CN111269370A - Synthesis method of brominated butadiene-styrene block copolymer - Google Patents
Synthesis method of brominated butadiene-styrene block copolymer Download PDFInfo
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Abstract
The invention relates to a synthesis method of a brominated butadiene-styrene block copolymer, which solves the technical problems of complex production process, low production efficiency, low bromine utilization rate, low product yield, more byproducts, low purity, poor stability, poor flame retardant property of products, difficult solvent recovery, environmental pollution and the like in the prior art. The method comprises the following steps: 1) adding butadiene-styrene block copolymer into an organic solvent, stirring for dissolving, adding water and an emulsifier, and stirring to obtain butadiene-styrene block copolymer emulsion; 2) mixing fatty alcohol with water, stirring, adding sodium bromide, inorganic acid and surfactant, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and a sodium bromate aqueous solution, carrying out bromination reaction, and keeping the temperature after dropwise adding is finished to obtain a brominated butadiene-styrene block copolymer crude product; 3) and (4) carrying out post-treatment to obtain a brominated butadiene-styrene block copolymer product. The invention is applied to the technical field of flame retardant synthesis.
Description
Technical Field
The invention belongs to the technical field of flame retardant synthesis, and particularly relates to a synthesis method of a brominated butadiene-styrene block copolymer.
Background
Hexabromocyclododecane (HBCD) is the most commonly used flame retardant for the current mandatory flame retardant building exterior wall insulation material, the annual usage amount exceeds 30 million tons, 5 months in 2013, and is determined by chemical meetings of united nations from more than 160 countries and organization representatives in the world: the use of the flame retardant HBCD is prohibited globally. HBCD is added to the list of annexes a for the stockholm convention on persistent organic pollutants to ban on chemicals. The convention holds that it belongs to persistent organic pollutants, is toxic, difficult to degrade, can accumulate in the organism, can be transported by air, water and migrating species and products and deposited in areas far from their discharge site, can accumulate in the ecosystem for a long time, can possibly cause cancers, damage the central and peripheral nervous systems, cause immune system diseases, reproductive disorders and interfere with the normal development of infants even when exposed to very low doses of POPs, and directly threatens human survival and sustainable development. The worldwide banning of hexabromocyclododecane is 2014 spring, and the national centre for environmental protection of geneva, switzerland sets a buffer period of 5 years (i.e. to 2019) for the use of HBCD in foamed and extruded polystyrene insulation for construction. In 2016, the national ministry of major committees approved "the stockholm convention for persistent organic pollutants") the new addition to hexabromocyclododecane amendments that prohibited the production, use, and import and export of HBCD from 2016, 12, 26, but due to the lack of suitable substitutes, HBCD used in building insulation XPS and EPS flame retardants acquired a 5-year exemption period that ended at 2021, 12, 25 days. In 2016, the ministry of environmental protection in China also added HBCD to the toxic chemicals catalog strictly restricting import and export in China, so that the search for a substitute for HBCD is a priority in XPS and EPS industries.
Brominated butadiene-styrene copolymer (brominated SBS) is listed in the catalogue of substitutes of toxic and harmful raw materials (products) encouraged by the state (2016 edition) at present, and brominated SBS is a novel high-molecular flame retardant material and accords with the development direction of flame retardant materials.
However, the existing brominated SBS production process has the technical problems of poor product performance (bromine content is about 63 percent, 5 percent thermal weight loss is only 245 ℃ and softening point is about 110 ℃), low yield (less than 90 percent), low bromine utilization rate (less than 70 percent), environmental pollution, complex synthesis process, low production efficiency, difficult solvent recovery, more byproducts, poor thermal stability and influence on flame retardant performance, and the large-scale production and the general application of brominated SBS are limited.
