.
The bromine chloride has a boiling point of 5 deg.C under normal pressure, the bromine chloride in liquid phase is stable, and the bromine chloride in gas phase can be rapidly decomposed into 60% BrCl and 20% Br2And 20% Cl2A mixture of (a). Bromine chloride can be dissolved in halogenated alkane solvent, 50% BrCl in dichloroethane, and the temperature of bubble appearance is 30 deg.C, and boiling point is higher than pure bromine chloride. Under the condition of solvent existence, bromine chloride is used as brominating agent for bromination reaction, the reaction temperature is controlled below 30 ℃, the decomposition of bromine chloride can be avoided, the product utilization rate is improved, and the generation of by-product chloride is reduced. Bromine chloride has low boiling point, is easy to volatilize, has high storage and transportation difficulty, and is ideal for on-site continuous production and use. Experiments show that the existence of the halogenated alkane solvent enables the synthesis rate of bromine chloride to be obviously higher than that under the condition of no solvent, and the reason is probably that the halogenated alkane solvent has liquefaction effect on raw material chlorine and is beneficial to the synthesis reaction of bromine chloride.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for producing tribromophenol by taking bromine chloride as an intermediate on the basis of the existing process technology for synthesizing tribromophenol and by combining the property characteristics of bromine chloride.
A process for preparing tribromophenol includes dropping the halogenated alkane solution of bromine chloride into the halogenated alkane solution of phenol, controlling the temp of reaction system not higher than 30 deg.C for reaction, separating by-product hydrogen chloride to obtain reaction liquid containing tribromophenol, separating tribromophenol from reaction liquid,
the mass concentration of bromine chloride in the halogenated alkane solution of bromine chloride is 25-60%; the mass concentration of phenol in the halogenated alkane solution of phenol is 5-10%.
The preparation method of tribromophenol is preferable, and the molar ratio of bromine chloride to phenol is 3.1-3.3: 1.
in the preferred preparation method of tribromophenol, the halogenated alkane is dichloroethane.
The preferred preparation method of tribromophenol of the invention, the method for separating hydrogen chloride is as follows: raising the temperature of the reaction system to 60 ℃ to drive away the hydrogen chloride; or extracting hydrogen chloride by adding water into the reaction system.
The preferred preparation method of tribromophenol of the invention, the hydrogen chloride after separation is converted into hydrochloric acid solution for the refining process of tribromophenol product. Specifically, the hydrochloric acid solution is used in the following steps: adding alkaline liquor into the reaction solution containing tribromophenol, stirring, standing for layering, converting tribromophenol into tribromophenol sodium, and dissolving in water phase.
The preparation method of the tribromophenol is preferable, and the method for separating the tribromophenol from the reaction liquid comprises the following steps: adding alkaline liquor into reaction liquid containing tribromophenol, stirring, standing for layering, converting tribromophenol into sodium tribromophenol, dissolving in water phase, separating oil phase which is halogenated alkane solvent, and recycling; and neutralizing the tribromophenol sodium in the water phase with a hydrochloric acid solution to precipitate a crude tribromophenol product, and filtering, washing and drying to obtain the tribromophenol product.
Further preferably, the obtained halogenated alkane solvent is separated and reused for the synthesis of the intermediate bromine chloride or/and the dissolution of the phenol raw material.
Further preferably, the residual bromine of the reaction system is eliminated with a sodium bisulfite solution before the addition of the alkali solution. Still more preferably, the alkali solution is a sodium hydroxide solution, and still more preferably a 10% sodium hydroxide solution.
The preferred preparation method of tribromophenol of the invention is that halogenated alkane solution of bromine chloride is prepared by the following method: dissolving bromine into a halogenated alkane solvent, wherein the mass concentration of the bromine is 20-50%, reacting the bromine with chlorine to synthesize a halogenated alkane solution of bromine chloride with the mass concentration of 25-60%, and adopting a microchannel reactor, a tubular reactor or a normal-pressure reaction kettle as a reactor.
In the technical scheme, the flow rate of the chlorine gas is preferably 0.5g/min, the ventilation time is determined according to the dosage of the raw materials, the raw materials are completely reacted, and unreacted chlorine gas can be absorbed by alkali liquor.
