CN101497673A - Process for preparing brominated polystyrene - Google Patents
Process for preparing brominated polystyrene Download PDFInfo
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- CN101497673A CN101497673A CNA2009101180320A CN200910118032A CN101497673A CN 101497673 A CN101497673 A CN 101497673A CN A2009101180320 A CNA2009101180320 A CN A2009101180320A CN 200910118032 A CN200910118032 A CN 200910118032A CN 101497673 A CN101497673 A CN 101497673A
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Abstract
The invention provides a preparation method of bromized polystyrene. The method is characterized in that sulfur is taken as the scavenging agent of a small amount of water in the electrophilic bromination reaction of the polystyrene and as the quencher of free radical in the electrophilic bromination reaction of the polystyrene, and the mass of the sulfur is 0.1 to 12 percent of that of the polystyrene. In the organic solvent of dichloroethane, chloroform, bromochloromethane, carbon tetrachloride or tetrachloroethane, the anhydrous aluminium trichloride, the anhydrous ferric chloride, the titanium tetrachloride, the antimonous chloride, the aluminum powder, the zinc powder or the iron powder is taken as the catalyst, the sulfur is taken as the scavenging agent of the small amount of water and as the quencher of the free radical, and the bromized polystyrene is prepared by the electrophilic bromination reaction between the polystyrene and the bromine.
Description
Technical field
The present invention relates to a kind of preparation method of brominated polymer.Be particularly related to and use the quencher of sulphur, and then prepare the method for brominated Polystyrene 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.
Technical background
Brominated Polystyrene is that the polystyrene dispersing and dissolving is in such as organic solvents such as ethylene dichloride, methylene dichloride, bromochloromethane, chloroform, tetracol phenixin or tetrachloroethane, use aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, titanium tetrachloride, butter of antimony, aluminium powder, zinc powder or iron powder etc. as catalyzer, bromine carries out the prepared a kind of brominated polymer of bromination reaction to benzene nucleus.Brominated Polystyrene is as a kind of organic polymer bromide fire retardant, have high flame retardant, Heat stability is good, good with the engineering plastics consistency, do not separate out, do not move, the surface is non-blooming, antistatic property is good, characteristics such as toxicity is low are widely used in engineering plastics and alloys thereof such as nylon, PBT, PET, PC.
Such as GB695826, GB715100, GB778761, US3050476, US3845146, US4200703, US4352909, US5328983, US5532322, US5723549, US5726252, US5882551, US6133381, US6326439, US6518368, WO02072645, WO0014125, EP0765887, EP0592858, CN20041008796, CN200580036583, numerous patents such as CN200710022496 and CN20081053940 prepare the bromination reaction technology of brominated Polystyrene at the close electric bromination reaction of polystyrene and bromine, the raw materials for production prescription, catalyzer is selected for use, technological process control, product colourity and product thermostability are improved, aspects such as brominated Polystyrene average molecular weight size control are studied, improved polystyrene bromination technology, brominated Polystyrene performance and multinomial technical indicator are improved.Yet brominated Polystyrene production technology and technology still need to be optimized, specifically:
The technician of this professional domain knows through the acid catalyzed polystyrene bromination reaction of Lewis and belongs to electrophilic substitution reaction mechanism, and bromination reaction occurs on the benzene nucleus of polystyrene.But in polystyrene bromination reaction system, if 1. irradiate light, 2. molecular oxygen exists, 3. temperature of reaction is higher or 4. under the condition such as radical initiator existence, all inevitable free radical mechanism bromination reaction occurs on the main chain of polystyrene, produces alpha-brominated brominated Polystyrene by product.Because alpha-brominated polystyrene by product is thermally-stabilised lower, be difficult to satisfy 280 ℃ of high temperature process condition needs of engineering plastics.So must take technical measures to stop the generation of free radical mechanism bromination reaction or the alpha-brominated polystyrene by product in the removing brominated Polystyrene product.
