CN117264093A - Method for synthesizing brominated polystyrene - Google Patents
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- CN117264093A CN117264093A CN202311567178.XA CN202311567178A CN117264093A CN 117264093 A CN117264093 A CN 117264093A CN 202311567178 A CN202311567178 A CN 202311567178A CN 117264093 A CN117264093 A CN 117264093A
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 57
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 32
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 30
- MZJUGRUTVANEDW-UHFFFAOYSA-N bromine fluoride Chemical compound BrF MZJUGRUTVANEDW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 24
- 239000011737 fluorine Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 14
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- JPOXNPPZZKNXOV-UHFFFAOYSA-N bromochloromethane Chemical compound ClCBr JPOXNPPZZKNXOV-UHFFFAOYSA-N 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000003112 inhibitor Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000003063 flame retardant Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000011534 incubation Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 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 class 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 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- -1 chlorine radicals Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of synthesis of high molecular brominated flame retardants, and in particular relates to a method for synthesizing brominated polystyrene, which takes polystyrene as a reaction raw material and bromine monofluoride as a brominating agent to react at the temperature of-10 to 20 ℃. The method for synthesizing the brominated polystyrene has the advantages of simple process, no need of catalyst and free radical inhibitor, and high whiteness, good thermal stability and high bromine content of the synthesized brominated polystyrene product.
Description
Technical Field
The invention belongs to the technical field of synthesis of high molecular brominated flame retardants, and particularly relates to a method for synthesizing brominated polystyrene.
Background
The brominated polystyrene is a polymer brominated flame retardant, has the advantages of high flame retardant efficiency, good heat resistance, good compatibility with a flame-retardant substrate, no migration, no frosting and the like, and can well solve the problems of dioxin and toxic smoke. In recent years, as an environment-friendly flame retardant, brominated polystyrene with high bromine content, high thermal stability and high whiteness is increasingly paid attention to. The brominated polystyrene can be widely applied to flame retardance of high polymer materials after industrial production.
The industrial method for synthesizing brominated polystyrene mainly comprises two technological routes of brominated polystyrene which is polymerized after bromination and brominated polystyrene which is polymerized after bromination. At present, a process route of brominated polystyrene which is polymerized and then brominated is adopted in China. The process route is to synthesize brominated polystyrene by using antimony trichloride or aluminum trichloride as a catalyst, polystyrene as a raw material and bromine chloride or bromine as a brominating agent through a batch kettle reactor. The synthetic route uses bromine chloride or bromine as a brominating agent, and can inevitably generate chlorine radicals or bromine radicals, so that the main chain of the polystyrene is brominated or subjected to chlorination reaction, and the thermal stability of the prepared brominated polystyrene product is reduced, and the color of the product is yellow. And the use of antimony trichloride or aluminum trichloride catalyst can lead to Friedel-crafts reaction of the solvent and polystyrene, which can further reduce the thermal stability of the product. In order to improve the quality of the product, chinese patent document with publication number of CN112898453A discloses an environment-friendly brominated polystyrene synthesis process, which synthesizes the environment-friendly brominated polystyrene product by adding a main chain inhibitor. The Chinese patent document with publication number of CN100540572C discloses a post-treatment method of brominated polystyrene, which comprises the steps of dissolving commercially available brominated polystyrene by tetrahydrofuran, adding a reducing agent, removing chlorine and bromine in a main chain of the brominated polystyrene, and greatly improving the thermal stability and the melt index of the product. Although the methods can improve the quality of the product, the method adds a free radical inhibitor or improves the quality of the product by a post-treatment method, thereby increasing the process flow and the production cost and being not beneficial to large-scale production.
Disclosure of Invention
The invention aims to provide a method for synthesizing brominated polystyrene, which takes bromine monofluoride as a brominating agent, and avoids the decomposition of the bromine monofluoride through low-temperature synthesis and the existing preparation method. The method does not need a catalyst and a free radical inhibitor, has the advantages of simple process, less waste water and low production cost, and the prepared brominated polystyrene has the advantages of high thermal stability, high bromine content and high whiteness.
