CN105504107A - Industrial preparation method of high heat stability brominated polystyrene - Google Patents
Industrial preparation method of high heat stability brominated polystyrene Download PDFInfo
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Abstract
The invention relates to an industrial preparation method of high heat stability brominated polystyrene. The industrial preparation method includes the steps that bromine chloride is prepared by controlling the proportion of chlorine gas to the bromine element when the bromine chloride is synthesized, then the polystyrene is dissolved in alkane solvent, the dissolving temperature is controlled, a certain amount of catalysts is added, and dissolved polystyrene is obtained; the dissolved polystyrene and the prepared bromine chloride are dropwise added into another bromination reaction kettle simultaneously according to a certain molar ratio, other reaction conditions are controlled, finally centrifugation and drying are conducted, and the finished brominated polystyrene is obtained. Compared with the prior art, the industrial preparation method has the advantages of being high in stability, high in mobility and capable of strictly controlling molecular weight distribution.
Description
Technical field
The present invention relates to a kind of industrial production process of high-heat stability bromized polystyrene.
Background technology
Brominated Polystyrene (being called for short BPS) take polystyrene as raw material, through a kind of bromine system organic fire-retardant of bromination, has height
flame retardant resistance, good mechanical-physical and the chemical property such as thermostability and light stability, be widely used in the engineering plastics such as polybutylene terephthalate, poly terephthalic acid ethylene alcoholester, polyphenylene oxide, nylon-66.BPS belongs to macromole type fire retardant, good with the consistency of base material, does not separate out, does not move, and surface is non-blooming, and antistatic effect is strong.
Number of patent application 201010146108.3, disclose a kind of preparation method of molecular weight-controllable brominated polystyrene, take vinylbenzene as raw material, tertiary butyl sodium is adopted to be reacted by cinnamic controllable polymerization as catalyzer, polystyrene is prepared under solution state, the polystyrene being in solution state is carried out bromination and prepares brominated Polystyrene, and by extracting brominated Polystyrene after precipitation or solvent distillation.
Number of patent application 200810053940.1; disclose the preparation method of high-heat stability bromized polystyrene; for raw material with polystyrene and bromine chloride; solvent made by haloalkane; under catalyzer, the protectant effect of main chain alkyl; obtain through bromination reaction, and add a kind of dispersion agent in separation solvent and brominated Polystyrene process, make obtained brominated Polystyrene uniform particles.
Number of patent application 200910118032.0, disclose a kind of preparation method of brominated Polystyrene, it is characterized in that the electric bromination reaction of parent of polystyrene and bromine obtains brominated Polystyrene with the quencher of sulphur as free radical in the scavenging agent of micro-moisture in the electric bromination reaction system of polystyrene parent and the electric bromination reaction of polystyrene parent.Above preparation method, the brominated polystyrenic product colourity that processes and product thermostability are improved, but the uncertainty due to bromine content causes quality product fluctuation comparatively large, and the aspects such as bromine content, thermostability, product colourity need to further improve.
Summary of the invention
The present invention proposes a kind of industrial production process of high-heat stability bromized polystyrene.
Technical scheme of the present invention is achieved in that a kind of industrial production process of high-heat stability bromized polystyrene, it is characterized in that, comprises the following steps:
1. drop in reactor by bromine, in reactor, then add bromine quality 1.1-1.3 alkane solvents doubly, then according to the ratio of bromine and chlorine mol ratio 1:0.80-0.85, in reactor, pass into chlorine, control temperature-10-5 DEG C, produces bromine chloride;
2. in another reactor, be dissolved in by polystyrene in alkane solvents, alkane solvents quality is 8-10 times of polystyrene quality, and solvent temperature controls at 10-20 DEG C, polystyrene dissolves 1-4h to after dissolving completely, adds the catalyzer of polystyrene quality 1%-3%;
3. the 2. solvent polystyrene feed liquid of bromine chloride step 1. produced and step drips according to the mol ratio of 3-3.5:1 simultaneously in another bromination reaction still, time for adding 2-6h, control temperature of reaction 20-30 DEG C, after two kinds of materials are added dropwise to complete, continue reaction 8h simultaneously;
4. in 3. step reacts obtained feed liquid, the sodium sulfite solution that concentration is 5%-15% is added, the addition of sodium sulfite solution is 5-6 times of polystyrene quality, neutralize unnecessary bromine chloride and the hydrogenchloride of generation, then wash with the dilute sulphuric acid that concentration is 10%, the consumption of dilute sulphuric acid is 5-6 times of polystyrene quality, then use the water washing three times of polystyrene quality 5 times, material is washed till neutrality;
5. joined by the material that 4. step has washed in the water of 95-100 DEG C, the time is 8h, steams solvent and obtains finished product, and then centrifugal oven dry obtains product.