US5328983 has proposed the polystyrene brominated product and has been dispersed in pressure cooking in the strong aqua, both can eliminate the α-bromine atoms in the brominated Polystyrene product, can remove the free bromine that the brominated Polystyrene product is carried secretly again, improve the thermostability and the whiteness of polystyrene brominated product.CN200710022496 proposes commercially available brominated Polystyrene is dissolved in the tetrahydrofuran (THF) of q.s, adds reductive agents such as Zn, Al or Na, and the α-bromine atoms that bromizates in the polystyrene product breaks away from brominated Polystyrene.More than adopt post processing mode that the brominated Polystyrene product is carried out thermostability and improve, must increase extra starting material, brominated Polystyrene raw materials for production unit consumption will improve, and production technique becomes complicated.CN200810053940 proposes to add the main chain protective material titanium tetrachloride or the tin tetrachloride of polystyrene in the bromination reaction system of polystyrene recently, preferred tin tetrachloride, and obtained brominated Polystyrene product is a white, 1% thermal weight loss temperature is 310 ℃.But so-called polystyrene main chain protective material titanium tetrachloride or tin tetrachloride should be the Lewis acid catalysts of electrophilic substitution reaction between polystyrene and the bromine.
In sum, US5328983, CN200710022496 or CN200810053940 not on polystyrene bromination production process, adopt direct method to eliminate the generation of free radical mechanism bromination reaction.
The technician of this professional domain also knows through acid catalyzed polystyrene bromination reactions of Lewis such as aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, titanium tetrachloride or butter of antimony and finishes under anhydrous condition.For high efficiency smooth carries out the acid catalyzed polystyrene bromination process of Lewis, in existing production process, all need to add the dewatering agent Vanadium Pentoxide in FLAKES.The Vanadium Pentoxide in FLAKES chemical property is very active, stores and uses inconvenience, usually pastes on the reactor wall, and result of use reduces.
Therefore, consider the acid catalyzed polystyrene bromination of above Lewis process control condition and the factor that influences the brominated Polystyrene quality product, there are a kind of like this needs: have a kind of material or technology can eliminate the generation of various free radicals in the polystyrene electrophilic substitution bromination reaction, thoroughly stop the generation of polystyrene main chain free radical bromination; Simultaneously, material of the present invention or technology can replace the micro-moisture in the dewatering agent Vanadium Pentoxide in FLAKES destruction polystyrene bromination reaction system, guarantee normally carrying out of polystyrene bromination process.Make brominated Polystyrene production operation handy and safe and economic benefit height.
Summary of the invention
The invention provides a kind of sulphur prepares brominated Polystyrene as the quencher of 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 method.Specifically, the polystyrene dissolving is scattered in such as in the organic solvents such as ethylene dichloride, methylene dichloride, bromochloromethane, chloroform, tetracol phenixin or tetrachloroethane, aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, titanium tetrachloride, butter of antimony, aluminium powder or iron powder etc. are as the Lewis acid catalyst, in 0～40 ℃ of scope, under the condition of normal pressure, add sulphur simultaneously, as bromizating agent, make brominated Polystyrene through bromination, washing, precipitating, drying process with bromine.
Sulphur of the present invention is as the scavenging agent of micro-moisture in the polystyrene bromination reaction system, its principles of chemistry are that sulphur and bromine rapid reaction in 0～40 ℃ of scope generate dibrominated sulphur, dibrominated sulphur runs into water hydrolysis reaction takes place at once, produces hydrogen bromide and sulfurous gas.
Sulphur of the present invention is as the quencher of free radical in the electric bromination reaction of polystyrene parent, its principles of chemistry be dibrominated sulphur of the present invention or sulfurous gas can with reactions such as molecular oxygen, molecular oxygen free radical, bromine free radical, produce bromine sulfur oxide and sulphur trioxide etc., thereby produce the effect of eliminating free radical in the polystyrene bromination reaction.
Sulphur of the present invention is as the quencher of free radical in the scavenging agent of micro-moisture in the polystyrene bromination reaction system and the electric bromination reaction of polystyrene parent, has the characteristics of cheap, safe in utilization efficient, the easy operation and control of a thing multiple-effect, the prices of raw and semifnished materials.
Sulphur provided by the invention prepares the method for brominated Polystyrene as the quencher of 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, may further comprise the steps:
1. polystyrene is dispersed in such as in the organic solvents such as ethylene dichloride, methylene dichloride, bromochloromethane, chloroform, tetracol phenixin or tetrachloroethane, heats up 35～40 ℃ and dissolve fully until polystyrene.Add 200 order SULPHUR POWDER, the add-on of SULPHUR POWDER is 0.1～12% of a polystyrene quality, add catalyzer such as aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, titanium tetrachloride, butter of antimony, aluminium powder, zinc powder or iron powder, the catalyzer add-on is 0.1～20% of a polystyrene quality.