The technical scheme of the invention is as follows: a method for synthesizing brominated polystyrene comprises the following specific steps:
(1) Preparing bromine and a chlorine-containing organic solvent into a mixed solution A, introducing fluorine gas into the mixed solution A at the temperature of minus 30 ℃ to minus 20 ℃ for 2-4 hours, and continuing to react for 0.5-1 hour after the introduction of the fluorine gas is finished to obtain a bromine fluoride solution;
(2) Preparing a mixed solution B from polystyrene and a chlorine-containing organic solvent, dropwise adding a bromine monofluoride solution into the mixed solution B at the temperature of-10-0 ℃ for 2-5h, controlling the temperature to be 0-20 ℃ after the dropwise adding is finished, and carrying out heat preservation reaction for 1-5h, wherein the chlorine-containing organic solvent is the same as that in the step (1);
(3) And after the heat preservation reaction is finished, adding sodium sulfite aqueous solution into the reaction solution until the color of the reaction solution becomes white or light yellow, then performing alkali washing and water washing on the organic layer to be neutral, dripping the organic layer into boiling water to remove the solvent, obtaining a brominated polystyrene crude product, and drying to constant weight to obtain a brominated polystyrene product.
In the step (1), the chlorine-containing organic solvent is one of 1, 2-dichloroethane, dichloromethane, chloroform and 1-bromochloromethane, the water content is lower than 50ppm, and the mass ratio of bromine to the chlorine-containing organic solvent is 30-60: 100.
in the step (1), the mass ratio of fluorine gas to bromine is 23-25: 100.
in the step (2), the mass ratio of the polystyrene to the chlorine-containing organic solvent is 5-15: 100.
in the step (2), the molar ratio of bromine monofluoride to polystyrene monomer is 1:2.86 to 3.25.
The beneficial effects are that: the method uses bromine monofluoride as a brominating agent, and the bromine monofluoride does not generate bromine free radicals due to strong electronegativity of fluorine atoms, but generates bromine positive ions more easily, namely bromine is +1 valent and fluorine is-1 valent. The use of bromine monofluoride as a brominating agent does not require a lewis acid catalyst to induce the production of bromide positive ions, and does not require a radical inhibitor to inhibit the formation of bromine radicals, as compared to bromine or bromine chloride. Therefore, the invention has the advantages of simple process, easy control, no use of catalyst and free radical inhibitor, simple post treatment, less waste water and low production cost, and is suitable for large-scale industrial application.
The method does not generate bromine free radicals or chlorine free radicals, so that bromination or chlorination reaction of a main chain of the brominated polystyrene can be avoided, and meanwhile, as a Lewis acid catalyst is not used, friedel-crafts reaction of a solvent and the polystyrene is greatly reduced, so that the synthesized brominated polystyrene has the advantages of high thermal stability, high bromine content and high whiteness.
Because bromine monofluoride has poor stability and is easy to decompose, no report of preparing brominated polystyrene by taking bromine monofluoride as a brominating agent exists. The method greatly inhibits the decomposition of bromine monofluoride by the modes of current preparation, limiting the water content of the solvent, low-temperature reaction and the like, so that the bromine monofluoride can be used as a brominating reagent to prepare brominated polystyrene.
Detailed Description
In order to better understand the technical solutions of the present invention, the following description will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
(1) 60g of bromine and 100g of methylene dichloride are added into a 500ml four-port bottle, the water content of the methylene dichloride is 50ppm, 13.8g of fluorine gas is introduced into the four-port bottle at the temperature of minus 30 ℃, the time for introducing the fluorine gas is 2 hours, and stirring is continued for 0.5 hour after the introduction of the fluorine gas is finished.
(2) Into another 1L four-mouth bottle, 27.3g polystyrene and 545g methylene dichloride are added, prepared bromine monofluoride is added dropwise at the temperature of minus 10 ℃ for 5 hours, the temperature is adjusted to 0 ℃ after the bromine monofluoride is added dropwise, and the reaction is continued for 5 hours.
(3) And after the heat preservation is finished, adding 10% sodium sulfite aqueous solution into the reaction solution until the reaction solution turns white or light yellow in color, then neutralizing and washing an organic layer with 100ml of 5% sodium hydroxide aqueous solution, washing the organic layer with deionized water to be neutral, dropwise adding the organic layer into boiling water to remove a solvent, obtaining a brominated polystyrene crude product, and drying the crude product to constant weight to obtain a brominated polystyrene product. The product quality is shown in Table 1.