Disclosure of Invention
Aiming at the technical problems, the invention provides the synthesis method of the brominated butadiene-styrene block copolymer, which has the advantages of simple production process, high production efficiency, high bromine utilization rate, high product yield, less side reactions, high purity, good stability, obviously improved flame retardant property of the product, production cost saving and environmental protection.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for synthesizing a brominated butadiene-styrene block copolymer comprises the following steps:
1) butadiene-styrene block copolymer emulsion preparation:
adding butadiene-styrene block copolymer into an organic solvent, stirring for dissolving, adding water and an emulsifier, and stirring for 1-3 hours to obtain butadiene-styrene block copolymer emulsion;
2) synthesis of crude brominated butadiene-styrene Block copolymer:
mixing fatty alcohol with water, stirring, adding sodium bromide, inorganic acid and surfactant, controlling the reaction temperature to be-10-2 ℃, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and a sodium bromate aqueous solution, carrying out bromination reaction, and keeping the temperature for 8-12 hours after dropwise adding to obtain a brominated butadiene-styrene block copolymer crude product;
3) and (3) post-treatment:
adding a reducing agent into the crude product of the brominated butadiene-styrene block copolymer prepared in the step 2) to remove residual bromine, adjusting the pH value to be neutral by using a neutralizing agent, filtering, recovering the organic solvent, and drying the residual reaction solution at 80 ℃ to obtain the brominated butadiene-styrene block copolymer product.
Preferably, in the step 1), the vinyl content of the butadiene-styrene block copolymer is more than 70%, and the molecular weight is 35000-50000.
Preferably, in the step 1), the organic solvent is halogenated alkane and/or halogenated aromatic hydrocarbon, the halogenated alkane is one or more of dichloromethane, dichloroethane, chloroform and carbon tetrachloride, and the halogenated aromatic hydrocarbon is one or more of chlorobenzene, o-dichlorobenzene and o-nitrochlorobenzene; the mass ratio of the organic solvent to the butadiene-styrene block copolymer is 5-10: 1.
Preferably, in the step 1), the mass ratio of the water to the organic solvent is 0.3-0.5: 1.
Preferably, in the step 1), the emulsifier is one or more of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ether, nonylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether and polyethylene glycol, and the mass of the emulsifier is 0.1-0.5% of that of water.
Preferably, in the step 2), the fatty alcohol is a long-chain fatty alcohol with a solubility of less than 20% in water, the fatty alcohol is one or more of n-butyl alcohol, isobutyl alcohol, n-hexyl alcohol and isooctyl alcohol, and the mass ratio of the fatty alcohol to the water is 1-3: 1.
Preferably, in the step 2), the mass of the sodium bromide is 2-3 times of that of the butadiene-styrene block copolymer in the step 1); the concentration of the sodium bromate aqueous solution is 10-30 wt.%, and the molar ratio of the sodium bromate to the sodium bromide is 1: 5.
Preferably, in step 2), the inorganic acid is sulfuric acid or hydrochloric acid, and the molar ratio of H ions to sodium bromide in the inorganic acid is 6: 5.
Preferably, in the step 2), the surfactant is one of sodium dodecyl benzene sulfonate or sodium dodecyl sulfonate, and the mass of the surfactant is 0.1-0.5% of that of the water.
Preferably, in the step 3), the reducing agent is one or more aqueous solutions of sodium sulfite, sodium bisulfite, sodium thiosulfate and hydrazine hydrate, and the concentration of the reducing agent is 10-25%; the neutralizing agent is one or more aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and potassium carbonate, and the concentration of the neutralizing agent is 10-25 wt.%.
The invention has the beneficial effects that:
the invention changes the conventional synthesis method of the brominated butadiene-styrene block copolymer, adopts halohydrocarbon, fatty alcohol and water as reaction solvents, converts a heterogeneous system into a homogeneous system through the combined action of an emulsifier and a surfactant, greatly improves the conversion rate of bromine in the bromination process of the butadiene-styrene block copolymer, and has the vinyl bromination rate of more than 99 percent;
the invention has high bromine utilization rate, high product yield, less side reaction and high purity, 5 percent of thermal weight loss is more than or equal to 250 ℃, and the flame retardant property of the product is obviously improved; the invention has simple production process, high production efficiency, convenient post-treatment and easy large-scale production.
Sodium bromate and sodium bromide are used as a bromine source, bromine is generated in situ under the action of inorganic acid, and accurate bromination of vinyl double bonds is realized at low temperature by controlling the dropping rate of the butadiene-styrene segmented copolymer emulsion and a sodium bromate aqueous solution, so that the technical problems of poor thermal stability and the like caused by ectopic bromination are solved.
