CN111116782A - Production process of brominated SBS - Google Patents
Production process of brominated SBS Download PDFInfo
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- CN111116782A CN111116782A CN201911348241.4A CN201911348241A CN111116782A CN 111116782 A CN111116782 A CN 111116782A CN 201911348241 A CN201911348241 A CN 201911348241A CN 111116782 A CN111116782 A CN 111116782A
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- 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
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Abstract
The invention discloses a production process of brominated SBS, belonging to the technical field of flame retardant production, comprising the following steps: adding SBS and isobutanol into a reaction kettle, heating to 20-40 ℃, stirring and keeping the temperature until the materials are completely dissolved; adding sodium bromide, introducing an oxidant chlorine, filling lime milk at the tail end of the reaction kettle to absorb the unreacted chlorine in the reaction kettle, and raising the temperature to 60-75 ℃ without raising the temperature; cooling to 20 ℃, adding a catalyst, and continuously heating to 75 ℃ to react for 1 hour, wherein the catalyst is stannic chloride and ferric trichloride; and (3) cooling to room temperature, adding peroxide and alkali metal alkoxide into the feed liquid after the reaction is finished, wherein the peroxide is hydrogen peroxide, the alkali metal alkoxide is sodium methoxide, heating to 30-40 ℃, keeping the temperature for 2 hours, filtering, washing, removing impurities, and drying to obtain the target product brominated SBS. The preparation of the brominated SBS is realized by adopting a direct bromination method, the reaction is mild, the bromine content, the yield and the thermal stability of the brominated SBS are improved, and the use requirement is met.
Description
Technical Field
The invention relates to the technical field of flame retardant production, in particular to a production process of brominated SBS.
Background
Brominated SBS is also called brominated styrene-butadiene-styrene triblock copolymer, is a flame retardant capable of replacing hexabromocyclododecane, and is a novel flame retardant applied to expanded polystyrene and extruded polystyrene foam boards. As hexabromocyclododecane has the possibility of one or more of bioaccumulation, toxicity to aquatic plants and durability on environmental influence, in addition, the dehydrobromination of hexabromocyclododecane becomes severe at the temperature of more than 190 ℃, the harm of hydrogen bromide steam is more obvious, toxic and harmful smoke is generated when the hexabromocyclododecane is used as a flame retardant, certain corrosion is caused to mechanical use, the brominated SBS flame retardant has higher thermal stability and good compatibility with polystyrene materials, the mechanical property and the like of the added materials cannot be negatively influenced, and the market prospect is wider. However, the existing production process of brominated SBS still has some problems, such as low bromine content, low yield, poor thermal stability and the like, which cause that the brominated SBS can not meet the use requirement, thereby limiting the large-scale production and the universal application of the brominated SBS.
Disclosure of Invention
The invention provides a production process of brominated SBS, which adopts a direct bromination method to realize the preparation of the brominated SBS, has mild reaction and easy control, improves the bromine content, yield and thermal stability of the brominated SBS, and meets the use requirements.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a production process of brominated SBS comprises the following steps:
(1) adding SBS and isobutanol into a reaction kettle, heating to 20-40 ℃, stirring and keeping the temperature until the materials are completely dissolved;
(2) adding sodium bromide, introducing an oxidant chlorine, filling lime milk at the tail end of the reaction kettle to absorb the unreacted chlorine in the reaction kettle, and raising the temperature to 60-75 ℃ without raising the temperature;
(3) cooling to 20 ℃, adding a catalyst, and continuously heating to 75 ℃ to react for 1 hour, wherein the catalyst is stannic chloride and ferric trichloride;
(4) and (3) cooling to room temperature, adding peroxide and alkali metal alkoxide into the feed liquid after the reaction is finished, wherein the peroxide is hydrogen peroxide, the alkali metal alkoxide is sodium methoxide, heating to 30-40 ℃, keeping the temperature for 2 hours, filtering, washing, removing impurities, and drying to obtain the target product brominated SBS.
Preferably, the mass ratio of the isobutanol to the SBS is 10-12: 1.
