CN116769073A - Method for continuously producing brominated polystyrene - Google Patents
Method for continuously producing brominated polystyrene Download PDFInfo
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- CN116769073A CN116769073A CN202310355798.0A CN202310355798A CN116769073A CN 116769073 A CN116769073 A CN 116769073A CN 202310355798 A CN202310355798 A CN 202310355798A CN 116769073 A CN116769073 A CN 116769073A
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- polystyrene
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- brominated polystyrene
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- continuously producing
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 77
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 13
- 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 claims abstract description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 3
- YSCVYRUCAPMZFG-UHFFFAOYSA-K trichlorotin Chemical compound Cl[Sn](Cl)Cl YSCVYRUCAPMZFG-UHFFFAOYSA-K 0.000 claims abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 15
- 238000005893 bromination reaction Methods 0.000 claims description 13
- 230000031709 bromination Effects 0.000 claims description 10
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000010517 secondary reaction Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- IRDQNLLVRXMERV-UHFFFAOYSA-N CCCC[Na] Chemical group CCCC[Na] IRDQNLLVRXMERV-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- JPOXNPPZZKNXOV-UHFFFAOYSA-N bromochloromethane Chemical compound ClCBr JPOXNPPZZKNXOV-UHFFFAOYSA-N 0.000 claims 2
- 238000004042 decolorization Methods 0.000 claims 2
- 238000007599 discharging Methods 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000010008 shearing Methods 0.000 abstract description 5
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 230000017525 heat dissipation Effects 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 238000005554 pickling Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- -1 polybutylene terephthalate Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 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 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 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
- 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
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- 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)
- 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)
Abstract
The invention relates to the technical field of preparation of high molecular brominated flame retardants, and discloses a method for continuously producing brominated polystyrene, wherein 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 are fed into a first-stage reaction kettle to react, the reaction temperature is controlled to be 4-26 ℃, the residence time is 3-6 hours, and the low-activity catalyst is one of antimony trichloride, tin trichloride and titanium tetrachloride. In the invention, the second section and the third section are initiator butyllithium metering and polymerization reaction sections, the temperature is 30-120 ℃, the fourth section and the fifth section are mainly melt conveying sections, the temperature is 120-190 ℃, the sixth section is a die section, the temperature is 150-200 ℃, the polymerization reaction temperature is too low, the polymerization rate is too low, the conversion rate is insufficient, and the mechanical shearing degradation of the polymer is easy to cause. The polymerization reaction temperature is too high, the polymerization rate is too high, the heat dissipation is insufficient, thermal degradation is caused, and the distribution of the polymerization reaction temperature is precisely controlled in a trapezoid shape.
Description
Technical Field
The invention relates to the technical field of preparation of high molecular brominated flame retardants, in particular to a method for continuously producing brominated polystyrene.
Background
The brominated polystyrene is an environment-friendly brominated flame retardant, and compared with the traditional brominated flame retardants, such as polybrominated diphenyl and decabromodiphenyl ether, the brominated polystyrene has the advantages of safety and low toxicity, and does not release a large amount of smoke and toxic gas. The brominated polystyrene has high thermal stability and excellent compatibility, and is widely applied to engineering plastics such as polybutylene terephthalate, polyethylene terephthalate, nylon-66 and the like, and the current industrial method for synthesizing the brominated polystyrene mainly comprises two technological routes of brominated polystyrene which is polymerized after bromination and brominated polystyrene which is polymerized after bromination. The existing process route is to take polystyrene as raw material, under the catalysis of Lewis acid, react with brominating agent bromine or bromine chloride to obtain brominated polystyrene, the process has the advantages of simple process and high bromine content of the product, but the process can lead to easy bromination reaction of the main chain, and easy Friedel-crafts alkylation reaction with solvent, so that the product has poor chromaticity and stability. The domestic manufacturers adopt a production process of firstly polymerizing and then brominating, but most manufacturers adopt an intermittent kettle type reactor to produce brominated polystyrene, so that the production efficiency is low, the production period is long, the equipment utilization rate is low, and the bromine content of the product, the thermal stability and the whiteness of the product cannot be considered.
For this purpose, we propose a process for the continuous production of brominated polystyrene.
Disclosure of Invention
The invention mainly solves the technical problems existing in the prior art and provides a method for continuously producing brominated polystyrene.
