CN101701046B - Preparation method of brominated polystyrene - Google Patents
Preparation method of brominated polystyrene Download PDFInfo
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- CN101701046B CN101701046B CN 200910070904 CN200910070904A CN101701046B CN 101701046 B CN101701046 B CN 101701046B CN 200910070904 CN200910070904 CN 200910070904 CN 200910070904 A CN200910070904 A CN 200910070904A CN 101701046 B CN101701046 B CN 101701046B
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- brominated polystyrene
- polystyrene
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 61
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 16
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012265 solid product Substances 0.000 claims abstract description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 3
- 238000005893 bromination reaction Methods 0.000 claims description 11
- 230000031709 bromination Effects 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 4
- 238000009775 high-speed stirring Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000003472 neutralizing effect Effects 0.000 abstract 3
- 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 abstract 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000000926 separation method Methods 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 compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of brominated polystyrene, comprising three steps of catalyzing and brominating, neutralizing washing, and solidifying and separating. The step of catalyzing and brominating comprises the following steps: dissolving polystyrene into dichloroethane solvent, adding antimony trichloride catalyst into the solution, dropwise adding bromine chloride into the solution which is added with antimony trichloride catalyst, wherein the mole ratio of bromine chloride to polystyrene monomer is 3.8:1-3.5:1, keeping the temperature at 10-25 DEG C and reacting for 3-4 hours; the step of neutralizing washing comprises the following steps: adding 5wt% of sodium sulfite or sodium bisulfite aqueous solution into the polystyrene reaction liquid after catalyzing and brominating to terminate the reaction, then adding 5wt% of sodium hydroxide solution to be in neutrality, and then washing with water; and the step of solidifying and separating comprises the following steps: adding the brominated polystyrene solution after neutralizing washing into a high-speed stirring device with high shearing force at a speed of 5mL/min-20mL/min, wherein the high-speed stirring device is filled with alcohol separating agent; regulating the rotating speed to be in a range of 2000-3000 r.p.m.; scattering the brominated polystyrene product in the alcohol to cure into small particles; separating solid products, washing with alcohol, then filtering and drying to obtain brominated polystyrene products.
Description
Technical field
The invention belongs to polymer bromide fire retardant technology of preparing, be specifically related to the preparation of brominated Polystyrene fire retardant and solidify isolating method.
Background technology
Brominated Polystyrene has the flame retardant resistance height as fire retardant, and the advantage of good fluidity is widely used in the engineering plastics such as PBP, PET.
In the prior art, utilize PS and bromizating agent prepared in reaction brominated Polystyrene, the preparation method comprises bromination, washing and sepn process.Sepn process adopts water fractionation by distillation or organic solvent to separate, and brominated Polystyrene is solidified from the brominated Polystyrene solution of bromination reaction completion liquid separate.Utilize nearly boiling water to make separating agent during the water fractionation by distillation, solvent is gone out by high temperature evaporation, bromizates the PS solid and on nearly boiling water, solidifies.When organism was made separating agent, solvent and organism were miscible, solidified to isolate the brominated Polystyrene solid.
The bromination reaction of PS is accomplished liquor ratio than thickness; With the separating agent is main chemical process solution bad dispersibility; Isolating brominated Polystyrene solid product is prone to form agglomerate; Have only the solvent on agglomerate surface to remove for separated dose, the solvent that major part is entrained in the product is in closed state, stays in the solid product of brominated Polystyrene.Even heat drying, the solvent of carrying secretly in the brominated Polystyrene solid product after the separation can not be removed, and bromizates the macrobead product that polystyrene products form entrapment solvent, influences quality product and color.
Summary of the invention
Defective to bad dispersibility, the product entrapment solvent in separating agent of reaction residual liquor in the preparation method of brominated polystyrene of prior art; The invention provides a kind of new Preparation of Brominated Polystyrene method; Use the high-speed mixing equipment that produces high shear, bromizate reaction residual liquor and disperse rapidly, increase the contact area of solvent and separating agent; Remove the solvent of carrying secretly in the brominated Polystyrene product with physics and chemofacies bonded method, improve the quality product of brominated Polystyrene.
Preparation method of brominated polystyrene involved in the present invention comprises catalytic bromination, neutralization washing, solidifies and separate three steps.
1. catalytic bromination
PS is dissolved in the ethylene dichloride solvent, forms the solution that contains PS 5wt%～15wt%, in solution, add the butter of antimony catalyzer that is equivalent to PS weight 5%～13%; Stirring makes its dissolving; The control solution temperature drips bromine chloride gradually in the solution of above-mentioned adding butter of antimony catalyzer under 10 ℃～25 ℃ conditions, bromine chloride and polystyrene monomers mol ratio are 3.8: 1～3.5: 1; After dropwising, keep temperature to continue reaction 3～4 hours.
