CN101343246B - Method of preparing bromobisphenol S diene propyl ether - Google Patents
Method of preparing bromobisphenol S diene propyl ether Download PDFInfo
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- CN101343246B CN101343246B CN2008101401649A CN200810140164A CN101343246B CN 101343246 B CN101343246 B CN 101343246B CN 2008101401649 A CN2008101401649 A CN 2008101401649A CN 200810140164 A CN200810140164 A CN 200810140164A CN 101343246 B CN101343246 B CN 101343246B
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- bisphenol
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Abstract
The invention discloses a preparation method of tetrabromobisphenol S diallyl oxide, which is characterized in that: tetrabromobisphenol S is reacted with chloropropene at a temperature of between 40 and 100 DEG C to generate the tetrabromobisphenol S diallyl oxide in an isopropyl alcohol-water-chlorobenzene mixed solvent in the presence of sodium hydroxide and tetraethyl ammonium bromide, wherein, the function of sodium hydroxide is to transform tetrabromobisphenol S into sodium salt, and the tetraethyl ammonium bromide is a catalyst. After the complete reaction, the tetrabromobisphenol S diallyl oxide is obtained through centrifugal separation, and the mother liquor can be used repeatedly. The method has advantages of good purity of prepared products, low energy consumption and high production efficiency.
Description
Technical field:
The present invention relates to a kind of method of manufacture of ignition dope, specifically is a kind of method of manufacture of tetrabromo-bisphenol s dual-allyl ether.
Background technology:
The tetrabromo-bisphenol s dual-allyl ether is a kind of BACN, also is the critical materials of synthetic fire retardant tetrabromo-bisphenol s two (2,3-dibromopropyl ether).Tetrabromo-bisphenol s two (2,3-dibromopropyl ether) is a kind of good additive flame retardant, has excellent heat resistance, photostabilization and scale resistance.Be widely used in Vestolen PP 7052, ABS and the polystyrene plastic.
Synthetic tetrabromo-bisphenol s dual-allyl ether is to be raw material with the tetrabromo-bisphenol s, and in the presence of sodium hydroxide, tetrabromo-bisphenol s and chlorallylene hydrocarbon generation substitution reaction generate the tetrabromo-bisphenol s dual-allyl ether.
Synthetic tetrabromo-bisphenol s dual-allyl ether uses isopropanol water solution to make solvent usually, uses Sodium Bromide to make catalyzer.Because two etherate tetrabromo-bisphenol s dual-allyl ethers and single etherate tetrabromo-bisphenol s mono allyl ether solubleness in this solvent are all less; Two etherates and single etherate coat serious mutually; Product purity is low, and fusing point is low, and the tetrabromo-bisphenol s mono allyl ether that is coated is difficult to react with propenyl chloride; Reaction time consumption is long, and the propenyl chloride hydrolysis is serious.
The complex phase solvent that synthetic tetrabromo-bisphenol s dual-allyl ether also can use vinyl trichloride or chlorobenzene and water to form uses quaternary amine Huo quaternary alkylphosphonium salt to make catalyzer.In the reaction process, the reaction of the tetrabromo-bisphenol s sodium salt of catalyzer and aqueous phase, formation can be dissolved in the tetrabromo-bisphenol s quaternary amine Huo quaternary alkylphosphonium salt of organic phase, and tetrabromo-bisphenol s is carried into organic phase and propenyl chloride reaction generation etherificate product.Because tetrabromo-bisphenol s dual-allyl ether and single etherate tetrabromo-bisphenol s mono allyl ether solubleness in vinyl trichloride or chlorobenzene are big, in the reaction process, there is not deposition coating problem, the product purity that obtains is high, and quality is good.But this technology all needs solvent steamed at every turn and can obtain product, and energy consumption is big, and solvent loss is big, and is seriously polluted, and in today of energy shortage and emphasical green production, this difficult technique is to use.
Summary of the invention:
Technical problem to be solved by this invention is the deficiency that exists to prior art; A kind of method of manufacture of new tetrabromo-bisphenol s dual-allyl ether is proposed; Use this method can simplify and steady operation conditions, help the recycling of solvent again, can effectively cut down the consumption of energy; Save production cost, increase economic efficiency.
Technical problem to be solved by this invention is to realize through following technical scheme.The present invention is a kind of method of manufacture of tetrabromo-bisphenol s dual-allyl ether, it is characterized in that:
(1) in Virahol-water-chlorobenzene mixed solvent; In the presence of sodium hydroxide and tetraethylammonium bromide, tetrabromo-bisphenol s and propenyl chloride react under certain temperature and generated the tetrabromo-bisphenol s dual-allyl ether in 8-10 hour, wherein; The effect of sodium hydroxide is to convert tetrabromo-bisphenol s to sodium salt; Usage quantity is 2.1:1-2.6:1 with the ratio of the amount of substance of used tetrabromo-bisphenol s, and tetraethylammonium bromide is a catalyzer, and usage quantity is the 1-3% of used tetrabromo-bisphenol s weight.Propenyl chloride is 2.1:1-3.0:1 with the ratio of the amount of substance of tetrabromo-bisphenol s.Virahol-water-chlorobenzene mixed solvent total amount is 1:1-5:1 with the ratio of tetrabromo-bisphenol s weight.After reacting completely, spinning obtains product tetrabromo-bisphenol s dual-allyl ether, and mother liquor repeats to apply mechanically.
(2) suitable reaction temperature is 40～100 ℃, is preferably in 50-80 ℃.
(3) in Virahol-water-chlorobenzene mixing solutions, the suitable Virahol and the ratio of water are 75:25-25:75,60:40-40:60 preferably, and the proper ratio of isopropanol water solution and chlorobenzene is 97:3-60:40, preferably 96:4-80:20.
