CN100432036C - Environment-friendly method for synthesizing tetrabromo bisphenol A diene propyl ether - Google Patents
Environment-friendly method for synthesizing tetrabromo bisphenol A diene propyl ether Download PDFInfo
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- CN100432036C CN100432036C CNB2006100405465A CN200610040546A CN100432036C CN 100432036 C CN100432036 C CN 100432036C CN B2006100405465 A CNB2006100405465 A CN B2006100405465A CN 200610040546 A CN200610040546 A CN 200610040546A CN 100432036 C CN100432036 C CN 100432036C
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- tetrabromo
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Abstract
The present invention relates to a method for synthesizing tetrabromo bisphenol A allyl ether in friendly environment. In the method, tetrabromo bisphenol A is taken as a raw material; phase transfer catalysts are added in a NaOH water solution; 3-chloropropene is dripped for carrying out reactions for generating Tetrabromo bisphenol A allyl ether which is made into finished products by separation, washing and drying; and only water is added in the reactions as a reaction solvent without any other organic solvent. On the technology, the method reduces the post processing of organic solvents, is friendly with environment, is easy of industrialized production, can cause reactions to be heated to high temperature and greatly accelerates the reaction speed.
Description
Technical field
The present invention relates to a kind of chemical synthesis process, be specifically related to a kind of method of environmental friendliness synthesizing tetrabromo bisphenol A diene propyl ether.
Background technology
Tetrabromo bisphenol A diene propyl ether can add tetrabromo-bisphenol and chlorallylene in lower aliphatic alcohols (referring to contain the alkanol of 1 to 3 carbon atom) carries out etherification reaction and obtains, but this method needs reclaim and rectifying solvent, has raffinate, slag to discharge.After reaction finishes simultaneously, there are a large amount of organic solvent uncontrollable discharges to bring environmental pollution when centrifugal.Owing to precipitation does not thoroughly bring by product, need further to separate, make the subsequent technique complexity.Particularly importantly carrying out tetrabromo bisphenol A diene propyl ether when synthetic with lower aliphatic alcohols as solvent, each operation operation has brought great potential safety hazard in the process because the existence of lower aliphatic alcohols is given.
Summary of the invention
The object of the invention is to improve the shortcoming of prior art and provides a kind of under the condition of the production unit that need not change existing tetrabromo bisphenol A diene propyl ether, cut down the solvent distillation recovery process in process of production, thoroughly eradicate potential safety hazard, environmental pollution, obtain the preparation method of steady quality, tetrabromo bisphenol A diene propyl ether that yield is high simultaneously because of using lower aliphatic alcohols to produce.
Purpose of the present invention can reach by following measure:
With the tetrabromo-bisphenol is raw material, in the NaOH aqueous solution, add quaternary ammonium salt or quaternary phosphine salt phase-transfer catalyst, dripping chlorallylene reacts, generate tetrabromo bisphenol A diene propyl ether, through centrifugal, separation, washing, the dry finished product that gets, add entry in the reaction and make reaction solvent again, do not add any other organic solvent.
Below content of the present invention is described in detail:
This phenolic hydroxyl group O-alkylated reaction is a nucleophilic substitution reaction, inorganic is the replacement bisphenol sodium salt of alkali mutually, organic phase is a propenyl chloride, the negative ion that tetrabromo-bisphenol generates under the alkali effect is as a nucleophilic reagent, brought in the organic phase by phase-transfer catalyst and to carry out nucleophilic substitution reaction with chlorallylene, the inorganic salt that the reaction back generates take water to by phase-transfer catalyst again.Like this by phase-transfer catalyst constantly transportation to and fro between the two phase reaction thing, reactant by a phase transition to another phase, make to be in the biphase reactant originally respectively and can be in contact with one another continually,, finally obtain tetrabromo bisphenol A diene propyl ether until reacting completely.
Its reaction formula is as follows:
Catalysis Principles is as shown in the formula (annotate: phase-transfer catalyst is with Q
+X
-Representative):
Water:
Oil phase:
Q
+X
-Water soluble, and Q
+Have lipophilicity, can enter organic phase, because positive and negative electric charge attracts Q mutually
+Can
Take to the organic phase by two-phase interface from water, because of
Expose, chemical property is active, and it and propenyl chloride nucleophilic substitution reaction takes place rapidly generate in organic phase
And Cl
-, Cl
-Again with Q
+In conjunction with transferring to water, so move in circles, until reacting completely.
Phase-transfer catalyst is a quaternary ammonium salt Huo phosphonium salt class, has following structure:
R wherein
1, R
2, R
3, R
4Be respectively aliphatic alkyl or aryl less than ten six carbon atoms, alkyl can be identical also can be different, quaternary ammonium salt is as phenyl triethyl ammonium chloride, tri-n-octyl methyl ammonium chloride; The phosphonium salt class is as hexadecyl tributyl phosphonium bromide, butyl phosphonium bromide, four normal-butyl bromination Phosphonium.