2. in and the washing
Add 5wt% S-WAT or aqueous solution of sodium bisulfite termination reaction in the polystyrene reactant liquid behind catalytic bromination; Remove the excessive bromine chloride and the hydrochloric acid of generation; S-WAT that adds or sodium sulfite anhy 96 to reaction residual liquor become till white or the faint yellow no longer variable color from redness; Add the 5wt% sodium hydroxide solution again, be neutral, use water washing again to solution.
3. solidify and separate
Brominated Polystyrene solution after the neutralization washing is told, added with the speed of 5mL/min～20mL/min and fill in the high-speed mixing equipment of separating agent alcoholic acid band high shear, control solvent and alcoholic acid volume ratio were less than 1: 2.Regulating rotating speed changes per minutes 2000～3000, and brominated Polystyrene solution disperses also desolventizing after fixing in ethanol, isolates solid product and refilters, dries after with washing with alcohol, promptly gets the brominated Polystyrene product.
The tripping device that the present invention adopts is for producing the high-speed mixing equipment of high shear; As be widely used in the homogenizing emulsifying equipment of industry-by-industry, and have and disperse efficiently and pulverize function, utilize high shear that the big breakup of drop is become small droplets; Improve the dispersiveness of brominated Polystyrene solution in separating agent with mechanical; Solution can fully be contacted with separating agent, be convenient to solvent is separated from product, significantly reduced the solvent that separated product is carried secretly; Solid brominated granules of polystyrene after the separation is careful evenly, and quality product is high.The brominated Polystyrene bromine content that makes is 66%～69%, and the thermal weight loss rate can reach more than 320 ℃ 1% o'clock temperature.
In addition, the present invention has adopted sodium sulfite solution or sodium sulfite solution washing to remove unnecessary bromine chloride, can improve the brominated Polystyrene whiteness, makes product color good.
Embodiment
Embodiment 1
Get the 10.4g PS and be dissolved in the 125mL ethylene dichloride solvent, after dissolving finishes, add butter of antimony 0.9g, stir and make it dissolving.Polystyrene solution is cooled to 12 ℃, drips the 41.4g bromine chloride, maintain the temperature at 12～15 ℃ in the dropping process, dropwised in 2.5 hours.Keep reacting liquid temperature to continue for 15 ℃ to stir 3 hours.Add 5wt% sodium sulfite anhy 96 54mL stopped reaction, and remove unnecessary bromine chloride, add the neutralization of 15mL5wt% sodium hydroxide solution, wash twice.Behind the water oil content layer; The speed adding of lower floor's oil phase with 20mL/min filled in the 350mL alcoholic acid emulsification refiner (a kind of homogenizing emulsifying equipment), open high-speed stirring, regulate rotating speed and change per minutes 2000; Treat that oil phase adds in the refiner fully, continue to keep rotating speed to stir 1 minute.The brominated Polystyrene of separating out with washing with alcohol once filters drying.The product particle is tiny evenly, does not reunite and the entrapment solvent phenomenon, and bromine content is 67.4%, and it is 322.2 ℃ that whiteness (ISO) 76.72, thermal weight loss rate reach 1% o'clock temperature.
Embodiment 2
Get the 10.4g PS and be dissolved in the 128mL ethylene dichloride solvent, the dissolving back adds butter of antimony 1.0g, after the catalyst dissolution; Polystyrene solution is cooled to 16 ℃; Drip the 43.3g bromine chloride, keep temperature of reaction in the dropping process, dropwised in 2 hours at 14～16 ℃.Keep reacting liquid temperature to continue for 14～16 ℃ to stir 3 hours.Add 5wt% S-WAT 110mL, remove unnecessary bromine chloride, add the neutralization of 38mL5wt% sodium hydroxide solution, wash twice.Behind the water oil content layer, the speed adding of oil phase with 5mL/min filled in the 350mL alcoholic acid emulsification refiner (a kind of homogenizing emulsifying equipment), regulate rotating speed and change per minutes, after all adding, keep mixing speed to continue stirring 2 minutes 3000.The brominated Polystyrene of separating out with washing with alcohol once filters drying.The product particle is tiny evenly, does not reunite and the entrapment solvent phenomenon, and bromine content is 66.0%, and it is 322 ℃ that whiteness (ISO) 90.4, thermal weight loss rate reach 1% o'clock temperature.