Further preferably, bromine is dehydrated and dissolved in dichloroethane, the dichloroethane is placed in a three-neck flask with the mass concentration of 40 percent, chlorine is slowly introduced for 4 hours at the temperature of-10 ℃, the chlorine flow is 0.5g/min, and unreacted chlorine is absorbed by alkali liquor to prepare the bromine chloride intermediate solution.
One preferable technical scheme of the preparation method of tribromophenol provided by the invention is as follows:
a preparation method of tribromophenol comprises the following process steps:
s1, synthesis of an intermediate bromine chloride: dissolving bromine into a halogenated alkane solvent, wherein the mass concentration of the bromine is 20-50%, and the bromine reacts with chlorine to synthesize a halogenated alkane solution of bromine chloride with the mass concentration of 25-60%;
s2, synthesis reaction of tribromophenol: dissolving phenol in halogenated alkane, wherein the mass concentration is 5-10%, slowly dropwise adding the halogenated alkane solution of bromine chloride obtained in the step S1 under the condition of stirring, controlling the temperature of a reaction system to be not higher than 30 ℃, reacting for 1-2 hours, and then separating by-product hydrogen chloride to obtain a reaction solution containing tribromophenol;
s3, separation and refining of tribromophenol products: adding alkali liquor into the reaction liquid containing tribromophenol obtained in the step S2, stirring, standing for layering, converting tribromophenol into tribromophenol sodium, and dissolving in water phase; the oil phase is halogenated alkane solvent, and is recycled for synthesizing intermediate bromine chloride or/and dissolving phenol raw material after separation; neutralizing the tribromophenol sodium in the water phase with hydrochloric acid solution to separate out crude tribromophenol, and filtering, washing and drying to obtain tribromophenol product;
wherein the molar ratio of bromine chloride to phenol is 3.1-3.3: 1.
compared with the prior art, the invention has the beneficial effects that:
the method of the invention uses bromine chloride as brominating agent to produce tribromophenol, bromine atoms can be completely utilized without adding oxidizing agent in the reaction system. Bromine chloride as an intermediate is prepared from bromine and chlorine gas as raw materials in the presence of a halogenated alkane solvent through a normal-pressure reaction kettle or a continuous flow reactor, and is used for the production of tribromophenol in situ. The bromination reaction of phenol is carried out in halogenated alkane solvent, the gasification and decomposition of bromine chloride intermediate are avoided by controlling the reaction temperature, hydrochloric acid is not added, and the discharge of acidic waste water is reduced. After bromination reaction, hydrogen chloride is separated and converted into hydrochloric acid solution, and all the hydrochloric acid solution is used in the product refining process (sodium tribromophenol is acidified to separate out tribromophenol products). Halogenated alkane solvent used in the tribromophenol synthesis process is separated in the product refining process, one part of the halogenated alkane solvent is used for synthesizing a bromine chloride intermediate after drying treatment, the other part of the halogenated alkane solvent is used for dissolving phenol raw materials, and the solvent is recycled in a system. The method is easy for industrial production, environment-friendly, small in three-waste yield, high in production efficiency, good in product quality, high in product yield of more than 96% and high in purity of tribromophenol product of 99%.
Drawings
Fig. 1 is a process flow diagram of a method for preparing tribromophenol.
Detailed Description
Example 1
S1, synthesis of an intermediate bromine chloride: after dehydration, bromine was dissolved in dichloroethane with a mass concentration of 40%, and the solution was placed in a three-necked flask, and chlorine gas was slowly introduced thereinto at-10 ℃ for 4 hours to prepare a bromine chloride intermediate solution (bromine chloride mass concentration of 49%).
S2, synthesis reaction of tribromophenol: 19.97 g of phenol is dissolved by 74.19 g of dichloroethane, 173.2 g of bromine chloride intermediate solution is slowly dropped into the solution under the condition of stirring, the temperature of a reaction system is kept at 20 ℃, the reaction time is 1 hour, the temperature of the system is raised to 60 ℃, and hydrogen chloride tail gas is separated by a condensing tube and absorbed as hydrochloric acid solution.