As preferred technical scheme, step 1. in alkane solvents be any one in methylene dichloride, ethylene dichloride.
As preferred technical scheme, step 2. in alkane solvents be any one in methylene dichloride, ethylene dichloride.
As preferred technical scheme, step 2. in catalyzer be the mixture of iron trichloride, butter of antimony, tin tetrachloride and aluminum chloride four kinds of materials.
As preferred technical scheme, the blending ratio of described iron trichloride, butter of antimony, tin tetrachloride and aluminum chloride four kinds of materials is 1:3:4:2.
Owing to have employed technique scheme, the present invention has following outstanding beneficial effect:
When the present invention passes through to control synthesizing chlorinated bromine, the ratio of chlorine and bromine, makes the brominated Polystyrene of synthesis have high stability, bromizates polystyrene have high workability by control product aftertreatment technology.Achieve simultaneously and strictly control molecular weight distribution, the number of the bromine atoms that phenyl ring connects is 2.7-2.8, and bromine content is high.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of industrial production process of high-heat stability bromized polystyrene, comprise the following steps:
1. drop in reactor by bromine, in reactor, then add bromine quality 1.1-1.3 alkane solvents doubly, then according to the ratio of bromine and chlorine mol ratio 1:0.80-0.85, in reactor, pass into chlorine, control temperature-10-5 DEG C, produces bromine chloride;
2. in another reactor, be dissolved in by polystyrene in alkane solvents, alkane solvents quality is 8-10 times of polystyrene quality, and solvent temperature controls at 10-20 DEG C, polystyrene dissolves 1-4h to after dissolving completely, adds the catalyzer of polystyrene quality 1%-3%;
3. the 2. solvent polystyrene feed liquid of bromine chloride step 1. produced and step drips according to the mol ratio of 3-3.5:1 simultaneously in another bromination reaction still, time for adding 2-6h, control temperature of reaction 20-30 DEG C, after two kinds of materials are added dropwise to complete, continue reaction 8h simultaneously;
4. in 3. step reacts obtained feed liquid, the sodium sulfite solution that concentration is 5%-15% is added, the addition of sodium sulfite solution is 5-6 times of polystyrene quality, neutralize unnecessary bromine chloride and the hydrogenchloride of generation, then wash with the dilute sulphuric acid that concentration is 10%, the consumption of dilute sulphuric acid is 5-6 times of polystyrene quality, then use the water washing three times of polystyrene quality 5 times, material is washed till neutrality;
5. joined by the material that 4. step has washed in the water of 95-100 DEG C, the time is 8h, steams solvent and obtains finished product, and then centrifugal oven dry obtains product.
Above-mentioned steps 1. in alkane solvents be any one in methylene dichloride, ethylene dichloride.
Above-mentioned steps 2. in alkane solvents be any one in methylene dichloride, ethylene dichloride.
Above-mentioned steps 2. in catalyzer be the mixture of iron trichloride, butter of antimony, tin tetrachloride and aluminum chloride four kinds of materials.
The blending ratio of above-mentioned iron trichloride, butter of antimony, tin tetrachloride and aluminum chloride four kinds of materials is 1:3:4:2.