Example 2
(1) 60g of bromine and 200g of 1, 2-dichloroethane with the water content of 42ppm are added into a 500ml four-port bottle, 15.0g of fluorine gas is introduced into the four-port bottle at the temperature of-20 ℃ for 4 hours, and stirring is continued for 1 hour after the introduction of the fluorine gas is finished.
(2) 24.0g of polystyrene and 160g of 1, 2-dichloroethane are added into another 1L four-necked flask, the prepared bromine monofluoride is dripped at the temperature of 0 ℃ for 5 hours, the temperature is adjusted to 20 ℃ after the bromine monofluoride is dripped, and the reaction is continued for 1 hour.
(3) After the end of the incubation period, the post-treatment was carried out in the same manner as in example 1, and the product quality was as shown in Table 1.
Example 3
(1) 60g of bromine and 120g of 1, 2-dichloroethane with the water content of 42ppm are added into a 500ml four-mouth bottle, 13.8g of fluorine gas is introduced into the four-mouth bottle at the temperature of minus 25 ℃ for 3 hours, and stirring is continued for 0.6 hours after the introduction of the fluorine gas is finished.
(2) 26.1g of polystyrene and 261g of 1, 2-dichloroethane are added into another 1L four-mouth bottle, the prepared bromine fluoride is dripped at the temperature of minus 5 ℃ for 2 hours, the temperature is adjusted to 10 ℃ after the bromine fluoride is dripped, and the reaction is continued for 3 hours.
(3) After the end of the incubation period, the post-treatment was carried out in the same manner as in example 1, and the product quality was as shown in Table 1.
Example 4
(1) 60g of bromine and 100g of 1-bromochloromethane are added into a 500ml four-port bottle, the water content of the 1-bromochloromethane is 35ppm, 13.8g of fluorine gas is introduced into the four-port bottle at the temperature of minus 20 ℃, the time for introducing the fluorine gas is 3 hours, and stirring is continued for 0.8 hour after the introduction of the fluorine gas is finished.
(2) 26.1g of polystyrene and 261g of 1-bromochloromethane are added into another 1L four-mouth bottle, the prepared bromine monofluoride is dripped at the temperature of minus 8 ℃ for 3 hours, the temperature is adjusted to 5 ℃ after the bromine monofluoride is dripped, and the reaction is continued for 3 hours.
(3) After the end of the incubation period, the post-treatment was carried out in the same manner as in example 1, and the product quality was as shown in Table 1.
Example 5
(1) 60g of bromine and 120g of chloroform with the water content of 30ppm are added into a 500ml four-port bottle, 13.8g of fluorine gas is introduced into the four-port bottle at the temperature of minus 25 ℃ for 2 hours, and stirring is continued for 0.5 hour after the introduction of the fluorine gas is finished.
(2) 25.0g of polystyrene and 250g of chloroform are added into another 1L four-mouth bottle, the prepared bromine fluoride is dripped at the temperature of minus 5 ℃ for 3 hours, the temperature is adjusted to 15 ℃ after the bromine fluoride is dripped, and the reaction is continued for 2 hours.
(3) After the end of the incubation period, the post-treatment was carried out in the same manner as in example 1, and the product quality was as shown in Table 1.
Example 6
(1) 60g of bromine and 120g of 1, 2-dichloroethane with the water content of 42ppm are added into a 500ml four-mouth bottle, 14.4g of fluorine gas is introduced into the four-mouth bottle at the temperature of-25 ℃ for 3 hours, and stirring is continued for 1 hour after the introduction of the fluorine gas is finished.
(2) 25.0g of polystyrene and 250g of 1, 2-dichloroethane are added into another 1L four-necked flask, the prepared bromine monofluoride is dripped at the temperature of minus 5 ℃ for 3 hours, the temperature is adjusted to 10 ℃ after the bromine monofluoride is dripped, and the reaction is continued for 4 hours.
(3) After the end of the incubation period, the post-treatment was carried out in the same manner as in example 1, and the product quality was as shown in Table 1.
Example 7
(1) 60g of bromine and 120g of methylene dichloride are added into a 500ml four-mouth bottle, wherein the water content of the methylene dichloride is 50ppm, 13.8g of fluorine gas is introduced into the four-mouth bottle at the temperature of minus 30 ℃, the time for introducing the fluorine gas is 3 hours, and stirring is continued for 0.7 hour after the introduction of the fluorine gas is finished.
