CN102010304B - Preparation method of tetrabromobisphenol A diene propyl ether - Google Patents
Preparation method of tetrabromobisphenol A diene propyl ether Download PDFInfo
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- CN102010304B CN102010304B CN 201010531322 CN201010531322A CN102010304B CN 102010304 B CN102010304 B CN 102010304B CN 201010531322 CN201010531322 CN 201010531322 CN 201010531322 A CN201010531322 A CN 201010531322A CN 102010304 B CN102010304 B CN 102010304B
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- bisphenol
- tetrabromo
- propyl ether
- tetrabromobisphenol
- diene propyl
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Abstract
The invention relates to a preparation method of a flame retardant tetrabromobisphenol A diene propyl ether. The preparation method comprises the following steps of: mixing methanol with water first, and then adding sodium sulfite or hydrazine carbonate; stirring the mixture for 5 to 30 minutes, then adding tetrabromobisphenol A and sodium hydroxide, and stirring to dissolve the tetrabromobisphenol A and the sodium hydroxide; heating the mixture until the temperature is between 30 and 60 DEG C; adding chloropropene to perform heat preservation reaction for 6 to 12 hours; cooling the mixture to reduce the temperature to be between 10 and 30 DEG C; performing suction filtration; and drying a solid sample to obtain a target product namely the tetrabromobisphenol A diene propyl ether, whereinthe weight ratio of the methanol to the water to the tetrabromobisphenol A to the sodium hydroxide to the chloropropene is 10-100:10-120:50:6-12:15-20, and the weight ratio of the sodium sulfite or the hydrazine carbonate to methanol aqueous solution is 0.1:99.9 to 1:99. The tetrabromobisphenol A diene propyl ether prepared by the method is pure white in color, and can be widely used for producing white or light color products; the application range of the tetrabromobisphenol A diene propyl ether is extended; and the mother liquor can be used repeatedly to save the production cost.
Description
Technical field
The present invention relates to a kind of manufacture method of fire retardant tetrabromo bisphenol A diene propyl ether.
Background technology
Tetrabromo bisphenol A diene propyl ether is a kind of reactive flame retardant, also is the critical materials of synthetic fire retardant tetrabromo-bisphenol two (2,3-dibromopropyl ether).Tetrabromo-bisphenol two (2,3-dibromopropyl ether) is a kind of good additive flame retardant, is widely used in polypropylene, ABS and the polystyrene plastic.
Bian Guangyu (sea lake salt and chemical industry, 1994,23 (3): 35-37)), the medium people of Wang Pei (CN86107776) has proposed with ethanol and water as solvent synthesizing tetrabromo bisphenol A diene propyl ether technology, be earlier tetrabromo-bisphenol to be dissolved in the ethanol, add aqueous sodium hydroxide solution then, add propenyl chloride down at 40 ℃, be warming up to reflux temperature after interpolation is finished and make its reaction, obtain target product.The product colourity that this technology obtains is higher, the increased frequency that repeats to apply mechanically along with mother liquor particularly, and it is very yellow that product becomes.
The Wang Hong of Jiangsu Jin Hai Investment Co., Ltd (Guangdong chemical industry, 2008,35 (8): 37-39) propose earlier with straight alcohol and mother liquor mixed solution dissolving tetrabromo-bisphenol, add liquid caustic soda then, propenyl chloride, be warming up to 50-60 ℃ of reaction and obtain target product, the product colourity that the product colourity that obtains obtains when being lower than mother liquid recycle.The problem that this technology exists has two, and at first, it is more big to cause the mother liquor amount also to be come during industrial production, the distillation of having to, and energy consumption is higher, and secondly, it is darker product colourity often to occur.
Suzhou Institute of Science and Technology Wang Yan woods (salt industry and chemical industry, 2007,36 (1): 4-6) proposing the water method and produce tetrabromo bisphenol A diene propyl ether, is that tetrabromo-bisphenol is dissolved in earlier in the aqueous sodium hydroxide solution, adds the phase-transfer catalyst quaternary amine then, be warming up to 45 ℃, add propenyl chloride, back flow reaction was 6 hours after interpolation was finished, and obtained target product, this technology has a large amount of propenyl chloride hydrolysis, and the product colourity that obtains is very big.