2. controlled step 1. the reactant system temperature of gained in step reactant system 1., splash under the normal pressure through the dry bromine of crossing of the vitriol oil at 0～40 ℃, the quality control of bromine is at 4.5～5.5 times of the polystyrene quality.The bromination reaction time was controlled at 2～8 hours.
3. after the completing steps operation 2., in the reaction product system, add entry, stop bromination reaction.The quality control of water is 50～200% of the organic solvent quality.And the reaction product system washed.
4. after the completing steps operation 3., the adding mass concentration is 20% caustic-soda aqueous solution in the reaction product system, and the phase of anhydrating is divided in neutralization reaction product system pH=7.0～7.5.
5. with step 4. gained organic phase just the reaction product system add in the methyl alcohol, the crystallization in methyl alcohol of brominated Polystyrene product is separated out.
6. through the centrifugal organic solvent that removes, filter cake makes the brominated Polystyrene product through 80～150 ℃ of dryings 6～10 hours.
Hydrolyzable bromine in the brominated Polystyrene product and free halogen macroanalysis method and TGA analyze the method with reference to WO0014125.
Following embodiment further specifies sulphur provided by the invention prepares brominated Polystyrene as the quencher of 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 method.
Embodiment 1
In 1000 milliliters of reaction flasks of lucifuge, polystyrene 50 grams of 400 milliliters of ethylene dichloride of adding, matter average molecular weight Mw=25000 and sulphur 1.8 grams splash into bromine 10 grams under stirring, and keep the interior material of reaction flask and dissolve until polystyrene near 30 ℃.Reduce the interior temperature of charge of reaction flask at 0～2 ℃, add aluminum trichloride (anhydrous) powder 2 grams, splash into the dry bromine of crossing 230 of the vitriol oil in 2 hours and restrain.The bromine tear drop finishes, and continues stirring reaction 2 hours under natural temperature.The reaction product system is washed through 3 * 300 ml waters, afterwards is 20% caustic-soda aqueous solution neutralization reaction product system pH=7.0～7.5 with mass concentration, divides the phase of anhydrating.Organic phase is splashed in 1000 ml methanol, and the brominated Polystyrene that crystallization is separated out is through the centrifugal organic solvent that removes, and 80～150 ℃ of dryings of filter cake 6～10 hours make white brominated Polystyrene powder 158.3 grams, yield 95.7%.The brominated Polystyrene product analysis the results are shown in Table 1.
Embodiment 2
In 1000 milliliters of reaction flasks of lucifuge, add polystyrene 52 grams of 400 milliliters of ethylene dichloride, matter average molecular weight Mw=25000, keep the interior material of reaction flask and near 30 ℃, dissolve until polystyrene.Reduce the interior temperature of charge of reaction flask at 0～2 ℃, add sulphur 1.6 grams, aluminum trichloride (anhydrous) powder 2.3 grams and zinc powder 0.3 gram, splash into bromine 235 grams that vitriol oil drying is crossed in 2 hours.The bromine tear drop finishes, and continues stirring reaction 2 hours under natural temperature.The reaction product system is washed through 3 * 300 ml waters, afterwards is 20% caustic-soda aqueous solution neutralization reaction product system pH=7.0～7.5 with mass concentration, divides the phase of anhydrating.Organic phase is splashed in 1000 ml methanol, and the brominated Polystyrene that crystallization is separated out is through the centrifugal organic solvent that removes, and 80～150 ℃ of dryings of filter cake 6～10 hours make white brominated Polystyrene powder 166.7 grams, yield 96.9%.The brominated Polystyrene product analysis the results are shown in Table 1.
Embodiment 3
In 1000 milliliters of reaction flasks of lucifuge, add polystyrene 50 grams of 400 milliliters of ethylene dichloride, matter average molecular weight Mw=25000, keep the interior material of reaction flask and near 30 ℃, dissolve until polystyrene.Reduce the interior temperature of charge of reaction flask at 0～2 ℃, add sulphur 3.0 grams, aluminum trichloride (anhydrous) powder 3.0 grams and zinc powder 0.5 gram, splash into bromine 250 grams that vitriol oil drying is crossed in 2 hours.The bromine tear drop finishes, and continues stirring reaction 2 hours under natural temperature.The reaction product system is washed through 3 * 300 ml waters, afterwards is 20% caustic-soda aqueous solution neutralization reaction product system pH=7.0～7.5 with mass concentration, divides the phase of anhydrating.Organic phase is splashed in 1000 ml methanol, and the brominated Polystyrene that crystallization is separated out is through the centrifugal organic solvent that removes, and 80～150 ℃ of dryings of filter cake 6～10 hours make white brominated Polystyrene powder 162.2 grams, yield 98.1%.The brominated Polystyrene product analysis the results are shown in Table 1.