The organic solvent is recycled in the post-treatment process, so that the production cost is saved and the environment is protected.
Detailed Description
The present invention will be further described with reference to specific examples to assist understanding of the invention. The method used in the invention is a conventional production method if no special provisions are made; the starting materials used, unless otherwise specified, are conventional commercial products.
Example 1
1) Butadiene-styrene block copolymer emulsion preparation:
adding 210g of trichloromethane and 30g of butadiene-styrene block copolymer into a 1000ml four-neck flask, stirring for dissolving, adding 100g of water and 0.3g of alkylphenol polyoxyethylene, and stirring for 3 hours to obtain butadiene-styrene block copolymer emulsion;
2) synthesis of brominated butadiene-styrene Block copolymer:
adding 500g of n-butanol and 200g of water into a reaction container, adding 76g of sodium bromide, 43.4g of sulfuric acid and 0.3g of sodium dodecyl benzene sulfonate, controlling the reaction temperature to be-4 ℃, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and 97.0g of 23 wt.% sodium bromate aqueous solution, carrying out bromination reaction, and preserving heat for 10 hours after the dropwise addition is finished to obtain a brominated butadiene-styrene block copolymer crude product;
the vinyl bromination rate was measured by sampling and found to be 99.5%.
3) Post-treatment
Adding a sodium sulfite aqueous solution with the concentration of 15 wt.% into the brominated butadiene-styrene block copolymer prepared in the step 2) to remove residual bromine, then adding a sodium carbonate aqueous solution with the concentration of 15 wt.% to adjust the pH to be neutral, filtering, recovering the organic solvent, and drying the residual reaction solution at 80 ℃ to obtain a brominated butadiene-styrene block copolymer product.
The product yield was calculated to be 98.1% with a purity of 99.0%.
The product is white flowable powder in appearance, has a molecular weight of 8-10 ten thousand, and has a bromine content of more than or equal to 64 percent, a 5 percent thermal weight loss of more than or equal to 250 ℃ and a softening point of more than or equal to 120 ℃.
Example 2
1) Butadiene-styrene block copolymer emulsion preparation:
adding 150g of dichloromethane and 30g of butadiene-styrene block copolymer into a 1000ml four-neck flask, stirring for dissolving, adding 45g of water and 0.045g of fatty alcohol-polyoxyethylene ether, and stirring for 1 hour to obtain butadiene-styrene block copolymer emulsion;
2) synthesis of crude brominated butadiene-styrene Block copolymer:
adding 200g of isobutanol and 200g of water into a reaction container, adding 60g of sodium bromide, 25.5g of hydrochloric acid and 0.2g of sodium dodecyl sulfate, controlling the reaction temperature to be-10 ℃, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and 175.9g of sodium bromate aqueous solution with the concentration of 10 wt.% for bromination reaction, and after the dropwise addition is finished, keeping the temperature for 8 hours to obtain a brominated butadiene-styrene block copolymer crude product;
the vinyl bromination rate was measured by sampling and found to be 99.1%.
3) Post-treatment
Adding 10 wt.% sodium bisulfite aqueous solution into the brominated butadiene-styrene block copolymer prepared in the step 2) to remove residual bromine, then adding 10 wt.% sodium hydroxide solution to adjust the pH to be neutral, filtering, recovering the organic solvent, and drying the residual reaction solution at 80 ℃ to obtain the brominated butadiene-styrene block copolymer product.
The product yield was calculated to be 97.0% with a purity of 98.2%.
The product is white flowable powder in appearance, has a molecular weight of 8-10 ten thousand, and has a bromine content of more than or equal to 64 percent, a 5 percent thermal weight loss of more than or equal to 250 ℃ and a softening point of more than or equal to 120 ℃.
