CN109485755B - BPS product and preparation method thereof by bromine chloride method - Google Patents
BPS product and preparation method thereof by bromine chloride method Download PDFInfo
- Publication number
- CN109485755B CN109485755B CN201811612403.6A CN201811612403A CN109485755B CN 109485755 B CN109485755 B CN 109485755B CN 201811612403 A CN201811612403 A CN 201811612403A CN 109485755 B CN109485755 B CN 109485755B
- Authority
- CN
- China
- Prior art keywords
- bromine
- chlorine
- temperature
- dichloromethane
- bromine chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
Abstract
The invention discloses a preparation method of a BPS product by a bromine chloride method, which comprises the following steps: preparing raw materials, synthesizing bromine chloride, carrying out bromination reaction and post-treatment, wherein in the synthesis of the bromine chloride, dichloromethane and bromine are mixed, the temperature is reduced to minus 10 to minus 13 ℃, then chlorine is slowly introduced, and after the chlorine is added, the low temperature is maintained, and the temperature is kept for 10 minutes; the invention also provides a BPS product, which has white or light yellow appearance, 1 percent TGA @350 ℃, 5 percent TGA @380 ℃, bromine content of more than or equal to 66 percent and thermal decomposition temperature of more than or equal to 270 ℃; according to the preparation method of the bromine chloride method, liquid chlorine is used for replacing chlorine gas, so that the chlorination time can be greatly shortened, and the energy consumption is saved; tin tetrabromide is used as a free radical quencher, so that the number of main chain halogen atoms is reduced, the thermal stability of the product is improved, the reaction period is shortened, the production efficiency is improved, and the method has great economic and social benefits.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a BPS product and a preparation method thereof by a bromine chloride method.
Background
Brominated Polystyrene (BPS) is an internationally recognized brominated organic environment-friendly flame retardant, does not contain polybrominated diphenyl ethers and polybrominated biphenyls, and meets the ROHS standard. Has the advantages of good compatibility with materials, no precipitation, no blooming, good electrical property, little influence on the mechanical properties of the materials, low price and the like.
Chinese patent publication No. cn101701046.a discloses a method of synthesizing brominated polystyrene by using antimony trichloride as a catalyst for the reaction of polystyrene and bromine chloride, and simultaneously, centrifugally separating by using an emulsifying homogenizer; chinese patent No. 200910118032.0 discloses a method for preparing brominated polystyrene by using sulfur as a water scavenger for the reaction of polystyrene and bromine and a quencher for the free radical reaction; chinese patent application No. 200410067961.0 discloses a method for preparing brominated polystyrene using a mixture of lewis acid and metal as a mixed catalyst.
In combination with the above patents, the existing preparation method of the BPS product still has the above defects: (1) the main chain of the existing BPS product is easily replaced by bromine, so that the product is easily yellowed in the using process, and the thermal stability of the product is reduced;
2) the existing preparation method of the BPS product has long reaction period and low production efficiency;
3) the existing preparation method of the BPS product has the defects of unstable reaction rate of bromination reaction, difficult control and low substitution efficiency of bromination reaction.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a BPS product by a bromine chloride method, so as to realize the following purposes:
1) according to the preparation method, tin tetrabromide is used as a free radical quencher, so that the number of main chain halogen atoms is reduced, and the thermal stability of the product is improved;
2) the preparation method of the invention is optimized in equipment and facilities, shortens the reaction period, and improves the production efficiency:
(a) the aeration time can be shortened by 30 to 50 percent by adding chlorine into a chlorine distributor;
(b) the bromination reaction adopts an inner coil pipe and an outer circulation to assist in cooling, so that the bromine chloride feeding time can be shortened, and the whole reaction period can be shortened;
(c) the dichloromethane is dewatered by adopting an inorganic membrane, so that no hazardous waste is generated, and the environment is protected;
3) the preparation method of the invention, the improvement in the process aspect, shortens the reaction period, and improves the production efficiency: the liquid chlorine is used for replacing chlorine gas, so that the chlorination time can be greatly shortened, and the energy consumption is saved;
4) according to the preparation method, the reaction rate of the bromination reaction is high and stable after the bromine chloride dispersion liquid is adopted, so that the bromination reaction efficiency is improved;
5) the prepared BPS product has white or light yellow appearance, high bromine content and high thermal decomposition temperature, and improves the thermal stability of the product.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the BPS product is white or light yellow in appearance, the chlorine content is 0, 1 percent TGA @350 ℃, 5 percent TGA @380 ℃, the bromine content is not less than 66 percent, and the thermal decomposition temperature is not less than 270 ℃.