Preferably, the molar ratio of the sodium bromide, the catalyst and the SBS is 1.2-1.5: 0.1-0.5: 1, and the mass ratio of the stannic chloride to the ferric trichloride is 0.8: 1.
Preferably, the dosage of the hydrogen peroxide and the sodium methoxide is 2 wt% of the SBS.
The beneficial effects of the invention are as follows:
the process adopts a direct bromination method to realize the preparation of the brominated SBS, has obvious cost advantage compared with the preparation process on the current market, and has the advantages of low cost, no pollution, no three wastes and simple preparation scale; the reaction of sodium bromide and chlorine is milder than that of direct bromine, and is easy to control, because the energy of bromine is higher, the bromine reacts with SBS to generate substitution reaction, which affects the thermal weight loss of the product, does not resist high temperature, and has the phenomena of melting and color change; the composite catalyst tin tetrachloride and ferric trichloride are adopted, so that the reaction rate and the utilization rate of bromine are improved, the reaction yield is over 97 percent, and the bromine content of the product is over 75 percent, so that the product has very good flame retardant property; peroxide and alkali metal alkoxide are used as a remover after aliphatic chain bromination, so that factors influencing the thermal stability of the product in the bromination process are controlled, and the thermal stability of the product is improved; by adopting normal temperature reaction, the thermal weight loss of the product can be improved, the 1% thermal weight loss temperature is 232-242 ℃, the 5% thermal weight loss temperature is 246-254 ℃, the 10% thermal weight loss temperature is 258-269 ℃, and the 50% thermal weight loss temperature is 285-300 ℃, the chromaticity is ensured, and the product is not easy to melt at high temperature and meets the use requirement.
Detailed Description
To facilitate understanding of those skilled in the art, the present invention will be further described with reference to specific examples:
example 1:
a production process of brominated SBS comprises the following steps:
(1) adding SBS and isobutanol into a reaction kettle, heating to 20 ℃, stirring and keeping the temperature until the materials are completely dissolved;
(2) adding sodium bromide, introducing an oxidant chlorine, filling lime milk at the tail end of the reaction kettle to absorb the unreacted chlorine in the reaction kettle, and raising the temperature to 60 ℃ without raising the temperature;
(3) cooling to 20 ℃, adding a catalyst, and continuously heating to 75 ℃ to react for 1 hour, wherein the catalyst is stannic chloride and ferric trichloride;
(4) and (3) cooling to room temperature, adding peroxide and alkali metal alkoxide into the feed liquid after the reaction is finished, wherein the peroxide is hydrogen peroxide, the alkali metal alkoxide is sodium methoxide, heating to 30 ℃, keeping the temperature for 2 hours, filtering, washing, removing impurities, and drying to obtain the target product brominated SBS.
The mass ratio of the isobutanol to the SBS is 10: 1. The molar ratio of the sodium bromide to the catalyst to the SBS is 1.2: 0.1: 1, and the mass ratio of the stannic chloride to the ferric trichloride is 0.8: 1. The dosage of the hydrogen peroxide and the sodium methoxide is 2 wt% of that of the SBS.
Example 2:
a production process of brominated SBS comprises the following steps:
(1) adding SBS and isobutanol into a reaction kettle, heating to 40 ℃, stirring and keeping the temperature until the materials are completely dissolved;
(2) adding sodium bromide, introducing an oxidant chlorine, filling lime milk at the tail end of the reaction kettle to absorb the unreacted chlorine in the reaction kettle, and raising the temperature to 75 ℃ without raising the temperature;
(3) cooling to 20 ℃, adding a catalyst, and continuously heating to 75 ℃ to react for 1 hour, wherein the catalyst is stannic chloride and ferric trichloride;
(4) and (3) cooling to room temperature, adding peroxide and alkali metal alkoxide into the feed liquid after the reaction is finished, wherein the peroxide is hydrogen peroxide, the alkali metal alkoxide is sodium methoxide, heating to 40 ℃, keeping the temperature for 2 hours, filtering, washing, removing impurities, and drying to obtain the target product brominated SBS.
