CN115403686B - Method for continuously synthesizing brominated polystyrene by micro-channel reactor - Google Patents
Method for continuously synthesizing brominated polystyrene by micro-channel reactor Download PDFInfo
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 60
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 43
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 43
- 229910052794 bromium Inorganic materials 0.000 claims description 43
- 239000000047 product Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 17
- 238000010791 quenching Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical group CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000000171 quenching effect Effects 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 5
- JPOXNPPZZKNXOV-UHFFFAOYSA-N bromochloromethane Chemical compound ClCBr JPOXNPPZZKNXOV-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000011437 continuous method Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 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 5
- 230000000694 effects Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000007921 spray 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
- 239000004677 Nylon Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 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 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YDVNLQGCLLPHAH-UHFFFAOYSA-N dichloromethane;hydrate Chemical compound O.ClCCl YDVNLQGCLLPHAH-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 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
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- 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
- C08F8/22—Halogenation by reaction with free halogens
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The utility model relates to a method for continuously synthesizing brominated polystyrene by a microchannel reactor, belonging to the technical field of organic synthesis processes. More specifically, polystyrene is taken as raw material, respectively dissolved in organic solvent and brominated by a micro-channel reactor, the material ratio, the residence time and the reaction temperature are controlled, the reacted material enters a gas-liquid separation device for gas-liquid separation, the gas is absorbed by water, and the liquid is quenched, alkali washed, water washed, flash evaporated, suction filtered, dried and the like to obtain the product brominated polystyrene. The process method of the utility model adopts a continuous method different from the traditional intermittent synthesis, and greatly improves the synthesis efficiency and safety of the brominated polystyrene.
Description
Technical Field
The utility model relates to a method for continuously synthesizing brominated polystyrene by a microchannel reactor, belonging to the technical field of organic synthesis processes.
Background
Brominated flame retardant is an organic flame retardant widely used at present, and representative products of polybrominated diphenyl and polybrominated diphenyl ether thereof take the dominant position in the flame retardant market at one time. The polybrominated diphenyl and polybrominated diphenyl ether can generate cancerogenic substances such as dioxin and the like to harm the health of human bodies when being burnt, so that the substitutes of the polybrominated diphenyl and polybrominated diphenyl ether are promoted to appear. The brominated Polystyrene (Brominated Polystyrene, BPS) is a brominated product of Polystyrene (PS), has the advantages of high bromine content, low toxicity, good thermal stability, good dispersibility in high molecular polymers, no frosting on the surface, no static electricity, no migration and the like, and is widely used for flame retardant treatment of nylon, ABS, PBT and other materials.
Brominated polystyrene is generally synthesized by direct bromination of polystyrene using a brominating agent, which may be bromine or bromine chloride, including non-solvent and solvent methods. The non-solvent method is to directly put polystyrene into brominating agent and heat to bromize, and the method has the advantages of simple operation, poor product quality and very low bromine content. The solvent method is to prepare polystyrene into solution and then react with brominating agent, and the brominating agent is low in consumption, good in product quality and high in bromine content due to homogeneous reaction. Yao Ying and the like are prepared by using polystyrene as a raw material, bromine chloride as a brominating agent, antimony trichloride as a catalyst and dichloroethane as a solvent, wherein the bromine content of the product prepared by the method is more than 65%, and the whiteness is more than 70. The method comprises the steps of brominating polystyrene with bromine under catalysis of aluminum trichloride, titanium tetrachloride and aluminum powder by taking dichloroethane as a solvent, so as to obtain brominated polystyrene with bromine content of more than 60%. In the production process of the non-solvent method or the solvent method, a large amount of brominating agent is needed to be used in order to ensure the flame retardant effect of the product, the brominating agent is extremely toxic and has great harm to human bodies, the brominating agent has strong corrosiveness, the requirement on production equipment is high, and the intermittent operation risk is great.