The technical scheme of the invention is optimized as follows:
the invention also provides a preparation method of the BPS product by a bromine chloride method, which is characterized in that,
the preparation method of the BPS product by the bromine chloride method comprises the following steps: preparing raw materials, synthesizing bromine chloride, carrying out bromination reaction and carrying out aftertreatment.
Mixing dichloromethane and bromine, cooling to-10 to-13 ℃, then slowly introducing chlorine, maintaining the low temperature after the chlorine is added, and keeping the temperature for 10 minutes;
the mass ratio of the dichloromethane to the bromine to the chlorine is 75: 50: 23.
the bromination reaction is carried out, PS and dichloromethane are added, the mixture is stirred until the PS and the dichloromethane are dissolved, then the temperature is reduced to 5 to 8 ℃, antimony tribromide and tin tetrabromide are added, and bromine chloride solution is dripped;
the mass ratio of PS to dichloromethane was 5: 46.
The mass ratio of the antimony tribromide to the tin tetrabromide is 1:1, and the addition amount of the antimony tribromide is 2.4% of the mass of the PS.
The bromination reaction is carried out, the dropping temperature of the bromine chloride solution is 5-8 ℃, the temperature is raised to 5-10 ℃ after the dropping is finished, and the heat preservation time is 5 hours.
The raw material preparation comprises the following steps: putting dichloromethane into a four-neck flask, adding phosphorus pentoxide, stirring for 5-6 hours until the water content is detected to be less than 0.03%.
And (3) after treatment, washing twice with deionized water, then dripping into hot water at 90 ℃, replacing the solvent, after the solvent replacement is finished, heating to 95 ℃, keeping the temperature for 1 hour, performing suction filtration, and drying the material at 120 ℃ for 6 hours.
The method comprises the steps of synthesizing bromine chloride dispersion liquid, dropwise adding a dispersing agent into the bromine chloride solution, controlling the dropwise adding speed to finish the dropwise adding within 1.6h, and then carrying out heat preservation reaction at 0-3 ℃ for 3-5h to prepare the bromine chloride dispersion liquid.
The dispersing agent is a mixed monomer solution consisting of an anionic monomer, a cationic monomer and a polyether macromonomer, wherein the mass ratio of the cationic monomer to the polyether macromonomer to the anionic monomer is (0.18-0.2) to 0.4: 1.
The BPS product obtained by the preparation method of the BPS product by the bromine chloride method has the advantages of 1 percent TGA @366 ℃, 5 percent TGA @397 ℃, 89.2 percent of bromine content, 90.2 percent of substitution rate of ortho-para-tri-substituted benzene, 0.76 percent of substitution rate of main chain halogen atoms and 348 ℃ of thermal decomposition temperature.
The invention has the following positive effects:
1) according to the preparation method, tin tetrabromide is used as a free radical quencher, so that the number of main chain halogen atoms is reduced, and the thermal stability of the product is improved;
2) the preparation method of the invention is optimized in equipment and facilities, shortens the reaction period, and improves the production efficiency:
(a) the aeration time can be shortened by 30 to 50 percent by adding chlorine into a chlorine distributor;
(b) the bromination reaction adopts an inner coil pipe and an outer circulation to assist in cooling, so that the bromine chloride feeding time can be shortened, and the whole reaction period can be shortened;
(c) the dichloromethane is dewatered by adopting an inorganic membrane, so that no hazardous waste is generated, and the environment is protected;
3) the preparation method of the invention, the improvement in the process aspect, shortens the reaction period, and improves the production efficiency: the liquid chlorine is used for replacing chlorine gas, so that the chlorination time can be greatly shortened, and the energy consumption is saved;
4) according to the preparation method, the reaction rate of the bromination reaction is high and stable after the bromine chloride dispersion liquid is adopted, the efficiency of the bromination reaction is improved, and the bromine content is more than or equal to 66%;
5) the prepared BPS product is white or light yellow in appearance, 1 percent TGA @350 ℃, 5 percent TGA @380 ℃, the bromine content is more than or equal to 66 percent, and the thermal decomposition temperature is more than or equal to 270 ℃.
Detailed Description
The following examples are further detailed descriptions of the present invention.
