CN105330520B - A kind of method for synthesizing double (2,3 dibromopropyl) ethers of tetrabromobisphenol A in water phase - Google Patents
A kind of method for synthesizing double (2,3 dibromopropyl) ethers of tetrabromobisphenol A in water phase Download PDFInfo
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
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Abstract
Synthesize tetrabromobisphenol A double (2 in a kind of water phase, 3 dibromopropyls) ether method, surfactant and tetrabromo bisphenol A diene propyl ether are mixed to prepare emulsion in water phase, bromine is then added dropwise, tetrabromo bisphenol A diene propyl ether occurs addition reaction and obtains tetrabromobisphenol A double (2 with bromine, 3 dibromopropyls) ether, after reaction terminates, cooling, filtering, washing, white solid product is obtained after drying.The inventive method does not use organic solvent with water as reaction medium, overcomes existing production technology because using the problem produced by organic solvent；And double (2,3 dibromopropyl) the ether crystalline deposit processes of tetrabromobisphenol A are avoided, post processing is simple, enormously simplify existing process route, effective reduces cost；Methods described is environmentally friendly, and product color is white, quality is good, high income, process is simple, is adapted to industrial applications.Products obtained therefrom yield can reach 93.1%, and purity can reach 95.5%.
Description
Technical field
The invention belongs to organic synthesis field, it is related to a kind of method of double (2, the 3- dibromopropyl) ethers of synthesis tetrabromobisphenol A,
The method for synthesizing double (2,3- dibromopropyls) ethers of tetrabromobisphenol A in more particularly to a kind of water phase.
Background technology
Tetrabromobisphenol A (2,3- dibromopropyl) ether (eight bromo ether) is important kind in bromide fire retardant, with good heat
Stability and photostability, are widely used in polypropylene, polyethylene, Corvic.Double (the 2,3- dibromos third of tetrabromobisphenol A
Base) ether good flame retardation effect, addition is few, is one of important kind of bromide fire retardant.
Double (2,3- dibromopropyls) the existing industrial production process of ether of tetrabromobisphenol A are generally adopted with the following method：With chloroform
It is solvent, tetrabromo bisphenol A diene propyl ether and bromine carry out addition reaction.Reaction is used in sodium sulfite, NaOH after terminating
With excess bromine in simultaneously reduction reaction, eight bromo ether chloroformic solution is obtained after cooling, washing.Above-mentioned organic solution is moved to and is filled
Crystallized in the reactor of lower aliphatic alcohols, be centrifuged, dry, crushing and to obtain finished product.Above-mentioned production technology with chloroform as solvent,
Chloroform has that volatility is big, toxicity big, there are problems that to workers ' health.The chloroform and rudimentary fat used in production process
Fat alcohol need to can be reclaimed by distillation, and post-reaction treatment is complicated time-consuming and process energy consumption is big.Meanwhile, because largely using lower aliphatic
Alcohol brings potential safety hazard to the subsequent unit operation such as separation, dry.
In double (2,3- dibromopropyl) ether preparation methods of tetrabromobisphenol A of current document and patent report, chlorine is generally used
For alkane as tetrabromo bisphenol A diene propyl ether and the solvent of the addition reaction of bromine, such as dichloromethane (Sun Wei people high-purity four
Double (2,3- dibromopropyls) ether new technique for synthesizing [J] the plastic additives of bromine bisphenol-A, 2004 (4):8-10.), dichloroethanes (Wang Yan
Woods, Wang Fang, study on the synthesis [J] the sea lake salts and chemical industry of double (the 2,3- dibromos pi-allyl) ethers of Tang rising star's fire retardants tetrabromobisphenol A,
2006,34(6):9-11.), (Yang Chunchang, Tang Xian reach synthesis [J] Liaoning of efficient flame-retarding agents-eight bromo ether to carbon tetrachloride
Work, 1989 (6):29-31.), chloroform (Wang Hong, Li Gehua, double (the 2,3- dibromos third of river army bisphenol-As synthesis tetrabromobisphenol A
Base) ether technical study [J] Guangdong chemical industry, 2008,35 (8)：37-39) etc..