CN114957517a discloses a method for continuously producing brominated polystyrene, firstly, feeding a material flow a containing polystyrene, a low-activity catalyst and a halogenated alkane solvent and a material flow B containing a brominating agent and a halogenated alkane solvent into a first-stage reaction kettle for reaction, feeding the material after the first-stage reaction into a second-stage reaction kettle, and simultaneously feeding a material flow C containing a brominating agent, a halogenated alkane solvent and a high-activity catalyst into the second-stage reaction kettle for continuous reaction; the brominated polystyrene is obtained through neutralization, water washing, evaporative crystallization, suction filtration and drying, the primary reaction kettle uses a catalyst with relatively weak activity and a lower reaction temperature, the secondary reaction kettle uses a catalyst with relatively strong activity and a higher reaction temperature, bromine on a main chain of a product can be effectively prevented, the defect of low bromine content of the product is avoided, and the high-quality brominated polystyrene with good thermal stability and high bromine content can be prepared. The method needs two-stage reaction, and the process is relatively complex.
CN214261888U utility model discloses a continuous production device of brominated polystyrene based on microreactor, comprising a reaction kettle, a microreactor and a first condenser which are circularly connected in series; the micro-reactor is also communicated with a bromine chloride storage tank; a discharge port of the reaction kettle is communicated with a decoloring kettle; a discharge hole of the decoloring kettle is communicated with a water washing kettle, and a water phase outlet of the water washing kettle is communicated with the decoloring kettle; the gas outlet at the top of the reaction kettle is communicated with a hydrogen chloride absorption tank through a second condenser; the upper part of the hydrogen chloride absorption tank is provided with a liquid distribution disc which is communicated with a liquid inlet pipe arranged at the top of the hydrogen chloride absorption tank; a plurality of porous spray pipes communicated with the liquid distribution disc are arranged below the liquid distribution disc; the porous spray pipe is circumferentially provided with a plurality of spoilers. The device can effectively avoid the by-product hydrogen chloride in the reaction to take away bromine chloride, and improves the quality of the product. The device also passes through the reaction kettle and then enters the micro-reactor, namely two-stage reaction is needed, and the process is complex.
Disclosure of Invention
The utility model aims to solve the problems in the background problems, and provides a method for continuously synthesizing brominated polystyrene by a microchannel reactor, which has the characteristics of simple process, high production efficiency, good safety, good thermal stability, high bromine content and low chromaticity.
The purpose of the utility model is realized in the following way: a method for continuously synthesizing brominated polystyrene in a microchannel reactor, the method comprising the steps of:
s01, respectively dissolving polystyrene and bromine in an organic solution, adding a catalyst into the solution in which the bromine is dissolved, and placing the two solutions in an ice bath for cooling;
s02, pumping the two solutions cooled in the step S01 into a microchannel reactor through a metering pump at a certain flow rate to carry out mixing and reaction, and after the reaction is finished, enabling the materials to enter a gas-liquid separation device to carry out gas-liquid separation and absorbing gas by using water;
s03, enabling the separated liquid in the step S02 to flow into water for quenching, standing for layering, and then conducting alkaline washing and water washing on the organic layer to be neutral;
s04, dropwise adding the organic layer washed to be neutral in the S03 into hot water to remove the solvent, separating out solids, performing suction filtration to obtain a crude product, and drying at a high temperature to constant weight to obtain the product.
In S01, the molar quantity of bromine is 2.5-3.0 times of the molar quantity of polystyrene benzene ring, the solvent is one or more of dichloromethane, trichloromethane, 1, 2-dichloroethane and bromochloromethane, the water content of the solvent is lower than 100ppm, the same quantity of the solvent dissolved with the brominating agent as that of the dissolved polystyrene is 4.5 times of the mass of the polystyrene, the catalyst is aluminum bromide, the adding quantity of the catalyst is 1-10% of the mass of the polystyrene, and the temperature is reduced to-5-15 ℃ in an ice bath (same as the reaction temperature).