People such as Zhang Tianlin people such as (CN101434520) proposes to use phase-transfer catalyst quaternary amine and iodide to do the catalyzer synthesizing tetrabromo bisphenol A diene propyl ether, and this method has effectively been accelerated etherification reaction, but product whiteness is not improved.
San Jing East presses the people (JP61286346) such as the refined husband of modern well of KCC that tetrabromo-bisphenol, sodium hydroxide are dissolved in acetone or the methyl-sulphoxide isopolarity solvent, produce tetrabromo bisphenol A diene propyl ether with the propenyl chloride reaction, the product fusing point that obtains has only 111-112 ℃, purity is not enough, and color is also darker.
The product ubiquity color that prior art obtains is darker, and the mother liquor utilization ratio in producing is low, its range of application and production cost have been influenced, by the synthetic tetrabromo-bisphenol two (2 of this tetrabromo bisphenol A diene propyl ether, 3-dibromopropyl ether) color jaundice is restricted because influencing plastics colourity when adding in the light plastics of white.
Summary of the invention
At the deficiency that prior art exists, the present invention proposes a kind of manufacture method of new tetrabromo bisphenol A diene propyl ether, and making the tetrabromo bisphenol A diene propyl ether product that obtains is pure white, thereby solves the dark problem of tetrabromo bisphenol A diene propyl ether color.
Technical problem to be solved by this invention is to realize by following technical scheme.
Earlier the first alcohol and water is mixed, add S-WAT or carbonic acid hydrazine then, stirred 5-30 minute, add tetrabromo-bisphenol, sodium hydroxide again, stirring makes its dissolving, heat temperature raising adds propenyl chloride, insulation reaction 6-12 hour to 30-60 ℃, cool to 10-30 ℃, suction filtration with the solid sample oven dry, obtains the target product tetrabromo bisphenol A diene propyl ether; Wherein the weight ratio of each material is methyl alcohol: water: tetrabromo-bisphenol: sodium hydroxide: propenyl chloride=10-100: 10-120: 50: 6-12: 15-20, the weight ratio of S-WAT or carbonic acid hydrazine and methanol aqueous solution is 0.1: 99.9-1: 99.
In order to improve the utilising efficiency of mother liquor, the methanol aqueous solution after first the use continues to repeat to apply mechanically as mother liquor, namely adds S-WAT or carbonic acid hydrazine in mother liquor, stir after 5-30 minute, add tetrabromo-bisphenol again, sodium hydroxide, stirring makes its dissolving, heat temperature raising adds propenyl chloride, insulation reaction 8 hours to 30-60 ℃, cool to 10-30 ℃, suction filtration with the solid sample oven dry, obtains the target product tetrabromo bisphenol A diene propyl ether; Wherein: the weight ratio of mother liquor and S-WAT or carbonic acid hydrazine is: 99.9: 0.1-99: 1, and the weight ratio of mother liquor and each material is mother liquor: tetrabromo-bisphenol: sodium hydroxide: propenyl chloride=100-200: 50: 6-12: 15-20.
Adopt and produce following positively effect after the technical scheme of the present invention: the tetrabromo bisphenol A diene propyl ether purity height that synthesize (1).(2) He Cheng tetrabromo bisphenol A diene propyl ether color is pure white, can be widely used in the production of white or light-coloured prods, has expanded its range of application, has improved economic benefit.(3) be that two (2, the 3-dibromopropyl ether) colors of the synthetic tetrabromo-bisphenol of raw material are pure white with the synthetic tetrabromo bisphenol A diene propyl ether of this technology, the quality height.(4) mother liquor can be repeatedly used, the production cost of having saved greatly.
Embodiment
In order to further specify the present invention, following examples are provided, but are not limited to these specific embodiments.