In order to achieve the aim, the invention adopts the following technical scheme that 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 are sent into a first-stage reaction kettle to react, the reaction temperature is controlled to be 4-26 ℃, the residence time is 3-6 hours, the low-activity catalyst is one of antimony trichloride, tin trichloride and titanium tetrachloride, the mass ratio of the low-activity catalyst to the polystyrene is 4-12:110, the halogenated alkane solvent is one of dichloromethane, dichloroethane, chloroform and bromoform, the mass ratio of the polystyrene to the halogenated alkane solvent is 3-15:50, the brominating agent is bromine or bromine chloride, the mole ratio of the brominating agent to the polystyrene monomer is 4.6-2:3, and the mass ratio of the brominating agent to the halogenated alkane solvent is 20-80:120.
Preferably, the reaction materials after the reaction of the first-stage reaction kettle are sent into a second-stage reaction kettle, and meanwhile, the reaction materials containing a brominating agent, a halogenated alkane solvent and a high-activity catalyst are sent into the second-stage reaction kettle to continue the reaction, the reaction temperature is controlled to be 18-35 ℃, the residence time is 2-5 hours, and the high-activity catalyst is one of aluminum trichloride, aluminum tribromide and ferric trichloride.
Preferably, after the secondary reaction is finished, the reaction finished product is subjected to gas-liquid separation, gas is treated to reach the standard and discharged, and the liquid is subjected to neutralization, water washing, evaporative crystallization, suction filtration and drying to obtain the product brominated polystyrene.
Preferably, the reaction temperature in the primary reaction kettle is 2-8 ℃, the reaction temperature in the secondary reaction kettle is 18-40 ℃, the mass ratio of polystyrene to halogenated alkane solvent is 20-40:140, and the mass ratio of brominating agent to halogenated alkane solvent is 20-30:110.
Preferably, the carrier and the modified ethylene double fatty acid amide are added into a pressurized overturning internal mixer, the temperature in the internal mixer is controlled to be 130-170 ℃, the rotating speed of a rotor is controlled to be 30-90, the internal mixing time is 6-18 minutes, brominated polystyrene powder is added into the internal mixer three times after materials are melted, each time of feeding is 3-7 minutes, and internal mixing is carried out for 8-22 minutes after all materials are added.
Preferably, in the polymerization step, styrene and a solvent are prepared into a styrene solution with the concentration of 2% -50%, 0.00005% -20% of tertiary butyl sodium with the mass of styrene is added as a catalyst, the reaction is carried out for 1-20 hours at the temperature of 1-90 ℃, and after the reaction is finished, methanol or water with the mass equal to that of the catalyst is added as a quenching agent, so that the solution of the polystyrene is obtained.
Preferably, in the bromination step, reduced iron powder with the mass of 1.8-19% of that of the styrene is added into a solution of the polystyrene as a catalyst, and bromination reactants with the molar quantity of 4.8-5 times that of the styrene are dropwise added for carrying out the australization, and the reaction is carried out for 6-20 hours at 15-40 ℃.
Preferably, the solvent is one of petroleum ether, n-hexane and cyclohexane, and the bromination reactant is one of Australian chloride or Australian.
Preferably, the pickling micro-mixing system further comprises a pickling mixing pipeline, the pickling micro-mixer is connected with the pickling phase separator through the pickling mixing pipeline, and the decoloring alkali-washing micro-mixing system further comprises a decoloring mixing pipeline and an alkali-washing mixing pipeline.
Advantageous effects
The invention provides a method for continuously producing brominated polystyrene. The beneficial effects are as follows:
(1) The method for continuously producing brominated polystyrene comprises the steps of cleaning a screw and a charging barrel of a double-screw extruder before extruding and polymerizing a styrene body, vacuumizing and introducing nitrogen for several times under preheating, wherein the temperature of each section of the screw is that the first section is a metering and conveying section of styrene, the temperature is 20-50 ℃, the second section and the third section are that an initiator butyl lithium is metered and added and polymerized, the temperature is 30-120 ℃, the fourth section and the fifth section are mainly melt conveying sections, the temperature is 120-190 ℃, the sixth section is a die section, the temperature is 150-200 ℃, the polymerization rate is too low when the polymerization reaction temperature is too low, the conversion rate is insufficient, and the mechanical shearing degradation of a polymer is easily caused. The polymerization reaction temperature is too high, the polymerization rate is too high, the heat dissipation is insufficient, thermal degradation is caused, and the distribution of the polymerization reaction temperature is precisely controlled in a trapezoid shape.