The mass ratio of the isobutanol to the SBS is 12: 1. The molar ratio of the sodium bromide to the catalyst to the SBS is 1.5: 0.5: 1, and the mass ratio of the stannic chloride to the ferric trichloride is 0.8: 1. The dosage of the hydrogen peroxide and the sodium methoxide is 2 wt% of that of the SBS.
Example 3:
a production process of brominated SBS comprises the following steps:
(1) adding SBS and isobutanol into a reaction kettle, heating to 30 ℃, stirring and keeping the temperature until the materials are completely dissolved;
(2) adding sodium bromide, introducing an oxidant chlorine, filling lime milk at the tail end of the reaction kettle to absorb the unreacted chlorine in the reaction kettle, and raising the temperature to 70 ℃ without raising the temperature;
(3) cooling to 20 ℃, adding a catalyst, and continuously heating to 75 ℃ to react for 1 hour, wherein the catalyst is stannic chloride and ferric trichloride;
(4) and (3) cooling to room temperature, adding peroxide and alkali metal alkoxide into the feed liquid after the reaction is finished, wherein the peroxide is hydrogen peroxide, the alkali metal alkoxide is sodium methoxide, heating to 35 ℃, keeping the temperature for 2 hours, filtering, washing, removing impurities, and drying to obtain the target product brominated SBS.
The mass ratio of the isobutanol to the SBS is 11: 1. The molar ratio of the sodium bromide to the catalyst to the SBS is 1.3: 0.2: 1, and the mass ratio of the stannic chloride to the ferric trichloride is 0.8: 1. The dosage of the hydrogen peroxide and the sodium methoxide is 2 wt% of that of the SBS.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the present invention as defined in the accompanying claims.
Claims (4)
1. A production process of brominated SBS is characterized by comprising the following steps:
(1) adding SBS and isobutanol into a reaction kettle, heating to 20-40 ℃, stirring and keeping the temperature until the materials are completely dissolved;
(2) adding sodium bromide, introducing an oxidant chlorine, filling lime milk at the tail end of the reaction kettle to absorb the unreacted chlorine in the reaction kettle, and raising the temperature to 60-75 ℃ without raising the temperature;
(3) cooling to 20 ℃, adding a catalyst, and continuously heating to 75 ℃ to react for 1 hour, wherein the catalyst is stannic chloride and ferric trichloride;
(4) and (3) cooling to room temperature, adding peroxide and alkali metal alkoxide into the feed liquid after the reaction is finished, wherein the peroxide is hydrogen peroxide, the alkali metal alkoxide is sodium methoxide, heating to 30-40 ℃, keeping the temperature for 2 hours, filtering, washing, removing impurities, and drying to obtain the target product brominated SBS.
2. The process for the production of brominated SBS according to claim 1, wherein the mass ratio of isobutanol to SBS is 10-12: 1.
3. The process according to claim 1, wherein the molar ratio of said sodium bromide, catalyst and SBS is 1.2-1.5: 0.1-0.5: 1, and the mass ratio of the stannic chloride to the ferric trichloride is 0.8: 1.
4. The process according to claim 1, wherein the amounts of hydrogen peroxide and sodium methoxide are both 2 wt% of SBS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911348241.4A CN111116782A (en) | 2019-12-24 | 2019-12-24 | Production process of brominated SBS |
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| CN201911348241.4A CN111116782A (en) | 2019-12-24 | 2019-12-24 | Production process of brominated SBS |
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| CN111116782A true CN111116782A (en) | 2020-05-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521232A (en) * | 2022-08-30 | 2022-12-27 | 山东重山光电材料股份有限公司 | Preparation method of high-purity perfluoroalkyl sulfonyl bromide |
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2019
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521232A (en) * | 2022-08-30 | 2022-12-27 | 山东重山光电材料股份有限公司 | Preparation method of high-purity perfluoroalkyl sulfonyl bromide |
| CN115521232B (en) * | 2022-08-30 | 2024-01-26 | 山东重山光电材料股份有限公司 | Preparation method of high-purity perfluoroalkyl sulfonyl bromide |
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Application publication date: 20200508 |