S3, separation and refining of tribromophenol products: after the reaction liquid is cooled, removing the residual bromine in the reaction system by using a sodium bisulfite solution, then adding a 10% sodium hydroxide solution to convert tribromophenol into tribromophenol sodium, dissolving the tribromophenol sodium in a water phase, oscillating, standing, extracting the water phase, and dehydrating and recycling an organic phase which is a dichloroethane solution. Adding a hydrochloric acid solution which is a byproduct of the reaction into the water phase, separating out a tribromophenol solid in the water phase, filtering, washing with water, and drying to obtain a white needle-shaped tribromophenol crystal, wherein the yield is 98.5%, the melting point is 90-92 ℃, and the product purity is 99.2%.
Example 2
After dehydration of bromine, the bromine was dissolved in dichloroethane to a 40% bromine solution by mass concentration, and a bromine chloride intermediate solution was prepared by a continuous flow reactor according to the method of CN 112794286. The subsequent steps were carried out with reference to example 1.
Example 3
S1, synthesis of an intermediate bromine chloride: after dehydration of bromine, the bromine was dissolved in dichloroethane to give a 20% bromine solution, and the solution was placed in a three-necked flask and chlorine gas was slowly introduced thereinto at-10 ℃ for 3 hours to obtain a bromine chloride intermediate solution (bromine chloride concentration: 26% by mass).
S2, synthesis reaction of tribromophenol: 15 g of phenol is dissolved by 180 g of dichloroethane, 100 g of bromine chloride intermediate solution is slowly dropped into the solution under the stirring condition, the temperature of the reaction system is kept at 20 ℃, and the reaction time is 2 hours. Then the temperature of the system rises to 60 ℃, and the hydrogen chloride tail gas is absorbed into hydrochloric acid solution after being separated by a condensing tube.
S3, separation and refining of tribromophenol products: after the reaction liquid is cooled, removing the residual bromine in the reaction system by using a sodium bisulfite solution, then adding a 10% sodium hydroxide solution to extract tribromophenol, and recycling the organic phase which is dichloroethane. Adding a hydrochloric acid solution into the water phase, separating out a tribromophenol solid in the water phase, filtering, washing with water, and drying to obtain a white needle-shaped tribromophenol crystal, wherein the yield is 98.3%, the melting point is 91-93 ℃, and the product purity is 99.4%.
Example 4
After dehydration of bromine, the bromine was dissolved in dichloroethane to give a bromine solution having a mass concentration of 20%, and a bromine chloride intermediate solution was prepared by a method of CN112794286 in a continuous flow reactor. The subsequent steps were carried out with reference to example 3.
Example 5
A bromine chloride intermediate solution was prepared as in example 3, and the bromination reaction was carried out by dropping the bromine chloride intermediate solution into the reaction system. After the reaction, 80 ml of water was directly added to the reaction system, and hydrogen chloride in the reaction was extracted to form hydrochloric acid. Standing for layering, separating hydrochloric acid phase, and using by oneself. Removing bromine residual in the reaction system by using a sodium bisulfite solution in an organic phase, adding a 10% sodium hydroxide solution to extract tribromophenol, dehydrating and recycling dichloroethane in the organic phase, adding a hydrochloric acid solution in a water phase, separating out tribromophenol solid, filtering, washing with water, and drying to obtain white needle-shaped crystals of tribromophenol, wherein the yield is 98.6%, the melting point is 89-92 ℃, and the product purity is 99.1%.
The scope of the invention is not limited to the disclosure of the above embodiments, and simple modifications and combinations of the embodiments are within the scope of the invention.
Claims (9)
1. A method for preparing tribromophenol is characterized in that halogenated alkane solution of bromine chloride is dripped into halogenated alkane solution of phenol, the temperature of a reaction system is controlled to be not higher than 30 ℃ for reaction, the reaction product contains tribromophenol and hydrogen chloride, by-product hydrogen chloride is separated to obtain reaction liquid containing tribromophenol, tribromophenol is separated from the reaction liquid, wherein,
the mass concentration of bromine chloride in the halogenated alkane solution of bromine chloride is 25-60%; the mass concentration of phenol in the halogenated alkane solution of phenol is 5-10%.