Example 3
1) Butadiene-styrene block copolymer emulsion preparation:
adding 300g of dichloroethane and 30g of butadiene-styrene block copolymer into a 1000ml four-neck flask, stirring for dissolving, adding 150g of water and 0.75g of fatty acid polyoxyethylene ether, and stirring for 3 hours to obtain butadiene-styrene block copolymer emulsion;
2) synthesis of brominated butadiene-styrene Block copolymer:
adding 600g of n-hexanol and 200g of water into a reaction container, adding 90g of sodium bromide, 51.4g of sulfuric acid and 1g of sodium dodecyl benzene sulfonate, controlling the reaction temperature to be 2 ℃, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and 88.0g of a 30 wt.% sodium bromate aqueous solution, carrying out bromination reaction, and after the dropwise addition is finished, keeping the temperature for 12 hours to obtain a brominated butadiene-styrene block copolymer crude product;
the vinyl bromination rate was measured by sampling and found to be 99.3%.
3) Post-treatment
Adding 25 wt.% sodium thiosulfate aqueous solution into the brominated butadiene-styrene block copolymer prepared in the step 2) to remove residual bromine, then adding 25 wt.% potassium hydroxide aqueous solution to adjust the pH to be neutral, filtering, recovering the organic solvent, and drying the residual reaction solution at 80 ℃ to obtain a brominated butadiene-styrene block copolymer product.
The product yield was calculated to be 97.8% with a purity of 98.7%.
The product is white flowable powder in appearance, has a molecular weight of 8-10 ten thousand, and has a bromine content of more than or equal to 64 percent, a 5 percent thermal weight loss of more than or equal to 250 ℃ and a softening point of more than or equal to 120 ℃.
Example 4
1) Butadiene-styrene block copolymer emulsion preparation:
adding 225g of carbon tetrachloride and 30g of butadiene-styrene block copolymer into a 1000ml four-neck flask, stirring for dissolving, adding 90g of water and 0.225g of nonylphenol polyoxyethylene ether, and stirring for 2 hours to obtain butadiene-styrene block copolymer emulsion;
2) synthesis of brominated butadiene-styrene Block copolymer:
adding 400g of isooctanol and 200g of water into a reaction container, adding 75g of sodium bromide, 31.9g of hydrochloric acid and 0.5g of sodium dodecyl sulfate, controlling the reaction temperature to be-4 ℃, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and 110.0g of a sodium bromate aqueous solution with the concentration of 20 wt.% for bromination reaction, and preserving heat for 10 hours after the dropwise adding is finished to obtain a brominated butadiene-styrene block copolymer crude product;
the vinyl bromination rate was measured by sampling and found to be 99.7%.
3) Post-treatment
Adding a hydrazine hydrate aqueous solution with the concentration of 18 wt.% into the brominated butadiene-styrene block copolymer prepared in the step 2) to remove residual bromine, then adding a sodium bicarbonate aqueous solution with the concentration of 18 wt.% to adjust the pH to be neutral, filtering, recovering the organic solvent, and drying the residual reaction solution at 80 ℃ to obtain a brominated butadiene-styrene block copolymer product.
The product yield was calculated to be 98.2% with a purity of 98.9%.
The product is white flowable powder in appearance, has a molecular weight of 8-10 ten thousand, and has a bromine content of more than or equal to 64 percent, a 5 percent thermal weight loss of more than or equal to 250 ℃ and a softening point of more than or equal to 120 ℃.
Example 5
1) Butadiene-styrene block copolymer emulsion preparation:
adding 180g of chlorobenzene and 30g of butadiene-styrene block copolymer into a 1000ml four-neck flask, stirring for dissolving, adding 81g of water and 0.162g of polyethylene glycol, and stirring for 1.5 hours to obtain butadiene-styrene block copolymer emulsion;
2) synthesis of brominated butadiene-styrene Block copolymer:
adding 250g of n-butanol, 250g of isobutanol and 200g of water into a reaction container, adding 66g of sodium bromide, 37.7g of sulfuric acid and 0.4g of sodium dodecyl benzene sulfonate, controlling the reaction temperature to be 0 ℃, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and 129.0g of sodium bromate aqueous solution with the concentration of 15 wt.% for bromination reaction, and preserving heat for 11 hours after the dropwise addition is finished to obtain a brominated butadiene-styrene block copolymer crude product;
the vinyl bromination rate was measured by sampling and found to be 99.0%.