Embodiment 1:
Dropped in reactor by 400g bromine, then in reactor, add 500g ethylene dichloride, then according to the ratio of bromine and chlorine mol ratio 1:0.80, in reactor, pass into chlorine, control temperature-6-3 DEG C, produces bromine chloride.In another reactor, be dissolved in by polystyrene in ethylene dichloride, ethylene dichloride quality is 8 times of polystyrene quality, and solvent temperature controls at 20 DEG C, and polystyrene dissolves 3h to after dissolving completely, adds the butter of antimony of polystyrene quality 2%.The bromine chloride produced and solvent polystyrene are dripped in another bromination reaction still according to the mol ratio of 3.2:1, time for adding 2h, controls temperature of reaction 20-30 DEG C simultaneously, after two kinds of materials are added dropwise to complete simultaneously, continues reaction 8h; Then in feed liquid, the sodium sulfite solution that concentration is 12% is added, the addition of sodium sulfite solution is 4 times of polystyrene quality, neutralize unnecessary bromine chloride and the hydrogenchloride of generation, then wash with the dilute sulphuric acid that concentration is 10%, the consumption of dilute sulphuric acid is 4 times of polystyrene quality, then use the water washing three times of polystyrene quality 5 times, material is washed till neutrality; The material washed joins in the water of 95-100 DEG C, and the time is 8h, steams solvent and obtains finished product, and then centrifugal oven dry obtains product.
Embodiment 2:
Dropped in reactor by 400g bromine, then in reactor, add 500g ethylene dichloride, then according to the ratio of bromine and chlorine mol ratio 1:0.85, in reactor, pass into chlorine, control temperature-6-3 DEG C, produces bromine chloride.In another reactor, be dissolved in by polystyrene in ethylene dichloride, ethylene dichloride quality is 8 times of polystyrene quality, and solvent temperature controls at 20 DEG C, and polystyrene dissolves 3h to after dissolving completely, adds the butter of antimony of polystyrene quality 2%.The bromine chloride produced and solvent polystyrene are dripped in another bromination reaction still according to the mol ratio of 3.2:1, time for adding 2h, controls temperature of reaction 20-30 DEG C simultaneously, after two kinds of materials are added dropwise to complete simultaneously, continues reaction 8h; Then in feed liquid, the sodium sulfite solution that concentration is 12% is added, the addition of sodium sulfite solution is 4 times of polystyrene quality, neutralize unnecessary bromine chloride and the hydrogenchloride of generation, then wash with the dilute sulphuric acid that concentration is 10%, the consumption of dilute sulphuric acid is 4 times of polystyrene quality, then use the water washing three times of polystyrene quality 5 times, material is washed till neutrality; The material washed joins in the water of 95-100 DEG C, and the time is 8h, steams solvent and obtains finished product, and then centrifugal oven dry obtains product.
Embodiment 3:
Dropped in reactor by 400g bromine, then in reactor, add 500g ethylene dichloride, then according to the ratio of bromine and chlorine mol ratio 1:0.83, in reactor, pass into chlorine, control temperature-6-3 DEG C, produces bromine chloride.In another reactor, be dissolved in by polystyrene in ethylene dichloride, ethylene dichloride quality is 8 times of polystyrene quality, and solvent temperature controls at 20 DEG C, and polystyrene dissolves 3h to after dissolving completely, adds the butter of antimony of polystyrene quality 2%.The bromine chloride produced and solvent polystyrene are dripped in another bromination reaction still according to the mol ratio of 3.2:1, time for adding 2h, controls temperature of reaction 20-30 DEG C simultaneously, after two kinds of materials are added dropwise to complete simultaneously, continues reaction 8h; Then in feed liquid, the sodium sulfite solution that concentration is 12% is added, the addition of sodium sulfite solution is 4 times of polystyrene quality, neutralize unnecessary bromine chloride and the hydrogenchloride of generation, then wash with the dilute sulphuric acid that concentration is 10%, the consumption of dilute sulphuric acid is 4 times of polystyrene quality, then use the water washing three times of polystyrene quality 5 times, material is washed till neutrality; The material washed joins in the water of 95-100 DEG C, and the time is 8h, steams solvent and obtains finished product, and then centrifugal oven dry obtains product.