(2) The method for continuously producing the brominated polystyrene further comprises the steps of controlling the average residence time of the materials in the double-screw extruder to be between 3 and 20 minutes, controlling the polymerization conversion rate to be too low when the residence time is lower than 3 minutes, controlling the molecular weight distribution to be too wide, and controlling the thermal oxidative degradation of the materials when the residence time exceeds 20 minutes, so that the production efficiency is greatly reduced. The rotation speed of the screw is controlled between 20 and 200, when the rotation speed is lower than 20, the stay time of materials is overlong, the mixing is uneven, the production efficiency is low, and when the rotation speed is higher than 200, the shearing degradation and the stay time of polystyrene are insufficient, so that the high-conversion rate polystyrene cannot be obtained.
(3) A process for continuously preparing brominated polystyrene includes such steps as adding terminator and antioxidizing agent to the molten polystyrene in the conveying segment of twin-screw extruder, preventing thermal oxidization reaction, extruding, dissolving in dichloroethane, stirring to obtain 5-15wt% solution, adding antimony trichloride catalyst to the solution, stirring at 20-35 deg.C, adding bromine chloride to the solution, and reacting for 3-4 hr.
(4) The method for continuously producing brominated polystyrene comprises the steps of further adding 5wt% sodium sulfite or sodium bisulphite aqueous solution into a reaction solution of the polystyrene after catalytic bromination to stop the reaction, removing excessive bromine chloride and generated hydrochloric acid, adding sodium sulfite or sodium bisulphite until the reaction solution is changed from red to white or light yellow and does not change color, adding 5wt% sodium hydroxide solution until the solution is neutral, washing with water, and separating the brominated polystyrene solution. With the mass of the brominated polystyrene being 120, 1 to 1.2 parts of epoxidized soybean oil, 0.5 to 1 part of 1890 stabilizer and 1 to 4.2 parts of mixed paraffin are respectively added into the brominated polystyrene solution.
(5) The method for continuously producing the brominated polystyrene comprises the steps of further injecting the brominated polystyrene solution into a solvent recovery section of a double-screw extruder by using a metering pump, wherein the double-screw extruder is a double-screw reverse-meshing extruder with the diameter of 60 mm and the L/D=24, the rotating speed of a host machine of the double-screw extruder is 150, the pressure of a first exhaust port is about 45 kilopascals, the temperature is 180-240 ℃ and the pressure of a second exhaust port is about 35 kilopascals, and the temperature is 120-160 ℃ so as to ensure the removal and recovery of a large amount of solvents. Nitrogen is added from a devolatilization auxiliary agent port, the pressure of the nitrogen is maintained at 0.58 kilopascal, the pressure of an exhaust port is about 20 kilopascal, the temperature is regulated at 150-270 ℃, the brominated polystyrene after devolatilization is extruded from a double screw extruder, and then air-cooled flour milling and granulating are carried out to prepare brominated polystyrene master batches, wherein the mass content of bromine in the obtained product is 63.6%.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent 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 invention without making any inventive effort, are intended to be within the scope of the invention.
The working principle of the invention is as follows:
before extruding and polymerizing the styrene, cleaning a screw and a charging barrel of a double screw extruder, vacuumizing and introducing nitrogen for several times under preheating, wherein the temperature of each section of the screw is 20-50 ℃, the temperature of the first section is a metering and conveying section of styrene, the temperature of the second section and the third section is an initiator butyllithium metering and polymerizing reaction section, the temperature is 30-120 ℃, the fourth section and the fifth section are mainly melt conveying sections, the temperature is 120-190 ℃, the sixth section is a neck mold section, the temperature is 150-200 ℃, the polymerization rate is too low when the polymerization temperature is too low, the conversion rate is insufficient, and the mechanical shearing degradation of the polymer is easy to cause. The polymerization reaction temperature is too high, the polymerization rate is too high, the heat dissipation is insufficient, thermal degradation is caused, and the distribution of the polymerization reaction temperature is precisely controlled in a trapezoid shape.