3) Post-treatment
Adding two aqueous solutions of sodium sulfite and sodium bisulfite, the concentrations of which are both 20 wt.%, into the brominated butadiene-styrene block copolymer prepared in the step 2) to remove residual bromine, then adding a potassium carbonate aqueous solution, the concentration of which is 14 wt.%, to adjust the pH to be neutral, filtering, recovering the organic solvent, and drying the residual reaction solution at 80 ℃ to obtain a brominated butadiene-styrene block copolymer product.
The product yield was calculated to be 97.5% with a purity of 98.3%.
The product is white flowable powder in appearance, has a molecular weight of 8-10 ten thousand, and has a bromine content of more than or equal to 64 percent, a 5 percent thermal weight loss of more than or equal to 250 ℃ and a softening point of more than or equal to 120 ℃.
Example 6
1) Butadiene-styrene block copolymer emulsion preparation:
adding 270g of o-dichlorobenzene and 30g of butadiene-styrene block copolymer into a 1000ml four-neck flask, stirring for dissolving, adding 94.5g of water, 0.189g of fatty alcohol-polyoxyethylene ether and 0.189g of fatty acid-polyoxyethylene ether, and stirring for 2.5 hours to obtain butadiene-styrene block copolymer emulsion;
2) synthesis of brominated butadiene-styrene Block copolymer:
adding 150g of n-hexanol, 150g of isooctanol and 200g of water into a reaction container, adding 84g of sodium bromide, 35.7g of hydrochloric acid and 0.8g of sodium dodecyl sulfate, controlling the reaction temperature to be-8 ℃, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and 98.5g of sodium bromate aqueous solution with the concentration of 25 wt.% for bromination reaction, and preserving heat for 9 hours after the dropwise addition is finished to obtain a brominated butadiene-styrene block copolymer crude product;
the vinyl bromination rate was measured by sampling and found to be 99.4%.
3) Post-treatment
Adding two aqueous solutions of sodium thiosulfate and hydrazine hydrate with the concentration of 14 wt.% into the brominated butadiene-styrene block copolymer prepared in the step 2) to remove residual bromine, then adding two aqueous solutions of sodium hydroxide and potassium hydroxide with the concentration of 20 wt.% to adjust the pH to be neutral, filtering, recovering the organic solvent, and drying the residual reaction solution at 80 ℃ to obtain a brominated butadiene-styrene block copolymer product.
The product yield was calculated to be 97.6% with a purity of 98.8%.
The product is white flowable powder in appearance, has a molecular weight of 8-10 ten thousand, and has a bromine content of more than or equal to 64 percent, a 5 percent thermal weight loss of more than or equal to 250 ℃ and a softening point of more than or equal to 120 ℃.
Example 7
1) Butadiene-styrene block copolymer emulsion preparation:
adding 225g of o-nitrochlorobenzene and 30g of butadiene-styrene block copolymer into a 1000ml four-neck flask, stirring for dissolving, adding 90g of water and 0.075g of nonylphenol polyoxyethylene ether, 0.075g of polyethylene glycol and 0.075g of alkylphenol polyoxyethylene ether, and stirring for 2 hours to obtain butadiene-styrene block copolymer emulsion;
2) synthesis of brominated butadiene-styrene Block copolymer:
adding 200g of n-butanol, 200g of isooctanol and 200g of water into a reaction container, adding 75g of sodium bromide, 42.8g of sulfuric acid and 0.5g of sodium dodecyl benzene sulfonate, controlling the reaction temperature to be-6 ℃, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and 110g of sodium bromate aqueous solution with the concentration of 20 wt.%, carrying out bromination reaction, and preserving heat for 10 hours after the dropwise addition is finished to obtain a brominated butadiene-styrene block copolymer crude product;
the vinyl bromination rate was measured by sampling and found to be 99.5%.
3) Post-treatment
Adding two aqueous solutions of sodium sulfite and hydrazine hydrate with the concentration of 22 wt.% into the brominated butadiene-styrene block copolymer prepared in the step 2) to remove residual bromine, then adding aqueous solutions of sodium carbonate, sodium bicarbonate and potassium carbonate with the concentration of 12 wt.% to adjust the pH to be neutral, filtering, recovering the organic solvent, and drying the residual reaction solution at 80 ℃ to obtain a brominated butadiene-styrene block copolymer product.
The product yield was calculated to be 97.7% with a purity of 98.5%.