Among the present invention, NaOH divided for two steps added, its process is for adding tetrabromo-bisphenol, part solid NaOH in reactor, phase-transfer catalyst and water, stir and heat temperature raising, when reaching 65 ℃～95 ℃, temperature drips chlorallylene, controlled temperature is 65 ℃～75 ℃ in the dropping process, stir 2h～4h and add residue NaOH again, react 1h～2h again, after after reaction finishes excessive chlorallylene being steamed, be cooled to below 40 ℃, suction filtration separates, the filter cake deionized water wash, and filter cake is dried to constant weight and gets finished product after will washing under 80 ℃～90 ℃.
NaOH divided for two steps added, and mixture alkalescence is not high in the time of can making the leading portion reaction, can prevent tetrabromo-bisphenol generation hydrolysis, and reduces reaction effect.
Temperature of reaction of the present invention is preferably 65 ℃～75 ℃, and the chlorallylene dropping time is 1h～2h; For the first time the NaOH add-on is 85%～90% of a NaOH total amount, and chlorallylene drips the afterreaction time and is preferably 3h～5h.
The amount that each raw material of the present invention adds is counted tetrabromo-bisphenol with mole: NaOH: chlorallylene=1: 2～2.2: 2～4, NaOH and water weight ratio are 1: 3～7, and the weight ratio of tetrabromo-bisphenol and phase-transfer catalyst is 1: 0.005～0.05.
The method of this environmental friendliness synthesizing tetrabromo bisphenol A diene propyl ether, owing to make water as solvent in the reaction, therefore steps such as organic solvent recovery and rectifying on technology, have been reduced, no waste liquid, waste residue, waste gas produce, environmentally friendly, be easy to suitability for industrialized production, and owing to do not contain organic solvent, the mixture of tetrabromo-bisphenol, the NaOH aqueous solution and phase-transfer catalyst can be heated to comparatively high temps, has accelerated the speed of response of itself and chlorallylene greatly.
Embodiment
Embodiment 1:
Be equipped with and add 90g tetrabromo-bisphenol, 12gNaOH, triethyl benzyl ammonia chloride 0.38g in the 500ml reactor of return line, thermometer, agitator and pressure equilibrium dropper, add 90ml water simultaneously, heat temperature raising to 95 ℃ begins to drip the 40g3-propenyl chloride, and 1.5h dropwises.About 70 ℃ of temperature of reaction, behind the back flow reaction 3h, add 2gNOH, back flow reaction 2h again is cooled to below 40 ℃ centrifugation after steaming excessive chlorallylene, filter cake washs with deionized water, filter cake after the washing is got finished product tetrabromo bisphenol A diene propyl ether 98.68g after being dried to constant weight under 85 ℃, yield is 95.5%, and product is through liquid-phase chromatographic analysis purity 98.7%.
Embodiment 2:
Be equipped with and add 90g tetrabromo-bisphenol, 12gNaOH, hexadecyl tributyl phosphonium bromide 0.84g in the 500ml reactor of return line, thermometer, stirring and pressure equilibrium dropper, add 84ml water simultaneously, heat temperature raising to 95 ℃, begin to drip the 40g3-propenyl chloride, 1.5h dropwise, temperature of reaction maintains about 74 ℃, behind the back flow reaction 3h, adds 2gNaOH back flow reaction again.Steam excessive chlorallylene behind the 2h and be cooled to again below 40 ℃, centrifugation, filter cake washs with deionized water, and the filter cake after the washing is dried under 85 ℃ to constant weight and is got tetrabromo bisphenol A diene propyl ether 97.5g, and yield is 94.4%.Product is 98.3% through the liquid-phase chromatographic analysis temperature.
Embodiment 3:
Be equipped with and add 80g tetrabromo-bisphenol, 10.1gNaOH, four normal-butyl bromination Phosphonium 1.62g in the 500ml reactor of return line, thermometer, stirring and pressure equilibrium dropper, add 80ml water simultaneously, heat temperature raising to 95 ℃, begin to drip the 34g3-propenyl chloride, 1h dropwises, temperature of reaction maintains about 66 ℃, behind the back flow reaction 2h, adds 1.7gNaOH again behind the back flow reaction 1.5h.Steam excessive chlorallylene and be cooled to again below 40 ℃, centrifugation, filter cake washs with deionized water, and the filter cake after the washing is dried under 85 ℃ to constant weight and is got tetrabromo bisphenol A diene propyl ether 87.26g, and yield is 95.09%.Product is 97.9% through the liquid-phase chromatographic analysis temperature.
Comparative example 1:
Except that 14gNaOH once added, other were operated with embodiment 1, and washing back filter cake is at 85 ℃ of heavy products 92.8 that get of oven dry, and yield is 89.9%.Product is through liquid-phase chromatographic analysis purity 91.2%.