Embodiment 1: agitator is being housed, and thermometer adds 100ml methyl alcohol in the 500ml four-hole bottle of prolong, 80ml water, the 0.5g S-WAT stirred 10 minutes, add the 50g tetrabromo-bisphenol then, 8g sodium hydroxide stirs and makes its dissolving, heating makes solution be warmed up to 60 ℃, at the pears type addition funnel 17g propenyl chloride of packing into, add propenyl chloride, add finish after, insulation reaction 8 hours, be cooled to 20 ℃, obtain white crystal, suction filtration, oven dry, the product tetrabromo bisphenol A diene propyl ether that obtains, 118 ℃ of fusing points, yield 95%, colourity (AHPA, 50% dichloromethane solution) 15.
Comparison example 1: agitator is being housed, and thermometer adds the 50g tetrabromo-bisphenol in the 500ml four-hole bottle of prolong, 100ml methyl alcohol, 80ml water, 8g sodium hydroxide stirs and makes its dissolving, heating makes solution be warmed up to 60 ℃, at the pears type addition funnel 17g propenyl chloride of packing into, add propenyl chloride, add finish after, insulation reaction 8 hours, be cooled to 20 ℃, obtain crystal product, suction filtration, oven dry, the product tetrabromo bisphenol A diene propyl ether that obtains, 118 ℃ of fusing points, yield 95%, colourity (AHPA, 50% dichloromethane solution) 37.
Embodiment 2: agitator is being housed, and thermometer adds 60ml methyl alcohol in the 500ml four-hole bottle of prolong, 40ml water, the 1.0g S-WAT stirred 5 minutes, add the 50g tetrabromo-bisphenol then, 10g sodium hydroxide stirs and makes its dissolving, heating makes solution be warmed up to 40 ℃, at the pears type addition funnel 15g propenyl chloride of packing into, add propenyl chloride, add finish after, insulation reaction 6 hours, be cooled to 15 ℃, obtain white crystal, centrifugation, oven dry, the product tetrabromo bisphenol A diene propyl ether that obtains, 119 ℃ of fusing points, yield 93%, colourity (AHPA, 50% dichloromethane solution) 10.
Embodiment 3: agitator is being housed, is adding 100ml methyl alcohol in the thermometer, the 500ml four-hole bottle of prolong, 120ml water, 2.0g carbonic acid hydrazine stirred 25 minutes, add the 50g tetrabromo-bisphenol then, 12g sodium hydroxide stirs and makes its dissolving, heating makes solution be warmed up to 30 ℃, at the pears type addition funnel 20g propenyl chloride of packing into, add propenyl chloride, add finish after, insulation reaction 10 hours, be cooled to 20 ℃, obtain white crystal, centrifugation, oven dry, the product tetrabromo bisphenol A diene propyl ether that obtains, 118 ℃ of fusing points, yield 92%, colourity (AHPA, 50% dichloromethane solution) 18.
Embodiment 4: agitator is being housed, is adding 100ml example 1 mother liquor in the thermometer, the 500ml four-hole bottle of prolong, 0.5g S-WAT stirred 20 minutes, added the 50g tetrabromo-bisphenol then, 10g sodium hydroxide, stirring makes its dissolving, and heating makes solution be warmed up to 40 ℃, at the pears type addition funnel 15g propenyl chloride of packing into, add propenyl chloride, after interpolation was finished, insulation reaction 8 hours was cooled to 20 ℃, obtain white crystal, suction filtration, oven dry, the product tetrabromo bisphenol A diene propyl ether that obtains, 118 ℃ of fusing points, yield 95%, colourity (AHPA, 50% dichloromethane solution) 12.
Embodiment 5: agitator is being housed, is adding 180ml example 3 mother liquors in the thermometer, the 500ml four-hole bottle of prolong, 0.3g the carbonic acid hydrazine stirred 12 minutes, added the 50g tetrabromo-bisphenol then, 8g sodium hydroxide, stirring makes its dissolving, and heating makes solution be warmed up to 60 ℃, the 17g propenyl chloride of packing in pears type addition funnel, add propenyl chloride, after interpolation was finished, insulation reaction 8 hours was cooled to 20 ℃, obtain white crystal, suction filtration, oven dry, the product tetrabromo bisphenol A diene propyl ether that obtains, 118 ℃ of fusing points, yield 94%, colourity (AHPA, 50% dichloromethane solution): 20.