The product is white flowable powder in appearance, has a molecular weight of 8-10 ten thousand, and has a bromine content of more than or equal to 64 percent, a 5 percent thermal weight loss of more than or equal to 250 ℃ and a softening point of more than or equal to 120 ℃.
Example 8
1) Butadiene-styrene block copolymer emulsion preparation:
adding 120g of dichloromethane, 120g of dichloroethane and 30g of butadiene-styrene block copolymer into a 1000ml four-neck flask, stirring for dissolving, adding 90g of water, 0.05g of fatty alcohol-polyoxyethylene ether, 0.05g of fatty acid-polyoxyethylene ether, 0.05g of nonylphenol polyoxyethylene ether and 0.05g of polyethylene glycol, and stirring for 2 hours to obtain butadiene-styrene block copolymer emulsion;
2) synthesis of brominated butadiene-styrene Block copolymer:
adding 140g of n-butanol, 140g of isobutanol, 140g of n-hexanol and 200g of water into a reaction container, adding 75g of sodium bromide, 31.9g of hydrochloric acid and 0.5g of sodium dodecyl sulfate, controlling the reaction temperature to be-2 ℃, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and 110.0g of sodium bromate aqueous solution with the concentration of 20 wt.% for bromination reaction, and preserving heat for 10 hours after the dropwise addition is finished to obtain a brominated butadiene-styrene block copolymer crude product;
the vinyl bromination rate was measured by sampling and found to be 99.4%.
3) Post-treatment
Adding sodium sulfite, sodium bisulfite and sodium thiosulfate aqueous solutions with the concentrations of 12 wt.% into the brominated butadiene-styrene block copolymer prepared in the step 2) to remove residual bromine, then adding sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate aqueous solutions with the concentrations of 22 wt.% to adjust the pH to be neutral, filtering, recovering the organic solvent, and drying the residual reaction solution at 80 ℃ to obtain a brominated butadiene-styrene block copolymer product.
The product yield was calculated to be 97.5% with a purity of 98.0%.
The product is white flowable powder in appearance, has a molecular weight of 8-10 ten thousand, and has a bromine content of more than or equal to 64 percent, a 5 percent thermal weight loss of more than or equal to 250 ℃ and a softening point of more than or equal to 120 ℃.
Example 9
1) Butadiene-styrene block copolymer emulsion preparation:
adding 50g of dichloromethane, 50g of dichloroethane, 50g of trichloromethane, 50g of carbon tetrachloride and 30g of butadiene-styrene block copolymer into a 1000ml four-neck flask, stirring for dissolving, adding 100g of water, 0.06g of fatty alcohol polyoxyethylene ether, 0.06g of fatty acid polyoxyethylene ether, 0.06g of nonylphenol polyoxyethylene ether, 0.06g of polyethylene glycol and 0.06g of alkylphenol polyoxyethylene ether, and stirring for 3 hours to obtain butadiene-styrene block copolymer emulsion;
2) synthesis of brominated butadiene-styrene Block copolymer:
adding 125g of n-butanol, 125g of isobutanol, 125g of n-hexanol, 125g of isooctanol and 200g of water into a reaction container, adding 76g of sodium bromide, 43.4g of sulfuric acid and 0.3g of sodium dodecyl benzene sulfonate, controlling the reaction temperature to be-4 ℃, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and 97.0g of 23 wt.% sodium bromate aqueous solution, carrying out bromination reaction, and after the dropwise addition is finished, keeping the temperature for 10 hours to obtain a brominated butadiene-styrene block copolymer crude product;
the vinyl bromination rate was measured by sampling and found to be 99.2%.
3) Post-treatment
Adding aqueous solution of sodium sulfite, sodium bisulfite, sodium thiosulfate and hydrazine hydrate with the concentration of 18 wt.% into the brominated butadiene-styrene block copolymer prepared in the step 2) to remove residual bromine, then adding aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and potassium carbonate with the concentration of 18 wt.% to adjust the pH to be neutral, filtering, recovering the organic solvent, and drying the residual reaction solution at 80 ℃ to obtain a brominated butadiene-styrene block copolymer product.
The product yield was calculated to be 97.3% with a purity of 98.0%.