Example 1: preparation method of BPS product by bromine chloride method
The preparation method of the BPS product by the bromine chloride method comprises the following steps:
step 1, raw material preparation:
(1) preparation of anhydrous dichloromethane: putting 360g of dichloromethane into a four-neck flask, adding 1.5g of phosphorus pentoxide, stirring for 5-6 hours until the water content is detected to be less than 0.03%;
(2) liquid chlorine vaporization: the liquid chlorine in the steel cylinder is vaporized by a vaporization tank and then stored in a buffer tank for later use.
Step 2, bromine chloride synthesis:
adding 75g of dichloromethane and 50g of bromine into a four-mouth bottle, cooling to minus 10 to minus 13 ℃, then slowly introducing 23g of chlorine into the four-mouth bottle, maintaining the low temperature after the chlorine is added, preserving the temperature for 10 minutes, and then transferring to a constant-pressure dropping funnel with a jacket for heat preservation for later use.
And step 3, bromination reaction:
adding 25gPS g and 230g of dichloromethane into a four-neck flask, stirring until the dichloromethane is dissolved, then cooling to 5-8 ℃, adding 0.6g of antimony tribromide and 0.6g of tin tetrabromide, dropwise adding the prepared bromine chloride solution into the four-neck flask, keeping the temperature at 15-20 ℃ for 5 hours after the dropwise adding is finished, dropwise adding a 13-15% sodium sulfite solution into the four-neck flask after the heat preservation is finished, decoloring until the color of the material is white or light yellow, stirring for 30 minutes, and standing for layering.
And 4, post-treatment:
washing the lower layer material twice with 100g deionized water, dripping into 90 ℃ hot water, replacing solvent, heating to 95 ℃ after solvent replacement is finished, keeping the temperature for 1 hour, performing suction filtration, and drying the material at 120 ℃ for 6 hours to obtain a solid product.
Example 1 product index: the product is white or light yellow in appearance, 1 percent TGA @350 ℃, 5 percent TGA @380 ℃, the bromine content is more than or equal to 66 percent, and the thermal decomposition temperature is more than or equal to 270 ℃.
Example 2: preparation method of BPS product by bromine chloride method
Step 1, raw material preparation:
(1) preparation of anhydrous dichloromethane: putting 360g of dichloromethane into a four-neck flask, adding 1.5g of phosphorus pentoxide, stirring for 5-6 hours until the water content is detected to be less than 0.03%;
(2) liquid chlorine vaporization: the liquid chlorine in the steel cylinder is vaporized by a vaporization tank and then stored in a buffer tank for later use.
Step 2, synthesizing bromine chloride dispersion liquid:
(1) adding 75g of dichloromethane and 50g of bromine into a four-mouth bottle, cooling to minus 10 to minus 13 ℃, then slowly introducing 23g of chlorine into the four-mouth bottle, maintaining the low temperature after the chlorine is added, preserving the heat for 10 minutes, and then transferring into a constant-pressure dropping funnel with a jacket for heat preservation to obtain a bromine chloride solution;
(2) and (3) dropwise adding 12g of dispersing agent into the bromine chloride solution, controlling the dropwise adding speed to finish the dropwise adding within 1.6h, and then carrying out heat preservation reaction at the temperature of 0-3 ℃ for 3-5h to prepare bromine chloride dispersion for later use.
The dispersing agent is a mixed monomer solution consisting of an anionic monomer, a cationic monomer and a polyether macromonomer, wherein the mass ratio of the cationic monomer to the polyether macromonomer to the anionic monomer is (0.18-0.2) to 0.4: 1;
the anion monomer is a mixture of sodium dodecyl sulfate and any one of sodium acrylate, sodium dodecyl sulfate, sodium allyl sulfonate, sodium methyl propylene sulfonate and sodium styrene sulfonate;
the cationic monomer is HTC-1 dimethyl diallyl ammonium chloride;
the polyether macromonomer is methylallyl polyethylene glycol with the relative molecular mass of 1100-1200.
And step 3, bromination reaction:
adding 25gPS g and 230g of dichloromethane into a four-neck flask, stirring until the dichloromethane is dissolved, then cooling to 12 ℃, adding 0.6g of antimony tribromide and 0.6g of tin tetrabromide, dropwise adding the prepared bromine chloride dispersion into the four-neck flask at a dropping speed of 0.05-0.08g/min and a dropping temperature of 10-12 ℃, after the dropwise adding is finished, keeping the temperature at 15-20 ℃ for 5 hours, after the keeping temperature is finished, dropwise adding a 13-15% sodium sulfite solution into the four-neck flask for decoloring until the material color becomes white or light yellow, stirring for 30 minutes, standing and layering.