(2) 26.1g of polystyrene and 261g of methylene dichloride are added into another 1L four-mouth bottle, the prepared bromine fluoride is dripped at the temperature of minus 3 ℃ for 3 hours, the temperature is adjusted to 10 ℃ after the bromine fluoride is dripped, and the reaction is continued for 3 hours.
(3) After the end of the incubation period, the post-treatment was carried out in the same manner as in example 1, and the product quality was as shown in Table 1.
Comparative example 1
(1) 60g of bromine and 120g of 1, 2-dichloroethane with the water content of 42ppm are added into a 500ml four-mouth bottle, 14.4g of chlorine gas is introduced into the four-mouth bottle at the temperature of minus 25 ℃ for 3 hours, and stirring is continued for 0.5 hour after the introduction of the chlorine gas is finished.
(2) 25.0g of polystyrene and 250g of 1, 2-dichloroethane are added into another 1L four-mouth bottle, prepared bromine chloride is dripped at the temperature of minus 5 ℃ for 3 hours, the temperature is adjusted to 10 ℃ after the bromine chloride is dripped, and the reaction is continued for 4 hours.
(3) After the end of the incubation period, the post-treatment was carried out in the same manner as in example 1, and the product quality was as shown in Table 1.
Comparative example 2
(1) 60g of bromine and 120g of 1, 2-dichloroethane were charged into a 500ml four-necked flask and the mixture was stirred for 0.5 hour, wherein the water content of 1, 2-dichloroethane was 42 ppm.
(2) 25.0g of polystyrene and 250g of 1, 2-dichloroethane are added into another 1L four-mouth bottle, the prepared bromine solution is dripped at the temperature of minus 5 ℃ for 3 hours, the temperature is adjusted to 10 ℃ after the dripping of the bromine solution is finished, and the reaction is continued for 4 hours.
(3) After the end of the incubation period, the post-treatment was carried out in the same manner as in example 1, and the product quality was as shown in Table 1.
After aging the samples of the above examples and comparative examples at 120 ℃, 1% TGA and 5% TGA were measured using a thermogravimetric instrument; measuring whiteness index with whiteness instrument; the bromine content is measured by a combustion method and a potentiometric titrator.
In addition to the above embodiments, the present invention also includes other embodiments, and all technical solutions that are formed by equivalent transformation or equivalent substitution should fall within the protection scope of the claims of the present invention.
Claims (5)
1. A method of synthesizing brominated polystyrene, comprising the steps of:
(1) Preparing bromine and a chlorine-containing organic solvent into a mixed solution A, introducing fluorine gas into the mixed solution A at the temperature of minus 30 ℃ to minus 20 ℃ for 2-4 hours, and continuing to react for 0.5-1 hour after the introduction of the fluorine gas is finished to obtain a bromine fluoride solution;
(2) Preparing a mixed solution B from polystyrene and a chlorine-containing organic solvent, dropwise adding a bromine monofluoride solution into the mixed solution B at the temperature of-10-0 ℃ for 2-5h, controlling the temperature to be 0-20 ℃ after the dropwise adding is finished, and carrying out heat preservation reaction for 1-5h, wherein the chlorine-containing organic solvent is the same as that in the step (1);
(3) And after the heat preservation reaction is finished, adding sodium sulfite aqueous solution into the reaction solution until the color of the reaction solution becomes white or light yellow, then performing alkali washing and water washing on the organic layer to be neutral, dripping the organic layer into boiling water to remove the solvent, obtaining a brominated polystyrene crude product, and drying to constant weight to obtain a brominated polystyrene product.
2. The method for synthesizing brominated polystyrene of claim 1, wherein in the step (1), the chlorine-containing organic solvent is one of 1, 2-dichloroethane, dichloromethane, chloroform and 1-bromochloromethane, the water content is lower than 50ppm, and the mass ratio of bromine to the chlorine-containing organic solvent is 30-60: 100.
3. the method for synthesizing brominated polystyrene of claim 1, wherein in the step (1), the mass ratio of fluorine gas to bromine is 23-25: 100.
4. the method for synthesizing brominated polystyrene of claim 1, wherein in the step (2), the mass ratio of polystyrene to chlorine-containing organic solvent is 5-15: 100.
5. the method of claim 1, wherein in step (2), the molar ratio of bromine monofluoride to polystyrene monomer is 1:2.86 to 3.25.
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