In S02, the reaction temperature is-5-15 ℃, the residence time is 10-30 min, and the flow rate is calculated according to the residence time.
In S03, alkali liquor of alkali washing is one or two of sodium hydroxide or sodium bicarbonate, and if effluent liquid contains bromine, sodium bisulphite is required to be added during quenching.
In S04, the temperature of hot water is 70-95 ℃, the drying temperature is 140-160 ℃, and the drying time is 1-3 h.
Compared with the prior art, the utility model has the following advantages:
the method for continuously synthesizing the brominated polystyrene by using the microchannel reactor takes the polystyrene as a raw material, respectively dissolves the polystyrene and the bromine in an organic solvent, controls the temperature by ice bath, continuously bromizes by using the microchannel reactor, and directly reacts in one step, thereby greatly improving the synthesis efficiency and the safety of the brominated polystyrene. The synthesized brominated polystyrene has the characteristics of good heat stability, high bromine content and low chromaticity.
Drawings
FIG. 1 shows the synthetic route of brominated polystyrene of the present utility model.
FIG. 2 is a flow chart of a process for continuously synthesizing brominated polystyrene in a microchannel reactor of the utility model.
Detailed Description
The present utility model is further described below with reference to examples, which are only for more clearly illustrating the technical solution of the present utility model, but are not to be construed as limiting the scope of the present utility model.
Example 1
20.0 g polystyrene was dissolved in 90g methylene chloride (moisture less than 100 ppm), 83.1 g bromine (2.7 times the molar amount of benzene ring) and 1.2g aluminum bromide in 90g methylene chloride; cooling the two materials to 0 ℃ in an ice bath, and continuously entering a micro-channel reactor through two metering pumps respectively for mixing and reacting, wherein the reaction temperature is 0 ℃ and the residence time is 20 min; the materials enter a gas-liquid separation device for gas-liquid separation, gas is introduced into an absorption device, liquid is introduced into water for quenching, and potassium iodide test paper is used for detecting that the water layer is not discolored.
The post-treatment mode comprises the following steps: standing and layering the oil-water mixture, adding 200g of 1% sodium hydroxide solution into an oil layer, stirring and washing for 30min, and standing and layering; dropwise adding the oil layer into hot water at 95 ℃ for flash evaporation, and removing the solvent to obtain a mixture containing a product and water; and (3) carrying out suction filtration after cooling, and drying the obtained wet material in a drying oven at 150 ℃ for 2 h to obtain 61.2 g brominated polystyrene products.
The bromine content of the product was 67.6%, the whiteness 87.3,1% TGA was 356 ℃.
Example 2
20.0 g polystyrene was dissolved in 90g of methylene chloride (moisture less than 100 ppm), 86.2 g bromine (2.8 times the molar amount of benzene ring) and 1.0g of aluminum bromide was dissolved in 90g of methylene chloride; cooling the two materials to 0 ℃ in an ice bath, and continuously entering a micro-channel reactor through two metering pumps respectively for mixing and reacting, wherein the reaction temperature is 0 ℃ and the residence time is 20 min; the material enters a gas-liquid separation device to carry out gas-liquid separation, gas is introduced into an absorption device, liquid is introduced into water to quench, a water layer is detected to be not discolored by potassium iodide test paper, and then post-treatment is carried out in the same way as in example 1. 62.5g of brominated polystyrene product was obtained.
The bromine content of the product was 68.4%, the whiteness was 86.8,1% TGA was 355 ℃.
Example 3
20.0 g polystyrene was dissolved in 90g of methylene chloride (moisture less than 100 ppm), 92.3 g bromine (3.0 times the molar amount of benzene rings) and 1.2g aluminum bromide was dissolved in 90g of methylene chloride; cooling the two materials to 0 ℃ in an ice bath, and continuously entering a micro-channel reactor through two metering pumps respectively for mixing and reacting, wherein the reaction temperature is 0 ℃ and the residence time is 20 min; the materials enter a gas-liquid separation device to carry out gas-liquid separation, gas is introduced into an absorption device, liquid is introduced into water to quench, a water layer is detected to change color by using potassium iodide test paper, 4g of sodium bisulphite is added, stirring is carried out for 30min, and then post treatment is carried out as in example 1. 61.7. 61.7 g brominated polystyrene product was obtained.