Comparative example 2:
Except that not with the phase-transfer catalyst, other are operated with embodiment 1, washing back filter cake 85 ℃ of oven dry to product be 63.1%, yield is 61.1%.Product is through liquid-phase chromatographic analysis, and purity is 79.3%.
Claims (1)
1, a kind of method of environmental friendliness synthesizing tetrabromo bisphenol A diene propyl ether, it is characterized in that in reactor, adding tetrabromo-bisphenol, account for 85%～90% solid NaOH of the total add-on of NaOH, water and quaternary phosphine salt phase-transfer catalyst, stir and heat temperature raising, when temperature reaches 65 ℃～95 ℃, slowly drip chlorallylene 1h～2h, behind stirring reaction 2h～4h, add residue NaOH again, react 1h～2h again, reaction distills out excessive chlorallylene after finishing, be cooled to below 40 ℃, centrifugation, the filter cake deionized water wash is dried to constant weight with the filter cake after the washing under 80 ℃～90 ℃;
Wherein the mol ratio of each raw material is tetrabromo-bisphenol: NaOH: chlorallylene=1: 2～2.2: 2～4, NaOH and water weight ratio are 1: 3～7, and the weight ratio of tetrabromo-bisphenol and phase-transfer catalyst is 1: 0.005～0.05;
Wherein the temperature of two secondary responses is 65 ℃～75 ℃;
Described quaternary phosphine salt phase-transfer catalyst is hexadecyl tributyl phosphonium bromide or four normal-butyl bromination Phosphonium.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999450B (en) * | 2007-01-08 | 2010-07-21 | 王彦林 | Preparation technology of polyhalogenated aryl allyl ether compound |
| CN102010304B (en) * | 2010-10-23 | 2013-09-25 | 中国石油大学(华东) | Preparation method of tetrabromobisphenol A diene propyl ether |
| CN102030620A (en) * | 2010-12-07 | 2011-04-27 | 尹华芳 | Method for preparing 2,2',6,6'-tetrabromobisphenol A diallyl ether |
| CN112778100A (en) * | 2021-02-02 | 2021-05-11 | 山东迈特新材料科技有限公司 | Preparation method of high-purity flame retardant methyl tetrabromoether |
| CN112979435A (en) * | 2021-02-26 | 2021-06-18 | 江苏欣舟化工科技有限公司 | Tetrabromo ether and preparation method and application thereof |
| CN114591152A (en) * | 2022-03-06 | 2022-06-07 | 潍坊裕凯化工有限公司 | Synthetic method of phenol-based alkenyl alkyl ether |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2343475A1 (en) * | 1973-08-29 | 1975-04-24 | Kalk Chemische Fabrik Gmbh | 2,2-bis(4-allyloxy-3,5-dibromophenyl)propane prepn. - from tetrabromo-bisphenol A and allyl halide in water |
| JPH05117223A (en) * | 1991-10-25 | 1993-05-14 | Mitsui Toatsu Chem Inc | Production of bis(4-allyloxy-3,5-dibromophenyl)sulfone |
| JPH1029956A (en) * | 1996-07-17 | 1998-02-03 | Teijin Chem Ltd | Production of tetrabromobisphenol derivative |
| JP2000026350A (en) * | 1998-07-09 | 2000-01-25 | Tosoh Corp | Production of 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane derivative |
-
2006
- 2006-05-23 CN CNB2006100405465A patent/CN100432036C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2343475A1 (en) * | 1973-08-29 | 1975-04-24 | Kalk Chemische Fabrik Gmbh | 2,2-bis(4-allyloxy-3,5-dibromophenyl)propane prepn. - from tetrabromo-bisphenol A and allyl halide in water |
| JPH05117223A (en) * | 1991-10-25 | 1993-05-14 | Mitsui Toatsu Chem Inc | Production of bis(4-allyloxy-3,5-dibromophenyl)sulfone |
| JPH1029956A (en) * | 1996-07-17 | 1998-02-03 | Teijin Chem Ltd | Production of tetrabromobisphenol derivative |
| JP2000026350A (en) * | 1998-07-09 | 2000-01-25 | Tosoh Corp | Production of 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane derivative |
Non-Patent Citations (4)
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| 相转移催化法合成双酚A二烯丙基醚的研究. 房强等人.四川联合大学学报（工程科学版），第vol.2卷第no.3期. 1998 |
| 相转移催化法合成双酚A二烯丙基醚的研究. 房强等人.四川联合大学学报（工程科学版），第vol.2卷第no.3期. 1998 * |
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Effective date of registration: 20170804 Address after: 222000 Jiangsu Province, Lianyungang City Lianyun District Banqiao Industrial Park, Xianghe Road No. 8 Patentee after: Lianyungang Engineering Investment Group Li Hai Chemical Co., Ltd. Address before: 222042 Jiangsu city in Lianyungang Province town of Xugou Lianyun District No. 175 hospital Patentee before: Lianyungang Sea Water Chemical Co., Ltd. |
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