Comparative Examples 1
In 1000 milliliters of reaction flasks of lucifuge, add polystyrene 48 grams of 400 milliliters of ethylene dichloride, matter average molecular weight Mw=25000, keep the interior material of reaction flask and near 30 ℃, dissolve until polystyrene.Reduce the interior temperature of charge of reaction flask at 0～2 ℃, add aluminum trichloride (anhydrous) powder 2.0 grams, splash into the dry bromine of crossing 230 of the vitriol oil in 2 hours and restrain.The bromine tear drop finishes, and continues stirring reaction 2 hours under natural temperature.The reaction product system is washed through 3 * 300 ml waters, afterwards is 20% caustic-soda aqueous solution neutralization reaction product system pH=7.0～7.5 with mass concentration, divides the phase of anhydrating.Organic phase is splashed in 1000 ml methanol, and the brominated Polystyrene that crystallization is separated out is through the centrifugal organic solvent that removes, and 80～150 ℃ of dryings of filter cake 6～10 hours make faint yellow brominated Polystyrene powder 154.5 grams, yield 97.3%.The brominated Polystyrene product analysis the results are shown in Table 1.
Comparative Examples 2
In 1000 milliliters of reaction flasks of lucifuge, add polystyrene 51 grams of 400 milliliters of ethylene dichloride, matter average molecular weight Mw=25000, keep the interior material of reaction flask and near 30 ℃, dissolve until polystyrene.Temperature of charge adds aluminum trichloride (anhydrous) powder 2.6 grams and 0.3 gram zinc powder at 0～2 ℃ in the reduction reaction flask, splashes into bromine 232 grams that vitriol oil drying is crossed in 2 hours.The bromine tear drop finishes, and continues stirring reaction 2 hours under natural temperature.The reaction product system is washed through 3 * 300 ml waters, afterwards is 20% caustic-soda aqueous solution neutralization reaction product system pH=7.0～7.5 with mass concentration, divides the phase of anhydrating.Organic phase is splashed in 1000 ml methanol, and the brominated Polystyrene that crystallization is separated out is through the centrifugal organic solvent that removes, and 80～150 ℃ of dryings of filter cake 6～10 hours make white brominated Polystyrene powder 162.1 grams, yield 96.1%.The brominated Polystyrene analytical results sees Table 1.
Brominated Polystyrene analytical results table 1
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 |
| The product outward appearance | White | White | White | Faint yellow | White |
| Total bromine content (mass percent) | 67.2 | 68.5 | 69.3 | 69.2 | 69.4 |
| Hydrolyzable bromine and free halogen total amount (ppm) | 167 | 1203 | 612 | 6350 | 1863 |
| TGA analyze weightless 1% temperature (℃) | 340 | 335 | 335 | 300 | 310 |
Claims (3)
1. Preparation of Brominated Polystyrene method, be polystyrene to be dissolved in the organic solvents such as ethylene dichloride, methylene dichloride, bromochloromethane, chloroform, tetracol phenixin or tetrachloroethane, in the presence of moisture scavenger and free radical quencher, be subjected to the katalysis of catalyzer such as aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, titanium tetrachloride, butter of antimony, aluminium powder, zinc powder or iron powder, 0～40 ℃ of control reaction temperature, carry out bromination reaction and make with bromine, it is characterized in that described moisture scavenger and free radical quencher are sulphur.
2. according to the described Preparation of Brominated Polystyrene method of claim 1, it is characterized in that described sulfur consumption is 0.1～12% of a described polystyrene quality.