The bromine content of the product was 68.9%, the whiteness was 85.2,1% TGA was 353 ℃.
Example 4
20.0 g polystyrene was dissolved in 90g of methylene chloride (moisture less than 100 ppm), 76.9 g bromine (2.5 times the molar amount of benzene rings) and 1.0g aluminum bromide was dissolved in 90g of methylene chloride; cooling the two materials to 0 ℃ in an ice bath, and continuously entering a micro-channel reactor through two metering pumps respectively for mixing and reacting, wherein the reaction temperature is 0 ℃ and the residence time is 20 min; the material enters a gas-liquid separation device to carry out gas-liquid separation, gas is introduced into an absorption device, liquid is introduced into water to quench, a water layer is detected to be not discolored by potassium iodide test paper, and then post-treatment is carried out in the same way as in example 1. 58.0. 58.0 g brominated polystyrene product was obtained.
The bromine content of the product was 65.5%, the whiteness 88.3,1% TGA was 344 ℃.
Example 5
20.0 g polystyrene was dissolved in 90g methylene chloride (moisture less than 100 ppm), 83.1 g bromine (2.7 times the molar amount of benzene ring) and 1.0g aluminum bromide in 90g methylene chloride; cooling the two materials to 5 ℃ in an ice bath, and continuously entering a microchannel reactor through two metering pumps respectively for mixing and reacting, wherein the reaction temperature is 5 ℃ and the residence time is 20 min; the material enters a gas-liquid separation device to carry out gas-liquid separation, gas is introduced into an absorption device, liquid is introduced into water to quench, a water layer is detected to be not discolored by potassium iodide test paper, and then post-treatment is carried out in the same way as in example 1. 61.5. 61.5 g brominated polystyrene product was obtained.
The bromine content of the product was 67.9%, the whiteness was 86.4,1% TGA was 355 ℃.
Example 6
20.0 g polystyrene was dissolved in 90g of methylene chloride (moisture less than 100 ppm), 83.1 g bromine (2.7 times the molar amount of benzene rings) and 1.0g aluminum bromide was dissolved in 90g of methylene chloride; cooling the two materials to 0 ℃ in an ice bath, and continuously entering a micro-channel reactor through two metering pumps respectively for mixing and reacting, wherein the reaction temperature is 0 ℃ and the residence time is 10min; the materials enter a gas-liquid separation device to carry out gas-liquid separation, gas is introduced into an absorption device, liquid is introduced into water to quench, a water layer is detected to change color by using potassium iodide test paper, 10g of sodium bisulphite is added, stirring is carried out for 30min, and then post treatment is carried out as in example 1. 53.7 g brominated polystyrene product was obtained.
The bromine content of the product was 62.9%, the whiteness was 81.5,1% TGA was 339 ℃.
Example 7
20.0 g polystyrene was dissolved in 90g of methylene chloride (moisture less than 100 ppm), 83.1 g bromine (2.7 times the molar amount of benzene rings) and 1.0g aluminum bromide was dissolved in 90g of methylene chloride; cooling the two materials to 15 ℃ in an ice bath, and continuously entering a microchannel reactor through two metering pumps respectively for mixing and reacting, wherein the reaction temperature is 15 ℃, and the residence time is 10min; the material enters a gas-liquid separation device to carry out gas-liquid separation, gas is introduced into an absorption device, liquid is introduced into water to quench, a water layer is detected to be not discolored by potassium iodide test paper, and then post-treatment is carried out in the same way as in example 1. This gives 60.4. 60.4 g brominated polystyrene product.