A kind of method of eight bromo ether for preparing heat decomposition temperature high that CN200610040547.X is related to, it is characterised in that halogen
Synthesize a kind of eight bromo ether of heat decomposition temperature high by means of emulsifying agent and heat stabilizer in hydrocarbon.The method that patent is provided does not reach
It is solvent to the effect for simplifying synthetic route and using chlorohydrocarbon.CN200810188470.X is related to a kind of catalysis tetrabromobisphenol A
Dual-allyl ether is reacted with bromine, and the process route of chloroform is reclaimed by spray atomization.This process route chloroform as solvent,
And there is a problem of that catalyst is reclaimed.
The content of the invention
Synthesize the side of double (2,3- dibromopropyls) ethers of tetrabromobisphenol A in water phase it is an object of the invention to provide one kind
Method.With water as solvent, there is addition reaction and tetrabromo be obtained in the double dilute propyl ethers of tetrabromobisphenol A and bromine to the inventive method in water phase
Double (2, the 3- dibromopropyl) ethers of bisphenol-A, overcome existing production technology because being deposited using the organic solvent produced by organic solvent
It is difficult, reclaim the problems such as energy consumption is big, potential safety hazard is big；And avoid double (2,3- dibromopropyls) the ether crystalline deposit mistakes of tetrabromobisphenol A
Journey, post processing is simple, enormously simplify existing process route, effective reduces cost；Methods described is environmentally friendly, product color
In vain, quality is good, high income, and process is simple is adapted to industrial applications.
Realize that the object of the invention is adopted the following technical scheme that：
A kind of method for synthesizing double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A in water phase, it is characterised in that：Its feature exists
In, using water as solvent, surfactant and tetrabromo bisphenol A diene propyl ether are mixed to prepare emulsion in water phase, heat up
To 40 DEG C of -55 DEG C of dropwise addition bromines, there is addition reaction, after being added dropwise to complete, 55 DEG C -75 in tetrabromo bisphenol A diene propyl ether with bromine
DEG C continue to reaction, reaction terminate after cooling, filtering, filter cake through washing, the tetrabromobisphenol A that obtains white after drying it is double (2,
3- dibromopropyls) ether.
The inventive method uses surfactant, makes reactant tetrabromo bisphenol A diene propyl ether (four bromo-ethers) dispersed
In water, and form a kind of emulsion of stabilization.Described surfactant is selected from anionic surfactant, cationic
Surfactant or nonionic surface active agent or compound.Wherein anion surfactant is preferably dodecyl
Sodium sulphate, neopelex.Cationic surfactant is preferably cetyl trimethylammonium bromide, benzalkonium chloride.
Nonionic surface active agent is preferably OPEO, polyoxyethylene 20 sorbitan trioleate, coconut grease
Fat acid diglycollic amide.
In methods described, the feed time of bromine is 4h-5h；Reaction temperature during bromine dropwise adding is 40-55 DEG C, reaction temperature
Degree need to coordinate with drop speed, and reaction temperature improves corresponding rate of addition can be accelerated, if the corresponding rate of addition of reaction temperature reduction can
To slow down.
In methods described, after the completion of bromine dropwise adding, continue to react curing more than 2h at 55 DEG C -75 DEG C.
In methods described, the ratio between amount of material of four bromo-ethers and surfactant is 1:0.03-0.10；Four bromo-ethers and bromine
The ratio between the amount of material be 1:2.05-2.25.
In methods described, the mother liquor that reaction is filtrated to get after terminating can be circulated and use.