Claims (2)
1. the preparation method of a tetrabromo bisphenol A diene propyl ether is characterized in that: earlier the first alcohol and water is mixed, add S-WAT or carbonic acid hydrazine then, stirred 5-30 minute, add tetrabromo-bisphenol, sodium hydroxide again, stir and make its dissolving, heat temperature raising is to 30-60 ℃, add propenyl chloride, insulation reaction 6-12 hour, cool to 10-30 ℃ suction filtration, with the solid sample oven dry, obtain the target product tetrabromo bisphenol A diene propyl ether; Wherein the weight ratio of each material is methyl alcohol: water: tetrabromo-bisphenol: sodium hydroxide: propenyl chloride=10-100: 10-120: 50: 6-12: 15-20, the weight ratio of S-WAT or carbonic acid hydrazine and methanol aqueous solution is 0.1: 99.9-1: 99.
2. the preparation method of tetrabromo bisphenol A diene propyl ether according to claim 1, it is characterized in that: the methanol aqueous solution after first the use continues to repeat to apply mechanically as mother liquor, namely in mother liquor, add S-WAT or carbonic acid hydrazine, stir after 5-30 minute, add tetrabromo-bisphenol again, sodium hydroxide, stirring makes its dissolving, heat temperature raising adds propenyl chloride, insulation reaction 8 hours to 30-60 ℃, cool to 10-30 ℃, suction filtration with the solid sample oven dry, obtains the target product tetrabromo bisphenol A diene propyl ether; Wherein: the weight ratio of mother liquor and S-WAT or carbonic acid hydrazine is: 99.9: 0.1-99: 1, and the weight ratio of mother liquor and each material is mother liquor: tetrabromo-bisphenol: sodium hydroxide: propenyl chloride=100-200: 50: 6-12: 15-20.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4302614A (en) * | 1979-02-13 | 1981-11-24 | Riedel-De Haen Aktiengesellschaft | 2,2-Bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl]-propane process |
| CN1752063A (en) * | 2005-08-01 | 2006-03-29 | 孔庆池 | Manufacturing technology of high whiteness tetrabromo biphenol A |
| CN1850759A (en) * | 2006-05-23 | 2006-10-25 | 连云港海水化工有限公司 | Environment-friendly method for synthesizing tetrabromo bisphenol A diene propyl ether |
| CN101429101A (en) * | 2008-12-15 | 2009-05-13 | 中国石油大学(华东) | Method for producing tetrabromobisphemol A with high whiteness degree |
| CN101434519A (en) * | 2008-12-16 | 2009-05-20 | 淮海工学院 | Preparation of tetrabromobisphenol A bis(2,3-dibromopropyl)ether |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4302614A (en) * | 1979-02-13 | 1981-11-24 | Riedel-De Haen Aktiengesellschaft | 2,2-Bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl]-propane process |
| CN1752063A (en) * | 2005-08-01 | 2006-03-29 | 孔庆池 | Manufacturing technology of high whiteness tetrabromo biphenol A |
| CN1850759A (en) * | 2006-05-23 | 2006-10-25 | 连云港海水化工有限公司 | Environment-friendly method for synthesizing tetrabromo bisphenol A diene propyl ether |
| CN101429101A (en) * | 2008-12-15 | 2009-05-13 | 中国石油大学(华东) | Method for producing tetrabromobisphemol A with high whiteness degree |
| CN101434519A (en) * | 2008-12-16 | 2009-05-20 | 淮海工学院 | Preparation of tetrabromobisphenol A bis(2,3-dibromopropyl)ether |
Non-Patent Citations (2)
| Title |
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| 孙卫民.高纯四溴双酚A双(2 3-二溴丙基)醚合成新工艺.《塑料助剂》.2004 |
| 高纯四溴双酚A双(2,3-二溴丙基)醚合成新工艺;孙卫民;《塑料助剂》;20040820(第04期);第8-10页 * |
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