3. according to the described Preparation of Brominated Polystyrene method of claim 1, it is characterized in that may further comprise the steps:
1. polystyrene is dispersed in such as in the organic solvents such as ethylene dichloride, methylene dichloride, bromochloromethane, chloroform, tetracol phenixin or tetrachloroethane, the quality of polystyrene is 5～20% of an organic solvent quality.Heat up 35～40 ℃ and dissolve fully until polystyrene.Add 200 order SULPHUR POWDER, the quality of SULPHUR POWDER is 0.1～12% of a polystyrene quality.Add catalyzer such as aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, titanium tetrachloride, butter of antimony, aluminium powder, zinc powder or iron powder, catalyst quality is 0.1～20% of a polystyrene quality.
2. controlled step 1. the reactant system temperature of gained in described reactant system, splash into through the dry bromine of crossing of the vitriol oil at 0～40 ℃, the quality of bromine is 4.5～5.5 times of polystyrene quality.The bromination reaction time was controlled at 2～8 hours.
3. after the completing steps operation 2., in the reaction product system, add entry, stop bromination reaction.The quality of water is 50～200% of an organic solvent quality.And the reaction product system washed.
4. after the completing steps operation 3., the adding mass concentration is 20% caustic-soda aqueous solution in the reaction product system, and the phase of anhydrating is divided in neutralization reaction product system pH=7.0～7.5.
5. with step 4. the reaction product system of gained add in the methyl alcohol, separate out as brominated Polystyrene crystallization in methyl alcohol of product.
6. through the centrifugal solvent that removes, filter cake makes brominated Polystyrene through 80～150 ℃ of dryings 6～10 hours.
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| CN103275040A (en) * | 2013-03-08 | 2013-09-04 | 菏泽爱赛特化学科技有限公司 | 5-bromo-2-furfural synthesis method |
| CN109694419A (en) * | 2018-12-27 | 2019-04-30 | 山东旭锐新材有限公司 | BPS product and preparation method thereof by full bromine method |
| CN109865522A (en) * | 2017-12-03 | 2019-06-11 | 潍坊双丰化工有限公司 | A kind of brominated Polystyrene catalyst for preparing |
| CN110483375A (en) * | 2019-09-11 | 2019-11-22 | 陈建江 | A kind of synthetic method of intermediate 4- piperidones |
| 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 |
| CN113185410A (en) * | 2021-04-07 | 2021-07-30 | 浙江禾本科技股份有限公司 | Synthesis process of pyraclostrobin intermediate o-nitrobenzyl bromide |
| CN115612006A (en) * | 2022-11-14 | 2023-01-17 | 山东海化集团有限公司 | Preparation method of brominated polystyrene |
| CN115746467A (en) * | 2022-12-23 | 2023-03-07 | 山东省海洋化工科学研究院 | Preparation method of brominated polystyrene-tubular kaolin composite material |
| 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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| CN103275040A (en) * | 2013-03-08 | 2013-09-04 | 菏泽爱赛特化学科技有限公司 | 5-bromo-2-furfural synthesis method |
| CN109865522A (en) * | 2017-12-03 | 2019-06-11 | 潍坊双丰化工有限公司 | A kind of brominated Polystyrene catalyst for preparing |
| CN109694419B (en) * | 2018-12-27 | 2021-07-30 | 山东旭锐新材有限公司 | BPS product and preparation method thereof by full bromine method |
| CN109694419A (en) * | 2018-12-27 | 2019-04-30 | 山东旭锐新材有限公司 | BPS product and preparation method thereof by full bromine method |
| CN110483375A (en) * | 2019-09-11 | 2019-11-22 | 陈建江 | A kind of synthetic method of intermediate 4- piperidones |
| 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 |
| CN113185410A (en) * | 2021-04-07 | 2021-07-30 | 浙江禾本科技股份有限公司 | Synthesis process of pyraclostrobin intermediate o-nitrobenzyl bromide |
| CN113185410B (en) * | 2021-04-07 | 2022-04-26 | 浙江禾本科技股份有限公司 | Synthesis process of pyraclostrobin intermediate o-nitrobenzyl bromide |
| CN115612006A (en) * | 2022-11-14 | 2023-01-17 | 山东海化集团有限公司 | Preparation method of brominated polystyrene |
| CN115746467A (en) * | 2022-12-23 | 2023-03-07 | 山东省海洋化工科学研究院 | Preparation method of brominated polystyrene-tubular kaolin composite material |
| CN115746467B (en) * | 2022-12-23 | 2024-04-05 | 山东省海洋化工科学研究院 | Preparation method of brominated polystyrene-tubular kaolin composite material |
| 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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