Reference examples 1:
Dropped in reactor by 400g bromine, then in reactor, add 500g ethylene dichloride, then according to the ratio of bromine and chlorine mol ratio 1:0.7, in reactor, pass into chlorine, control temperature-6-3 DEG C, produces bromine chloride.In another reactor, be dissolved in by polystyrene in ethylene dichloride, ethylene dichloride quality is 8 times of polystyrene quality, and solvent temperature controls at 20 DEG C, and polystyrene dissolves 3h to after dissolving completely, adds the butter of antimony of polystyrene quality 2%.The bromine chloride produced and solvent polystyrene are dripped in another bromination reaction still according to the mol ratio of 3.2:1, time for adding 2h, controls temperature of reaction 20-30 DEG C simultaneously, after two kinds of materials are added dropwise to complete simultaneously, continues reaction 8h; Then in feed liquid, the sodium sulfite solution that concentration is 12% is added, the addition of sodium sulfite solution is 4 times of polystyrene quality, neutralize unnecessary bromine chloride and the hydrogenchloride of generation, then wash with the dilute sulphuric acid that concentration is 10%, the consumption of dilute sulphuric acid is 4 times of polystyrene quality, then use the water washing three times of polystyrene quality 5 times, material is washed till neutrality; The material washed joins in the water of 95-100 DEG C, and the time is 8h, steams solvent and obtains finished product, and then centrifugal oven dry obtains product.
Reference examples 2:
Dropped in reactor by 400g bromine, then in reactor, add 500g ethylene dichloride, then according to the ratio of bromine and chlorine mol ratio 1:0.95, in reactor, pass into chlorine, control temperature-6-3 DEG C, produces bromine chloride.In another reactor, be dissolved in by polystyrene in ethylene dichloride, ethylene dichloride quality is 8 times of polystyrene quality, and solvent temperature controls at 20 DEG C, and polystyrene dissolves 3h to after dissolving completely, adds the butter of antimony of polystyrene quality 2%.The bromine chloride produced and solvent polystyrene are dripped in another bromination reaction still according to the mol ratio of 3.2:1, time for adding 2h, controls temperature of reaction 20-30 DEG C simultaneously, after two kinds of materials are added dropwise to complete simultaneously, continues reaction 8h; Then in feed liquid, the sodium sulfite solution that concentration is 12% is added, the addition of sodium sulfite solution is 4 times of polystyrene quality, neutralize unnecessary bromine chloride and the hydrogenchloride of generation, then wash with the dilute sulphuric acid that concentration is 10%, the consumption of dilute sulphuric acid is 4 times of polystyrene quality, then use the water washing three times of polystyrene quality 5 times, material is washed till neutrality; The material washed joins in the water of 95-100 DEG C, and the time is 8h, steams solvent and obtains finished product, and then centrifugal oven dry obtains product.
Reference examples 3:
Dropped in reactor by 400g bromine, then in reactor, add 500g ethylene dichloride, then according to the ratio of bromine and chlorine mol ratio 1:0.80, in reactor, pass into chlorine, control temperature-6-3 DEG C, produces bromine chloride.In another reactor, be dissolved in by polystyrene in ethylene dichloride, ethylene dichloride quality is 8 times of polystyrene quality, and solvent temperature controls at 30 DEG C, and polystyrene dissolves 3h to after dissolving completely, adds the butter of antimony of polystyrene quality 2%.The bromine chloride produced and solvent polystyrene are dripped in another bromination reaction still according to the mol ratio of 3.2:1, time for adding 2h, controls temperature of reaction 20-30 DEG C simultaneously, after two kinds of materials are added dropwise to complete simultaneously, continues reaction 8h; Then in feed liquid, the sodium sulfite solution that concentration is 12% is added, the addition of sodium sulfite solution is 4 times of polystyrene quality, neutralize unnecessary bromine chloride and the hydrogenchloride of generation, then wash with the dilute sulphuric acid that concentration is 10%, the consumption of dilute sulphuric acid is 4 times of polystyrene quality, then use the water washing three times of polystyrene quality 5 times, material is washed till neutrality; The material washed joins in the water of 95-100 DEG C, and the time is 8h, steams solvent and obtains finished product, and then centrifugal oven dry obtains product.