The product is white flowable powder in appearance, has a molecular weight of 8-10 ten thousand, and has a bromine content of more than or equal to 64 percent, a 5 percent thermal weight loss of more than or equal to 250 ℃ and a softening point of more than or equal to 120 ℃.
Example 10
1) Butadiene-styrene block copolymer emulsion preparation:
adding 70g of chlorobenzene, 70g of o-dichlorobenzene, 70g of o-nitrochlorobenzene and 30g of butadiene-styrene block copolymer into a 1000ml four-neck flask, stirring for dissolving, adding 100g of water and 0.3g of alkylphenol polyoxyethylene, and stirring for 3 hours to obtain butadiene-styrene block copolymer emulsion;
2) synthesis of brominated butadiene-styrene Block copolymer:
adding 500g of n-butanol and 200g of water into a reaction container, adding 76g of sodium bromide, 43.4g of sulfuric acid and 0.3g of sodium dodecyl benzene sulfonate, controlling the reaction temperature to be-4 ℃, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and 97.0g of 23 wt.% sodium bromate aqueous solution, carrying out bromination reaction, and preserving heat for 10 hours after the dropwise addition is finished to obtain a brominated butadiene-styrene block copolymer crude product;
the vinyl bromination rate was measured by sampling and found to be 99.6%.
3) Post-treatment
Adding a sodium sulfite aqueous solution with the concentration of 15 wt.% into the brominated butadiene-styrene block copolymer prepared in the step 2) to remove residual bromine, then adding a sodium carbonate aqueous solution with the concentration of 15 wt.% to adjust the pH to be neutral, filtering, recovering the organic solvent, and drying the residual reaction solution at 80 ℃ to obtain a brominated butadiene-styrene block copolymer product.
The product yield was calculated to be 97.4% with a purity of 99.0%.
The product is white flowable powder in appearance, has a molecular weight of 8-10 ten thousand, and has a bromine content of more than or equal to 64 percent, a 5 percent thermal weight loss of more than or equal to 250 ℃ and a softening point of more than or equal to 120 ℃.
Example 11
1) Butadiene-styrene block copolymer emulsion preparation:
adding 30g of dichloromethane, 30g of dichloroethane, 30g of trichloromethane, 30g of carbon tetrachloride, 30g of chlorobenzene, 30g of o-dichlorobenzene, 30g of o-nitrochlorobenzene and 30g of butadiene-styrene block copolymer into a 1000ml four-neck flask, stirring for dissolving, adding 90g of water and 0.225g of nonylphenol polyoxyethylene ether, and stirring for 2 hours to obtain butadiene-styrene block copolymer emulsion;
2) synthesis of brominated butadiene-styrene Block copolymer:
adding 400g of isooctanol and 200g of water into a reaction container, adding 75g of sodium bromide, 31.9g of hydrochloric acid and 0.5g of sodium dodecyl sulfate, controlling the reaction temperature to be-4 ℃, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and 110.0g of a sodium bromate aqueous solution with the concentration of 20 wt.% for bromination reaction, and preserving heat for 10 hours after the dropwise adding is finished to obtain a brominated butadiene-styrene block copolymer crude product;
the vinyl bromination rate was measured by sampling and found to be 99.5%.
3) Post-treatment
Adding a hydrazine hydrate aqueous solution with the concentration of 18 wt.% into the brominated butadiene-styrene block copolymer prepared in the step 2) to remove residual bromine, then adding a sodium bicarbonate aqueous solution with the concentration of 18 wt.% to adjust the pH to be neutral, filtering, recovering the organic solvent, and drying the residual reaction solution at 80 ℃ to obtain a brominated butadiene-styrene block copolymer product.
The product yield was calculated to be 97.1% with a purity of 98.2%.
The product is white flowable powder in appearance, has a molecular weight of 8-10 ten thousand, and has a bromine content of more than or equal to 64 percent, a 5 percent thermal weight loss of more than or equal to 250 ℃ and a softening point of more than or equal to 120 ℃.
In conclusion, the invention has the advantages of high bromine utilization rate, high product yield, less side reaction and high purity, the 5 percent thermal weight loss is more than or equal to 250 ℃, and the flame retardant property of the product is obviously improved.
Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that the embodiments may be modified or changed without departing from the spirit of the present invention within the scope of the claims.
Claims (10)
1. A method for synthesizing a brominated butadiene-styrene block copolymer is characterized by comprising the following steps:
1) butadiene-styrene block copolymer emulsion preparation:
adding butadiene-styrene block copolymer into an organic solvent, stirring for dissolving, adding water and an emulsifier, and stirring for 1-3 hours to obtain butadiene-styrene block copolymer emulsion;
2) synthesis of crude brominated butadiene-styrene Block copolymer:
mixing fatty alcohol with water, stirring, adding sodium bromide, inorganic acid and surfactant, controlling the reaction temperature to be-10-2 ℃, simultaneously dropwise adding the butadiene-styrene block copolymer emulsion prepared in the step 1) and a sodium bromate aqueous solution, carrying out bromination reaction, and keeping the temperature for 8-12 hours after dropwise adding to obtain a brominated butadiene-styrene block copolymer crude product;
3) and (3) post-treatment:
adding a reducing agent into the crude product of the brominated butadiene-styrene block copolymer prepared in the step 2) to remove residual bromine, adjusting the pH value to be neutral by using a neutralizing agent, filtering, recovering the organic solvent, and drying the residual reaction solution at 80 ℃ to obtain the brominated butadiene-styrene block copolymer product.
2. The method for synthesizing a brominated butadiene-styrene block copolymer according to claim 1, wherein in step 1), the butadiene-styrene block copolymer has a vinyl content of more than 70% and a molecular weight of 35000 to 50000.
3. The method for synthesizing the brominated butadiene-styrene block copolymer according to claim 1, wherein in the step 1), the organic solvent is halogenated alkane and/or halogenated aromatic hydrocarbon, the halogenated alkane is one or more of dichloromethane, dichloroethane, trichloromethane and carbon tetrachloride, and the halogenated aromatic hydrocarbon is one or more of chlorobenzene, o-dichlorobenzene and o-nitrochlorobenzene; the mass ratio of the organic solvent to the butadiene-styrene block copolymer is 5-10: 1.
4. The method for synthesizing a brominated butadiene-styrene block copolymer according to claim 1, wherein in the step 1), the mass ratio of water to the organic solvent is 0.3 to 0.5: 1.
5. The method for synthesizing a brominated butadiene-styrene block copolymer according to claim 1, wherein in step 1), the emulsifier is one or more of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ether, nonylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether, and polyethylene glycol, and the mass of the emulsifier is 0.1-0.5% of the mass of water.
6. The method for synthesizing the brominated butadiene-styrene block copolymer according to claim 1, wherein in the step 2), the fatty alcohol is a long-chain fatty alcohol with a solubility in water of less than 20%, the fatty alcohol is one or more of n-butanol, isobutanol, n-hexanol and isooctanol, and the mass ratio of the fatty alcohol to the water is 1-3: 1.
7. The method for synthesizing a brominated butadiene-styrene block copolymer according to claim 1, wherein in the step 2), the mass of sodium bromide is 2 to 3 times that of the butadiene-styrene block copolymer in the step 1); the concentration of the sodium bromate aqueous solution is 10-30 wt.%, and the molar ratio of the sodium bromate to the sodium bromide is 1: 5.
8. The method for synthesizing a brominated butadiene-styrene block copolymer according to claim 1, wherein in the step 2), the inorganic acid is sulfuric acid or hydrochloric acid, and the molar ratio of H ions to sodium bromide in the inorganic acid is 6: 5.
9. The method for synthesizing a brominated butadiene-styrene block copolymer according to claim 1, wherein in the step 2), the surfactant is one of sodium dodecylbenzenesulfonate or sodium dodecylbenzenesulfonate, and the mass of the surfactant is 0.1 to 0.5% of the mass of water.
10. The method for synthesizing brominated butadiene-styrene block copolymer according to claim 1, wherein in the step 3), the reducing agent is one or more aqueous solution of sodium sulfite, sodium bisulfite, sodium thiosulfate and hydrazine hydrate, and the concentration of the reducing agent is 10-25%; the neutralizing agent is one or more aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and potassium carbonate, and the concentration of the neutralizing agent is 10-25 wt.%.
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