2. The method according to claim 1, wherein the molar ratio of bromine chloride to phenol is 3.1 to 3.3: 1.
3. the process according to claim 1, characterized in that the process for separating hydrogen chloride is: raising the temperature of the reaction system to 60 ℃ to drive away the hydrogen chloride; or extracting hydrogen chloride by adding water into the reaction system.
4. A process according to any one of claims 1 to 3, characterized in that the separated hydrogen chloride is converted into a hydrochloric acid solution for use in the tribromophenol product refining process.
5. The method according to claim 1, wherein the method for separating tribromophenol from the reaction solution comprises: adding alkaline liquor into the reaction solution containing tribromophenol, stirring, standing for layering, converting tribromophenol into sodium tribromophenol, and dissolving in water phase; the oil phase is halogenated alkane solvent, and is separated and recycled; and neutralizing the tribromophenol sodium in the water phase with a hydrochloric acid solution to precipitate a crude tribromophenol product, and filtering, washing and drying to obtain the tribromophenol product.
6. The process according to claim 5, wherein the halogenated alkane solvent obtained is separated and reused for the synthesis of intermediate bromine chloride or/and the dissolution of phenol raw material.
7. The process of claim 1 wherein the solution of bromine chloride in haloalkane is prepared by: dissolving bromine into a halogenated alkane solvent, wherein the mass concentration of the bromine is 20-50%, reacting the bromine with chlorine to synthesize a halogenated alkane solution of bromine chloride with the mass concentration of 25-60%, and adopting a microchannel reactor, a tubular reactor or a normal-pressure reaction kettle as a reactor.
8. The method according to claim 1, characterized by the following process steps:
s1, synthesis of an intermediate bromine chloride: dissolving bromine into a halogenated alkane solvent, wherein the mass concentration of the bromine is 20-50%, and the bromine reacts with chlorine to synthesize a halogenated alkane solution of bromine chloride with the mass concentration of 25-60%;
s2, synthesis reaction of tribromophenol: dissolving phenol in halogenated alkane, wherein the mass concentration is 5-10%, slowly dropwise adding the halogenated alkane solution of bromine chloride obtained in the step S1 under the condition of stirring, controlling the temperature of a reaction system to be not higher than 30 ℃, reacting for 1-2 hours, and then separating by-product hydrogen chloride to obtain a reaction solution containing tribromophenol;
s3, separation and refining of tribromophenol products: adding alkali liquor into the reaction liquid containing tribromophenol obtained in the step S2, stirring, standing for layering, converting tribromophenol into tribromophenol sodium, and dissolving in water phase; the oil phase is halogenated alkane solvent, and is recycled for synthesizing intermediate bromine chloride or/and dissolving phenol raw material after separation; and neutralizing the tribromophenol sodium in the water phase with a hydrochloric acid solution to precipitate a crude tribromophenol product, and filtering, washing and drying to obtain the tribromophenol product.
9. The method of any one of claims 1 to 8, wherein the haloalkane is dichloroethane.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3845146A (en) * | 1969-10-06 | 1974-10-29 | Dow Chemical Co | Bromination with bromine chloride under pressure |
| JPS5444603A (en) * | 1977-09-09 | 1979-04-09 | Asahi Glass Co Ltd | Bromination |
| JPS5444625A (en) * | 1977-09-16 | 1979-04-09 | Asahi Glass Co Ltd | Production of tribromophenol |
| CN112794286A (en) * | 2021-03-26 | 2021-05-14 | 大连海惠博科技有限公司 | Continuous flow method synthesis system and synthesis process of bromine chloride |
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- 2021-12-16 CN CN202111539727.3A patent/CN114230444A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3845146A (en) * | 1969-10-06 | 1974-10-29 | Dow Chemical Co | Bromination with bromine chloride under pressure |
| JPS5444603A (en) * | 1977-09-09 | 1979-04-09 | Asahi Glass Co Ltd | Bromination |
| JPS5444625A (en) * | 1977-09-16 | 1979-04-09 | Asahi Glass Co Ltd | Production of tribromophenol |
| CN112794286A (en) * | 2021-03-26 | 2021-05-14 | 大连海惠博科技有限公司 | Continuous flow method synthesis system and synthesis process of bromine chloride |
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