Reference examples 4:
Dropped in reactor by 400g bromine, then in reactor, add 500g ethylene dichloride, then according to the ratio of bromine and chlorine mol ratio 1:0.80, in reactor, pass into chlorine, control temperature-6-3 DEG C, produces bromine chloride.In another reactor, be dissolved in by polystyrene in ethylene dichloride, ethylene dichloride quality is 8 times of polystyrene quality, and solvent temperature controls at 20 DEG C, and polystyrene dissolves 3h to after dissolving completely, adds the butter of antimony of polystyrene quality 2%.Drip time different according to the mol ratio of 3.2:1 to the bromine chloride produced and solvent polystyrene in another bromination reaction still, time for adding 2h, control temperature of reaction 20-30 DEG C, after two kinds of materials are added dropwise to complete, continue reaction 8h simultaneously; Then in feed liquid, the sodium sulfite solution that concentration is 12% is added, the addition of sodium sulfite solution is 4 times of polystyrene quality, neutralize unnecessary bromine chloride and the hydrogenchloride of generation, then wash with the dilute sulphuric acid that concentration is 10%, the consumption of dilute sulphuric acid is 4 times of polystyrene quality, then use the water washing three times of polystyrene quality 5 times, material is washed till neutrality; The material washed joins in the water of 95-100 DEG C, and the time is 8h, steams solvent and obtains finished product, and then centrifugal oven dry obtains product.
Embodiment 1, embodiment 2, embodiment 3, reference examples 1, reference examples 2, reference examples 3 and reference examples 4 are processed the finished product brominated Polystyrene obtained and carries out analytical test respectively, obtain test result as shown in Table 1.
Table one:
Can be found by the data of table one gained, bromine and chlorine mol ratio control in the scope of 1:0.80-0.85 by embodiment 1-embodiment 3, other conditions all do not change, through finished product test, embodiment 1-embodiment 3 three embodiment bromine content percentage ratios and 1% thermal weight loss temperature maintain higher scope, and product colour is white.Reference examples 1 and reference examples 2 change bromine and chlorine mol ratio, and beyond the scope of 1:0.80-0.85, and through finished product test, reference examples 1 and reference examples 2 bromine content percentage ratio and 1% thermal weight loss temperature parameter value start to decline.When illustrating that bromine and chlorine mol ratio control in the scope of 1:0.80-0.85, the finished product brominated Polystyrene thermal stability obtained is best.
Reference examples 3 is relative to embodiment 1, temperature increase when polystyrene dissolves by reference examples 3 is 30 DEG C, other conditions are identical with embodiment 1, through finished product test, reference examples 3 bromine content percentage ratio and 1% thermal weight loss temperature parameter value obviously decline relative to embodiment 1, and product colour becomes faint yellow, illustrate that solvent temperature controls 20 DEG C time, solute effect is best.Reference examples 4 is relative to embodiment 1, the mode dripped when bromine chloride adopts different with solvent polystyrene by reference examples 4 is added drop-wise in reactor, other conditions are identical with embodiment 1, through finished product test, reference examples 4 bromine content percentage ratio and 1% thermal weight loss temperature parameter value obviously decline relative to embodiment 1, and product colour becomes faint yellow.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. an industrial production process for high-heat stability bromized polystyrene, is characterized in that, comprises the following steps:
1. drop in reactor by bromine, in reactor, then add bromine quality 1.1-1.3 alkane solvents doubly, then according to the ratio of bromine and chlorine mol ratio 1:0.80-0.85, in reactor, pass into chlorine, control temperature-10-5 DEG C, produces bromine chloride;
2. in another reactor, be dissolved in by polystyrene in alkane solvents, alkane solvents quality is 8-10 times of polystyrene quality, and solvent temperature controls at 10-20 DEG C, polystyrene dissolves 1-4h to after dissolving completely, adds the catalyzer of polystyrene quality 1%-3%;
3. the 2. solvent polystyrene feed liquid of bromine chloride step 1. produced and step drips according to the mol ratio of 3-3.5:1 simultaneously in another bromination reaction still, time for adding 2-6h, control temperature of reaction 20-30 DEG C, after two kinds of materials are added dropwise to complete, continue reaction 8h simultaneously;
4. in 3. step reacts obtained feed liquid, the sodium sulfite solution that concentration is 5%-15% is added, the addition of sodium sulfite solution is 5-6 times of polystyrene quality, neutralize unnecessary bromine chloride and the hydrogenchloride of generation, then wash with the dilute sulphuric acid that concentration is 10%, the consumption of dilute sulphuric acid is 5-6 times of polystyrene quality, then use the water washing three times of polystyrene quality 5 times, material is washed till neutrality;
5. joined by the material that 4. step has washed in the water of 95-100 DEG C, the time is 8h, steams solvent and obtains finished product, and then centrifugal oven dry obtains product.