Beneficial effects of the present invention：Compared with existing industrial process, the inventive method with water as reaction medium,
Synthesize double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A in water phase, the problems such as in the absence of solvent recovery, effective reducing energy consumption and into
This；Post processing is simple, it is to avoid eight bromo ether crystalline deposit process；Reaction mother liquor is recycled, it is to avoid sewage disposal and discharge
Problem.The present invention enormously simplify the process route of double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A, environmentally friendly, product matter
Measure, high income, and do not influence product color, process is simple is adapted to industrial applications.It is double using the inventive method production tetrabromo
Double (2, the 3- dibromopropyl) ethers of phenol A, up to 85-95%, purity is up to more than 90% for the yield of products obtained therefrom.Specifically include following
Advantage：
(1) present invention is with water as reaction medium, it is to avoid the use of chloralkane, effective reduces cost；
(2) harm of the chloralkane to operator's health, environmental protection are avoided；
(3) Distillation recovery of chloralkane and lower aliphatic alcohols is avoided, existing production technology is simplified, is substantially reduced anti-
Should be able to consume；
(4) product only needs simple filtration to dry and can obtain product, and mother liquor can be recycled, it is to avoid tetrabromobisphenol
Double (2,3- dibromopropyl) the ether crystalline deposit processes of A, enormously simplify process route；
(5) with water as reaction medium, potential potential safety hazard is greatly reduced, is suitable to industrialized production.
Below by embodiment, the present invention will be described in detail, described embodiment contribute to the understanding of the present invention and
Implement, be not construed as limiting the invention；Protection scope of the present invention is defined in the claims.
Specific embodiment
Embodiment 1
Added water in the four-neck flask equipped with constant pressure funnel, electric mixer and thermometer 70mL, four bromo-ether 9.8g,
Lauryl sodium sulfate 0.2g and cetyl trimethylammonium bromide 0.2g, stirs to obtain homogeneous emulsion.It is warming up to about 45 DEG C -50 DEG C
When start be added dropwise liquid bromine 5.6g, be added dropwise control 4h or so complete.After being added dropwise to complete, reflux condensate device is added and opens,
60 DEG C -70 DEG C are warming up to, cooling, suction filtration after reaction 2h, the mother liquor that will be obtained are put into stand-by, filter cake washing in reagent bottle, dry,
Obtain white solid, and filtrate is transferred to stand-by in reagent bottle.Product weight 13.97g, yield 94.3%, through liquid-phase chromatographic analysis
Purity is 93.9%.
Embodiment 2
Mother liquor in adding embodiment 1 in the four-neck flask equipped with constant pressure funnel, electric mixer and thermometer,
And a small amount of water to 70mL is added, and four bromo-ether 9.8g are put into, stir to obtain homogeneous emulsion.Start to be added dropwise when being warming up to about 45 DEG C -50 DEG C
Liquid bromine 5.3g, is added dropwise control and is completed in 4h or so.After being added dropwise to complete, add and open reflux condensate device, be warming up to 60 DEG C-
70 DEG C, cooling, suction filtration after reaction 2h, the mother liquor that will be obtained are put into stand-by, filter cake washing in reagent bottle, dry to obtain white solid product
Product weight 13.94g, yield 94.0% is 93.6% through liquid-phase chromatographic analysis purity.Circulate in this approach, lived without surface
Property agent in the case of, when Recycling Mother Solution is to the 6th time, yield is 90.6%, liquid-phase chromatographic analysis purity be 89.3%.
Embodiment 3
Added water in the four-neck flask equipped with constant pressure funnel, electric mixer and thermometer 70mL, four bromo-ether 9.8g,
Benzalkonium chloride 0.2g and cocoanut fatty acid diethanolamide 0.2g, stirs to obtain homogeneous emulsion.Opened when being warming up to about 50 DEG C -55 DEG C
Begin that liquid bromine 5.6g is added dropwise, control is added dropwise and is completed in 5h.After being added dropwise to complete, reflux condensate device is added and opened, be warming up to 60
DEG C -65 DEG C, cooling, suction filtration after reaction 2h, the mother liquor that will be obtained is put into stand-by in reagent bottle, and filter cake washing, drying obtains white
Solid 13.79g, gross production rate 93.1% is 95.5% through liquid-phase chromatographic analysis purity.