Further, the average residence time of the materials in the double-screw extruder is controlled to be between 3 and 20 minutes, when the residence time is lower than 3 minutes, the polymerization conversion rate is too low, the molecular weight distribution is too wide, and when the residence time exceeds 20 minutes, the materials are subjected to thermooxidative degradation, so that the production efficiency is greatly reduced. The rotation speed of the screw is controlled between 20 and 200, when the rotation speed is lower than 20, the stay time of materials is overlong, the mixing is uneven, the production efficiency is low, and when the rotation speed is higher than 200, the shearing degradation and the stay time of polystyrene are insufficient, so that the high-conversion rate polystyrene cannot be obtained.
Further, in the melt conveying section of polystyrene, a terminator and an antioxidant are added from the side direction of a double-screw extruder, so that the thermal oxidation reaction can be prevented, the polystyrene can be directly dissolved and brominated in a bromination reaction kettle after extrusion, polystyrene in a bulk state is directly dissolved in a dichloroethane solvent in the bromination reaction kettle, stirring is carried out to dissolve the polystyrene to form a solution containing 5-15wt% of polystyrene, an antimony trichloride catalyst which is equivalent to 5-13wt% of polystyrene is added into the polystyrene solution, stirring is carried out to dissolve the polystyrene, the solution temperature is controlled to be 20-35 ℃, bromine chloride is slowly added into the solution added with the antimony trichloride catalyst, the molar ratio of the bromine chloride to the polystyrene monomer is 3.5:1-3.8:1, and the reaction is continued for 3-4 hours after the addition is finished.
Further, 5wt% sodium sulfite or sodium bisulphite aqueous solution is added into the polystyrene reaction liquid after catalytic bromination to stop the reaction, excessive bromine chloride and generated hydrochloric acid are removed, the sodium sulfite or sodium bisulphite is added until the reaction liquid is changed from red to white or light yellow and does not change color, then 5wt% sodium hydroxide solution is added until the solution is neutral, and the solution is washed by water to separate brominated polystyrene solution. With the mass of the brominated polystyrene being 120, 1 to 1.2 parts of epoxidized soybean oil, 0.5 to 1 part of 1890 stabilizer and 1 to 4.2 parts of mixed paraffin are respectively added into the brominated polystyrene solution.
Further, the brominated polystyrene solution is injected into a solvent recovery section of a double-screw extruder by a metering pump, the double-screw extruder is a double-screw reverse-meshing extruder with the diameter of 60 mm and the L/D=24, the rotating speed of a main machine of the double-screw extruder is 150, the pressure of a first exhaust port is about 45 kilopascals, the temperature is 180-240 ℃, the pressure of a second exhaust port is about 35 kilopascals, and the temperature is 120-160 ℃, so that the removal and recovery of a large amount of solvents are ensured. Nitrogen is added from a devolatilization auxiliary agent port, the pressure of the nitrogen is maintained at 0.58 kilopascal, the pressure of an exhaust port is about 20 kilopascal, the temperature is regulated at 150-270 ℃, the brominated polystyrene after devolatilization is extruded from a double screw extruder, and then air-cooled flour milling and granulating are carried out to prepare brominated polystyrene master batches, wherein the mass content of bromine in the obtained product is 63.6%.
Thus, the following detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate orientations or positional relationships based on the indicated orientations or positional relationships are merely for convenience in describing the present invention and simplify the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "above" or "below" a second feature may include both the first and second features being in direct contact, as well as the first and second features not being in direct contact but being in contact with each other through additional features therebetween. Moreover, a first feature being "above," "over" and "on" a second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly under and obliquely below the second feature, or simply means that the first feature is less level than the second feature.
Claims (9)
1. A method for continuously producing brominated polystyrene, which is characterized in that: the material flow A containing polystyrene, a low-activity catalyst and a halogenated alkane solvent and the material flow B containing a brominating agent and a halogenated alkane solvent are sent into a first-stage reaction kettle to react, the reaction temperature is controlled to be 4-26 ℃, the residence time is controlled to be 3-6 hours, the low-activity catalyst is one of antimony trichloride, tin trichloride and titanium tetrachloride, the mass ratio of the low-activity catalyst to the polystyrene is 4-12:110, the halogenated alkane solvent is one of dichloromethane, dichloroethane, chloroform and bromochloromethane, the mass ratio of the polystyrene to the halogenated alkane solvent is 3-15:50, the brominating agent is bromine or bromine chloride, the mole ratio of the brominating agent to the polystyrene monomer is 4.6-2:3, and the mass ratio of the brominating agent to the halogenated alkane solvent is 20-80:120.