The bromine content of the product was 67.0%, the whiteness was 84.6,1% TGA at 351 ℃.
Comparative example 1
Based on example 1, this comparative example differs from example 1 only in that the reaction was carried out at room temperature without an ice bath.
The result was a product with a bromine content of 67.2% and a whiteness of 79.7,1% TGA of 344 ℃, which is much lower than example 1.
Comparative example 2
This comparative example differs from example 1 only in that the amount of aluminum bromide used is 0.1g.
As a result, the reaction was incomplete, a large amount of bromine was unreacted, 50g of sodium hydrogensulfite was added at the time of quenching, the bromine content of the product was 44.3%, the whiteness was 73.4,1% TGA was 332℃and the bromine content was low.
Comparative example 3
The comparative example differs from example 1 only in that the methylene chloride water content is 200 to 300ppm. [
The result was a product with a bromine content of 67.5% and a whiteness of 85.9,1% TGA of 354 ℃ and a whiteness lower than example 1.
Comparative example 4
The comparative example differs from example 1 only in that the residence time is 5 min.
As a result, the reaction was incomplete, part of bromine was unreacted, 20. 20 g sodium bisulphite was added during quenching, the bromine content of the product was 51.1%, the whiteness was 76.3,1% TGA was 334℃and the bromine content was low.
The foregoing is merely a specific application example of the present utility model, and the protection scope of the present utility model is not limited in any way. All technical schemes formed by equivalent transformation or equivalent substitution fall within the protection scope of the utility model.
Claims (7)
1. A method for continuously synthesizing brominated polystyrene in a microchannel reactor, the method comprising the steps of:
s01, respectively dissolving polystyrene and bromine in an organic solvent, adding a catalyst into a solution in which the bromine is dissolved, and placing the two solutions in an ice bath for cooling;
s02, pumping the two solutions cooled in the step S01 into a microchannel reactor through a metering pump at a certain flow rate to carry out mixing and reaction, and after the reaction is finished, enabling the materials to enter a gas-liquid separation device to carry out gas-liquid separation and absorbing gas by using water;
s03, enabling the separated liquid in the step S02 to flow into water for quenching, standing for layering, and then conducting alkaline washing and water washing on the organic layer to be neutral;
s04, dropwise adding the organic layer washed to be neutral in the S03 into hot water to remove a solvent, separating out solids, performing suction filtration to obtain a crude product, and drying at a high temperature to constant weight to obtain a product;
in S01, the organic solvent is one or more of dichloromethane, chloroform, 1, 2-dichloroethane and bromochloromethane, and the water content of the organic solvent is lower than 100ppm.
2. A method for continuous synthesis of brominated polystyrene in a microchannel reactor as set forth in claim 1, wherein: in S01, the molar quantity of bromine is 2.5-3.0 times of the molar quantity of polystyrene benzene ring.
3. A method for continuous synthesis of brominated polystyrene in a microchannel reactor as set forth in claim 1, wherein: the catalyst is aluminum bromide, and the adding amount of the catalyst is 1-10% of the mass of the polystyrene.
4. A method for continuous synthesis of brominated polystyrene in a microchannel reactor as set forth in claim 1, wherein: and in S01, cooling to-5-15 ℃ in an ice bath.
5. A method for continuous synthesis of brominated polystyrene in a microchannel reactor as set forth in claim 1, wherein: in S02, the reaction temperature is-5-15 ℃ and the residence time is 10-30 min.
6. A method for continuous synthesis of brominated polystyrene in a microchannel reactor as set forth in claim 1, wherein: in S03, alkali liquor of alkali washing is one or two of sodium hydroxide or sodium bicarbonate, and if effluent liquid contains bromine, sodium bisulphite is required to be added during quenching.
7. A method for continuous synthesis of brominated polystyrene in a microchannel reactor as set forth in claim 1, wherein: in S04, the temperature of hot water is 70-95 ℃, the drying temperature is 140-160 ℃, and the drying time is 1-3 h.
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