The present invention finds that in Virahol-water-chlorobenzene double solvents, the solubleness of tetrabromo-bisphenol s mono allyl ether is bigger; The solubleness of tetrabromo-bisphenol s dual-allyl ether is less, uses this double solvents to make solvent, and the reaction times is short; Product purity is high, and fusing point is high, and product is separated out with precipitation forms; Need not to steam solvent, can obtain high-quality product, process energy consumption reduces significantly.
The present invention finds that also in this double solvents, it is very effective using tetraethylammonium bromide to make catalyzer.
The present invention finds that also in this double solvents, suitable reaction temperature is 40～100 ℃, is preferably in 50-80 ℃.Temperature is low, and speed of response is slow; Temperature is high, the product jaundice.
Compared with prior art, adopt and produce following positively effect after the technical scheme of the present invention: the manufacturing cost of (1) tetrabromo-bisphenol s dual-allyl ether obviously reduces.(2) both simplify and stablized operational condition, guaranteed the final quality of product, helped the recycling of solvent again, practiced thrift production cost, improved economic benefit.(3) reduced energy consumption.(4) reduce solvent loss, reduce environmental pollution.
Embodiment:
In order to further specify the present invention, following instance is provided, the present invention is not limited to these specific embodiments.
Embodiment 1
Whisking appliance is being housed, and TM adds the 30g tetrabromo-bisphenol s in the 500ml four-hole bottle of prolong, 40ml Virahol, 60ml water; The 5ml chlorobenzene, 4.5g sodium hydroxide, the 0.5g tetraethylammonium bromide, at the pears type addition funnel 9g propenyl chloride of packing into, heating makes solution be warmed up to 80 ℃; Drip chloro propylene, in the process of reaction, keeping reaction solution is alkalescence, if pH value less than 8, can suitably add NaOH; Insulation reaction 10 hours, cooling obtains white crystal, spinning; Oven dry obtains product tetrabromo-bisphenol s dual-allyl ether, 183 ℃ of fusing points, yield 95%.
Embodiment 2
Whisking appliance is being housed, and TM adds the 60ml Virahol in the 250ml there-necked flask of prolong, 30g tetrabromo-bisphenol s, 40ml water; 4.5g NaOH stirs and makes its dissolving, adds the 0.5g tetraethylammonium bromide then, the 20ml chlorobenzene, and 9g chlorine third is rare; Be heated to 65 ℃, insulation reaction 9 hours, cooling obtains white crystal, spinning; Oven dry obtains product tetrabromo-bisphenol s dual-allyl ether, 184 ℃ of fusing points, yield 92%.
Embodiment 3
Whisking appliance is being housed, and TM adds the 30g tetrabromo-bisphenol s in the 500ml four-hole bottle of prolong, 25ml Virahol, 30ml water; The 4ml chlorobenzene, 5g sodium hydroxide, the 1g tetraethylammonium bromide, at the pears type addition funnel 10g propenyl chloride of packing into, heating makes solution be warmed up to 70 ℃; Drip chloro propylene, in the process of reaction, keeping reaction solution is alkalescence, if pH value less than 8, can suitably add NaOH; Insulation reaction 8 hours, cooling obtains white crystal, spinning; Oven dry obtains product tetrabromo-bisphenol s dual-allyl ether, 184 ℃ of fusing points, yield 94%.
Claims (1)
1. method of preparing bromobisphenol S diene propyl ether; It is characterized in that: in Virahol-water-chlorobenzene mixed solvent; In the presence of sodium hydroxide and tetraethylammonium bromide, tetrabromo-bisphenol s and propenyl chloride react under 50-80 ℃ of temperature and generated the tetrabromo-bisphenol s dual-allyl ether in 8-10 hour, wherein; Tetraethylammonium bromide is a catalyzer, and usage quantity is the 1-3% of used tetrabromo-bisphenol s weight; The usage quantity of sodium hydroxide is 2.1 with the ratio of the amount of substance of used tetrabromo-bisphenol s: 1-2.6: 1; Propenyl chloride is 2.1 with the ratio of the amount of substance of tetrabromo-bisphenol s: 1-3.0: 1; Virahol-water-chlorobenzene mixed solvent total amount is 1 with the ratio of tetrabromo-bisphenol s weight: 1-5: 1; After reacting completely, spinning obtains tetrabromo-bisphenol s diallyl ether product, and mother liquor repeats to apply mechanically; In Virahol-water-chlorobenzene mixed solvent, the ratio of Virahol and water is 60: 40-40: 60, and the ratio of isopropanol water solution and chlorobenzene is 96: 4-80: 20.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008101401649A CN101343246B (en) | 2008-08-18 | 2008-08-18 | Method of preparing bromobisphenol S diene propyl ether |
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| CN2008101401649A CN101343246B (en) | 2008-08-18 | 2008-08-18 | Method of preparing bromobisphenol S diene propyl ether |
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| CN101343246A CN101343246A (en) | 2009-01-14 |
| CN101343246B true CN101343246B (en) | 2012-04-18 |
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| CN115124875B (en) * | 2022-05-29 | 2023-04-21 | 北京化工大学 | Self-cleaning multi-quaternary phosphonium cation antibacterial coating and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847223A (en) * | 2005-04-04 | 2006-10-18 | 孔庆池 | Production process of tetrabromobispheno S bis (2,3-dibromopropyl) ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847223A (en) * | 2005-04-04 | 2006-10-18 | 孔庆池 | Production process of tetrabromobispheno S bis (2,3-dibromopropyl) ether |
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