2. A method for continuously producing brominated polystyrene as claimed in claim 1, wherein: the reaction materials after the reaction of the first-stage reaction kettle are sent into a second-stage reaction kettle, and meanwhile, the reaction materials containing a brominating agent, a halogenated alkane solvent and a high-activity catalyst are sent into the second-stage reaction kettle to continue the reaction, the reaction temperature is controlled to be 18-35 ℃, the residence time is 2-5 hours, and the high-activity catalyst is one of aluminum trichloride, aluminum tribromide and ferric trichloride.
3. A method for continuously producing brominated polystyrene as claimed in claim 2, wherein: and after the secondary reaction is finished, carrying out gas-liquid separation on the reaction finished product, treating and discharging the gas after reaching standards, and neutralizing, washing, evaporating and crystallizing the liquid, carrying out suction filtration and drying to obtain the product brominated polystyrene.
4. A method for continuously producing brominated polystyrene as claimed in claim 3, wherein: the reaction temperature in the primary reaction kettle is 2-8 ℃, the reaction temperature in the secondary reaction kettle is 18-40 ℃, the mass ratio of polystyrene to halogenated alkane solvent is 20-40:140, and the mass ratio of brominating agent to halogenated alkane solvent is 20-30:110.
5. A method for continuously producing brominated polystyrene as claimed in claim 4, wherein: the carrier and the modified ethylene double fatty acid amide are added into a pressurized overturning internal mixer, the temperature in the internal mixer is controlled to be 130-170 ℃, the rotating speed of a rotor is controlled to be 30-90, the internal mixing time is 6-18 minutes, brominated polystyrene powder is added into the internal mixer three times after materials are melted, each time of feeding is 3-7 minutes, and internal mixing is carried out for 8-22 minutes after all materials are added.
6. A method for continuously producing brominated polystyrene as claimed in claim 1, wherein: in the polymerization step, styrene and a solvent are prepared into a styrene solution with the concentration of 2% -50%, 0.00005% -20% of tertiary butyl sodium with the mass of styrene is added as a catalyst, the reaction is carried out for 1-20 hours at the temperature of 1-90 ℃, and after the reaction is finished, methanol or water with the mass equal to that of the catalyst is added as a quenching agent, so that the solution of the polystyrene is obtained.
7. A method for continuously producing brominated polystyrene as claimed in claim 6, wherein: in the bromination step, reducing iron powder with the mass of 1.8-19% of that of the styrene is added into a polystyrene solution as a catalyst, and bromination reactants with the molar quantity of 4.8-5 times that of the styrene are dropwise added for australization, and the reaction is carried out for 6-20 hours at 15-40 ℃.
8. A method for continuously producing brominated polystyrene as claimed in claim 7, wherein: the solvent is one of petroleum ether, normal hexane and cyclohexane, and the bromination reactant is one of Australian chloride or Australian.
9. A method for continuously producing brominated polystyrene as claimed in claim 8, wherein: the micro-mixing system for the decolorization and alkaline washing further comprises a decolorization mixing pipeline and an alkaline washing mixing pipeline.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117106109A (en) * | 2023-10-25 | 2023-11-24 | 山东海化集团有限公司 | Method for continuously preparing brominated polystyrene |
| CN117247482A (en) * | 2023-11-17 | 2023-12-19 | 山东旭锐新材股份有限公司 | High-thermal-stability brominated polystyrene synthesis method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117106109A (en) * | 2023-10-25 | 2023-11-24 | 山东海化集团有限公司 | Method for continuously preparing brominated polystyrene |
| CN117106109B (en) * | 2023-10-25 | 2024-06-04 | 山东海化集团有限公司 | Method for continuously preparing brominated polystyrene |
| CN117247482A (en) * | 2023-11-17 | 2023-12-19 | 山东旭锐新材股份有限公司 | High-thermal-stability brominated polystyrene synthesis method |
| CN117247482B (en) * | 2023-11-17 | 2024-02-20 | 山东旭锐新材股份有限公司 | High-thermal-stability brominated polystyrene synthesis method |
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