2. the industrial production process of a kind of high-heat stability bromized polystyrene according to claim 1, is characterized in that: step 1. in alkane solvents be any one in methylene dichloride, ethylene dichloride.
3. the industrial production process of a kind of high-heat stability bromized polystyrene according to claim 1, is characterized in that: step 2. in alkane solvents be any one in methylene dichloride, ethylene dichloride.
4. the industrial production process of a kind of high-heat stability bromized polystyrene according to claim 1, is characterized in that: step 2. in catalyzer be the mixture of iron trichloride, butter of antimony, tin tetrachloride and aluminum chloride four kinds of materials.
5. the industrial production process of a kind of high-heat stability bromized polystyrene according to claim 4, is characterized in that: the blending ratio of described iron trichloride, butter of antimony, tin tetrachloride and aluminum chloride four kinds of materials is 1:3:4:2.
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| CN107474165A (en) * | 2017-08-03 | 2017-12-15 | 山东日兴新材料股份有限公司 | A kind of high-heat stability bromized SBS synthetic method |
| CN109485755A (en) * | 2018-12-27 | 2019-03-19 | 山东旭锐新材有限公司 | BPS product and preparation method thereof by bromine chloride method |
| CN109762082A (en) * | 2018-12-27 | 2019-05-17 | 山东旭锐新材有限公司 | A kind of small-molecular-weight BPS product and preparation method thereof |
| CN109867739A (en) * | 2017-12-03 | 2019-06-11 | 潍坊双丰化工有限公司 | A kind of preparation method of brominated Polystyrene |
| CN110615862A (en) * | 2019-10-30 | 2019-12-27 | 泰州百力化学股份有限公司 | Method for synthesizing brominated polystyrene |
| CN116535553A (en) * | 2023-07-04 | 2023-08-04 | 潍坊双丰化工有限公司 | Preparation method of high-thermal-stability brominated polystyrene |
| 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 |
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| CN107474165A (en) * | 2017-08-03 | 2017-12-15 | 山东日兴新材料股份有限公司 | A kind of high-heat stability bromized SBS synthetic method |
| CN109867739A (en) * | 2017-12-03 | 2019-06-11 | 潍坊双丰化工有限公司 | A kind of preparation method of brominated Polystyrene |
| CN109867739B (en) * | 2017-12-03 | 2021-07-16 | 潍坊双丰化工有限公司 | Preparation method of brominated polystyrene |
| CN109485755A (en) * | 2018-12-27 | 2019-03-19 | 山东旭锐新材有限公司 | BPS product and preparation method thereof by bromine chloride method |
| CN109762082A (en) * | 2018-12-27 | 2019-05-17 | 山东旭锐新材有限公司 | A kind of small-molecular-weight BPS product and preparation method thereof |
| CN109485755B (en) * | 2018-12-27 | 2021-05-11 | 山东旭锐新材有限公司 | BPS product and preparation method thereof by bromine chloride method |
| CN109762082B (en) * | 2018-12-27 | 2021-07-30 | 山东旭锐新材有限公司 | Low-molecular-weight BPS product and preparation method thereof |
| CN110615862A (en) * | 2019-10-30 | 2019-12-27 | 泰州百力化学股份有限公司 | Method for synthesizing brominated polystyrene |
| CN116535553A (en) * | 2023-07-04 | 2023-08-04 | 潍坊双丰化工有限公司 | Preparation method of high-thermal-stability brominated polystyrene |
| CN116535553B (en) * | 2023-07-04 | 2023-09-26 | 潍坊双丰化工有限公司 | Preparation method of high-thermal-stability brominated polystyrene |
| 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 |
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