And 4, post-treatment:
washing the lower layer material with 100g of deionized water twice, adjusting the pH value, decoloring with active carbon, dripping into 90 ℃ hot water, replacing the solvent, heating to 95 ℃ after the solvent replacement is finished, keeping the temperature for 1 hour, performing suction filtration, and drying the material at 120 ℃ for 6 hours to obtain a solid product.
The properties of the BPS product obtained according to the bromine chloride process for the BPS product described in example 2 are as follows:
example 2 product index: the product is pure white in appearance, uniform in particle, free of agglomeration and not easy to yellow, and has the advantages of 1% TGA @366 ℃, 5% TGA @397 ℃, 89.2% of bromine content, 90.2% of substitution rate of ortho-para-tri-substituted benzene, 0.76% of substitution rate of main chain halogen atoms and 348 ℃ of thermal decomposition temperature.
Example 3: BPS product
The BPS product in the embodiment 2 of the invention and antimony trioxide are prepared into the composite flame retardant according to a certain proportion by a conventional method, and the composite flame retardant is added into engineering plastics, so that the compatibility is good, the yellowing is not easy, the flame retardant effect is good, the flame retardant grade reaches the V-0 grade standard after the composite flame retardant is added, and the influence on the mechanical properties of the plastics is small. The method comprises the following specific steps:
(1) 22 percent of composite flame retardant is added into the Pbt, and the addition standard can reach UL94V-0 grade;
(2) 16 percent of composite flame retardant is added into the Pet, and the addition standard can reach UL94V-0 level;
(3) 23 percent of composite flame retardant is added into PA6, which can reach UL94V-0 grade addition standard;
(4) the PA66 is added with 14 percent of composite flame retardant, which can reach UL94V-0 grade addition standard.
Unless otherwise stated, the percentages used in the present invention are percentages by weight, and the proportions described in the present invention are proportions by mass.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
1. A preparation method of BPS products is characterized in that,
the preparation method of the BPS product comprises the following steps: preparing raw materials, synthesizing bromine chloride, carrying out bromination reaction and carrying out post-treatment;
the raw material preparation comprises the following steps: putting dichloromethane into a four-neck flask, adding phosphorus pentoxide, stirring for 5-6 hours until the water content is detected to be less than 0.03%;
mixing dichloromethane and bromine, cooling to-10 to-13 ℃, then slowly introducing chlorine, maintaining the low temperature after the chlorine is added, and keeping the temperature for 10 minutes; the aeration time can be shortened by 30 to 50 percent by adding chlorine into a chlorine distributor;
the mass ratio of the dichloromethane to the bromine to the chlorine is 75: 50: 23;
the bromination reaction is carried out, PS and dichloromethane are added, the mixture is stirred until the PS and the dichloromethane are dissolved, then the temperature is reduced to 5 to 8 ℃, antimony tribromide and tin tetrabromide are added, and bromine chloride solution is dripped; the bromination reaction adopts an inner coil pipe and an outer circulation to assist in cooling, so that the bromine chloride feeding time can be shortened, and the whole reaction period can be shortened;
the mass ratio of PS to dichloromethane is 5: 46;
the mass ratio of the antimony tribromide to the tin tetrabromide is 1:1, and the addition amount of the antimony tribromide is 2.4% of the mass of the PS;
the BPS product is white or light yellow in appearance, the chlorine content is 0, 1 percent TGA @350 ℃, 5 percent TGA @380 ℃, the bromine content is not less than 66 percent, and the thermal decomposition temperature is not less than 270 ℃.
2. The method of claim 1, wherein the BPS product is prepared by a single process,
the bromination reaction is carried out, the dropping temperature of the bromine chloride solution is 5-8 ℃, the temperature is raised to 5-10 ℃ after the dropping is finished, and the heat preservation time is 5 hours.