Embodiment 4
Add water 70mL, four bromo-ether 9.8g in the four-neck flask equipped with constant pressure funnel, electric mixer and thermometer
And lauryl sodium sulfate 0.4g, stir to obtain homogeneous emulsion.Start that liquid bromine 5.6g, drop is added dropwise when being warming up to about 40 DEG C -45 DEG C
Plus control is completed in 5h or so.After being added dropwise to complete, reflux condensate device is added and opened, be warming up to 60 DEG C -70 DEG C, after reaction 2h
Cooling, suction filtration, the mother liquor that will be obtained are put into stand-by, filter cake washing in reagent bottle, dry, and obtain white solid 13.02g, total yield
Rate 87.9%, through liquid-phase chromatographic analysis purity 90.3%.
Embodiment 5
Added water in the four-neck flask equipped with constant pressure funnel, electric mixer and thermometer 70mL, four bromo-ether 9.8g,
Lauryl sodium sulfate 0.3g and cocoanut fatty acid diethanolamide 0.1g, stirs to obtain homogeneous emulsion.It is warming up to about 50 DEG C -55
DEG C when start be added dropwise liquid bromine 5.6g, be added dropwise control 4h complete.After being added dropwise to complete, reflux condensate device is added and opened, rise
To 60 DEG C -65 DEG C, cooling, suction filtration after reaction 2h, the mother liquor that will be obtained are put into stand-by, filter cake washing in reagent bottle to temperature, dry, and obtain
To white solid 13.89g, gross production rate 93.8% is 94.3% through liquid-phase chromatographic analysis purity.
Claims (10)
1. a kind of method for synthesizing double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A in water phase, it is characterised in that using water as molten
Agent, emulsion is mixed to prepare by surfactant and tetrabromo bisphenol A diene propyl ether in water phase, is warming up to 40 DEG C of -55 DEG C of dropwise additions
There is addition reaction in bromine, tetrabromo bisphenol A diene propyl ether, after being added dropwise to complete, 55 DEG C -75 DEG C continue to reaction with bromine,
Reaction is cooled down after terminating, filtering, and filter cake obtains double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A through washing after drying.
2. the method for synthesizing double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A in water phase according to claim 1, its feature exists
In：Described surfactant is selected from anionic surfactant, cationic surface active agent or non-ionic surface and lives
Property agent, or two of which surfactant compound.
3. the method for synthesizing double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A in water phase according to claim 2, its feature exists
In：Described anion surfactant is lauryl sodium sulfate or neopelex.
4. the method for synthesizing double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A in water phase according to claim 2, its feature exists
In：Described cationic surfactant is cetyl trimethylammonium bromide or benzalkonium chloride.
5. the method for synthesizing double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A in water phase according to claim 2, its feature exists
In：Described nonionic surface active agent is OPEO, polyoxyethylene 20 sorbitan trioleate or coconut palm
Seed oil fatty diglycollic amide.
6. the method for synthesizing double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A in water phase according to claim 1, its feature exists
In：The ratio between described tetrabromo bisphenol A diene propyl ether and the amount of material of surfactant are 1:0.03-0.10.
7. the method for synthesizing double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A in water phase according to claim 1, its feature exists
In：The ratio between described tetrabromo bisphenol A diene propyl ether and the amount of material of bromine are 1:2.05-2.25.
8. the method for synthesizing double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A in water phase according to claim 1, its feature exists
In：In described method, the time for adding of bromine is 4-5h.
9. the method for synthesizing double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A in water phase according to claim 1, its feature exists
In：In described method, the maintenance reaction time after the completion of bromine dropwise adding is more than 2h.
10. the method for synthesizing double (2, the 3- dibromopropyl) ethers of tetrabromobisphenol A in water phase according to claim 1, its feature
It is：In methods described, the Recycling Mother Solution that reaction terminates to be filtrated to get is used.
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| CN1004626B (en) * | 1986-11-13 | 1989-06-28 | 山东省农药氯碱工业协会 | Process for proparation of tetrabromo-bisphenol-a bis (2,3-dibromo-propyl ether) |
| JP2784882B2 (en) * | 1994-04-28 | 1998-08-06 | 第一工業製薬株式会社 | Process for producing powdery high melting point 2,2-bis [4 '-(2 ", 3" -dibromopropoxy) -3', 5'-dibromophenyl] propane |
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