Embodiment 3
Get the 21.0g PS and be dissolved in the 158mL ethylene dichloride solvent, after dissolving finishes, add butter of antimony 1.8g, stir.After treating catalyst dissolution, polystyrene solution is cooled to 15 ℃, drips the 86.3g bromine chloride, temperature dropwised at 12～15 ℃ in 3 hours in the dropping process.Keep reacting liquid temperature to continue for 12～15 ℃ to stir 4 hours.Add 5wt% sodium sulfite anhy 96 142mL termination reaction, remove unnecessary bromine chloride, add 5wt% sodium hydroxide solution 65mL neutralization, wash twice.The speed of lower floor's oil phase with 15mL/min is added in the emulsification refiner, and regulating the high-speed stirring rotating speed is 2500 commentaries on classics per minutes, adds 320mL ethanol in the refiner.The brominated Polystyrene bromine content of separating out is 68.0%, and the product particle is tiny evenly, does not reunite and the entrapment solvent phenomenon, and it is 335.3 ℃ that the thermal weight loss rate reaches 1% o'clock temperature.
Claims (3)
1. a preparation method of brominated polystyrene utilizes PS and bromizating agent prepared in reaction brominated Polystyrene, it is characterized in that: comprise catalytic bromination, neutralization washing, solidify and separate three steps; Catalytic bromination; Be that PS is dissolved in the ethylene dichloride solvent, form the solution that contains PS 5wt%～15wt%, add the butter of antimony catalyzer again; Drip bromine chloride then gradually, bromine chloride and polystyrene monomers mol ratio are 3.8: 1～3.5: 1; The neutralization washing; Be to add 5wt% S-WAT or aqueous solution of sodium bisulfite in the polystyrene reactant liquid behind catalytic bromination; Make reaction residual liquor from redness become white or faint yellow till, add the 5wt% sodium hydroxide solution again to neutral, use water washing then; Solidify and separate; Be that will neutralize brominated Polystyrene solution after the washing adds with the speed of 5mL/min～20mL/min and fills in the high-speed mixing equipment of alcoholic acid band high shear; Said high-speed mixing equipment is that mixing speed is the homogenizing emulsifying equipment that 2000-3000 changes per minute, and brominated Polystyrene solution disperses in ethanol and the desolventizing after fixing, isolates solid product and uses washing with alcohol; Refilter, dry, get the brominated Polystyrene product.
2. preparation method of brominated polystyrene according to claim 1 is characterized in that, in the said catalytic bromination step, in solution, adds the butter of antimony catalyzer that is equivalent to PS weight 5%～13%.
3. preparation method of brominated polystyrene according to claim 1 is characterized in that, in the said catalytic bromination step, control solution reaction temperature is 10 ℃～25 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200910070904 CN101701046B (en) | 2009-10-22 | 2009-10-22 | Preparation method of brominated polystyrene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200910070904 CN101701046B (en) | 2009-10-22 | 2009-10-22 | Preparation method of brominated polystyrene |
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| CN101701046A CN101701046A (en) | 2010-05-05 |
| CN101701046B true CN101701046B (en) | 2012-04-11 |
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| CN 200910070904 Expired - Fee Related CN101701046B (en) | 2009-10-22 | 2009-10-22 | Preparation method of brominated polystyrene |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105504106A (en) * | 2015-12-24 | 2016-04-20 | 深圳爱易瑞科技有限公司 | Brominated polystyrene with high thermal stability and preparation method of brominated polystyrene |
| CN105504107B (en) * | 2016-01-12 | 2018-04-10 | 潍坊鑫洋化工有限公司 | A kind of industrial production process of high-heat stability bromized polystyrene |
| CN106565875B (en) * | 2016-11-01 | 2019-07-30 | 珠海澳圣聚合物材料有限公司 | A method of continuously preparing molecular weight-controllable brominated polystyrene master batch |
| CN106565876B (en) * | 2016-11-01 | 2019-03-12 | 珠海澳圣聚合物材料有限公司 | A method of continuously preparing molecular weight-controllable brominated polystyrene |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275992A (en) * | 1997-11-18 | 2000-12-06 | 费罗公司 | Process for the preparation of brominated polystyrene having improved color characteristics |
| CN101319017A (en) * | 2008-07-23 | 2008-12-10 | 天津长芦海晶集团有限公司 | Method of preparing high-heat stability bromized polystyrene |
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2009
- 2009-10-22 CN CN 200910070904 patent/CN101701046B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275992A (en) * | 1997-11-18 | 2000-12-06 | 费罗公司 | Process for the preparation of brominated polystyrene having improved color characteristics |
| CN101319017A (en) * | 2008-07-23 | 2008-12-10 | 天津长芦海晶集团有限公司 | Method of preparing high-heat stability bromized polystyrene |
Non-Patent Citations (2)
| Title |
|---|
| 张永华等."溴代聚苯乙烯的合成".《北京师范学院学报（自然科学版）》.1992,第13卷(第4期),第53-55页. |
| 张永华等."溴代聚苯乙烯的合成".《北京师范学院学报(自然科学版)》.1992,第13卷(第4期),第53-55页. * |
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| CN101701046A (en) | 2010-05-05 |
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