3. The method of claim 1, wherein the BPS product is prepared by a single process,
and (3) after treatment, washing twice with deionized water, then dripping into hot water at 90 ℃, replacing the solvent, after the solvent replacement is finished, heating to 95 ℃, keeping the temperature for 1 hour, performing suction filtration, and drying the material at 120 ℃ for 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811612403.6A CN109485755B (en) | 2018-12-27 | 2018-12-27 | BPS product and preparation method thereof by bromine chloride method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811612403.6A CN109485755B (en) | 2018-12-27 | 2018-12-27 | BPS product and preparation method thereof by bromine chloride method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109485755A CN109485755A (en) | 2019-03-19 |
| CN109485755B true CN109485755B (en) | 2021-05-11 |
Family
ID=65712601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811612403.6A Active CN109485755B (en) | 2018-12-27 | 2018-12-27 | BPS product and preparation method thereof by bromine chloride method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109485755B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0047549A2 (en) * | 1980-08-20 | 1982-03-17 | Ferro Corporation | Process for the bromination of polystyrenes |
| CN102504067A (en) * | 2011-10-26 | 2012-06-20 | 山东润科化工股份有限公司 | Method for preparing bromination polystyrene |
| CN105504107A (en) * | 2016-01-12 | 2016-04-20 | 潍坊鑫洋化工有限公司 | Industrial preparation method of high heat stability brominated polystyrene |
-
2018
- 2018-12-27 CN CN201811612403.6A patent/CN109485755B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0047549A2 (en) * | 1980-08-20 | 1982-03-17 | Ferro Corporation | Process for the bromination of polystyrenes |
| CN102504067A (en) * | 2011-10-26 | 2012-06-20 | 山东润科化工股份有限公司 | Method for preparing bromination polystyrene |
| CN105504107A (en) * | 2016-01-12 | 2016-04-20 | 潍坊鑫洋化工有限公司 | Industrial preparation method of high heat stability brominated polystyrene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109485755A (en) | 2019-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106633189B (en) | A kind of efficient water resistance expanding fire retardant and its application in polypropylene | |
| CN110819009B (en) | High-melt-index halogen-free flame-retardant polypropylene material and preparation method thereof | |
| CN109485755B (en) | BPS product and preparation method thereof by bromine chloride method | |
| CN102504067B (en) | Method for preparing bromination polystyrene | |
| US20120041115A1 (en) | Pelletized Low Molecular Weight Brominated Aromatic Polymer Compositions | |
| KR20120060939A (en) | Bromination of low molecular weight aromatic polymer compositions | |
| CN103097298A (en) | Brine purification process | |
| CN104211999A (en) | Modified graphene cable material | |
| EP3008109A1 (en) | Method for continuously producing polyamide oligomers and for producing semicrystalline or amorphous polyamides that can be thermoplastically processed | |
| CN105504107A (en) | Industrial preparation method of high heat stability brominated polystyrene | |
| CN104558305A (en) | Process for synthesizing chlorinated polyvinyl chloride by virtue of acid-phase suspension method | |
| CN114957517B (en) | Method for continuously producing brominated polystyrene | |
| CN109694419A (en) | BPS product and preparation method thereof by full bromine method | |
| CN109762082B (en) | Low-molecular-weight BPS product and preparation method thereof | |
| CN106565876A (en) | Continuous preparation method of controlled-molecular-weight brominated polystyrene | |
| CN104204033B (en) | The manufacture method of polycarbonate resin and poly carbonate resin composition | |
| CN107118290B (en) | A kind of method that environment-friendly type water phase method prepares haloflex | |
| CN105367754B (en) | A kind of metaphenylene epoxy vinyl ester fiber glass resin and its synthetic method | |
| CN105837791B (en) | A kind of preparation method of glycolylurea epoxide resin | |
| CN102849789A (en) | Preparation method for stannic chloride pentahydrate | |
| CN110467584A (en) | A kind of continuous production method of 1,2- benzisothiazole-3-ketone | |
| CN104119676A (en) | Halogen-free flame retardant for PA66 and environment-friendly flame-retardant PA66 material prepared thereby | |
| CN109762120B (en) | Brominated SBS product with narrow molecular weight distribution and high thermal stability and preparation method thereof | |
| CN102583397A (en) | Method for preparing silicon dioxide and hydrogen chloride by means of hydrolysis of polysilicon by-product silicon tetrachloride | |
| WO2009122438A1 (en) | Improved process for heat stable chlorinated paraffin wax |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 262714 Shouguang Yangkou Chemical Industrial Park, Weifang City, Shandong Province (West of Yanglin road and north of Donghai Road) Patentee after: Shandong XURUI New Material Co.,Ltd. Address before: 262714 Bohai Industrial Park, Yangkou Town, Shouguang City, Weifang City, Shandong Province Patentee before: SHANDONG SUNRIS CO.,LTD. |
|
| CP03 | Change of name, title or address | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A BPS product and its preparation method using bromine chloride method Effective date of registration: 20230815 Granted publication date: 20210511 Pledgee: Zhejiang Commercial Bank Co.,Ltd. Weifang branch Pledgor: Shandong XURUI New Material Co.,Ltd. Registration number: Y2023980052362 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |