CN105418388B - Preparation method of flame retardant 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane - Google Patents
Preparation method of flame retardant 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane Download PDFInfo
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C41/01—Preparation of ethers
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Abstract
The invention relates to a synthetic preparation method of a brominated flame retardant 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane, which takes bisphenol A, 3-halogenated methyl propylene and liquid bromine as raw materials to prepare the 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane by a two-step method; the invention avoids the three-step method of firstly preparing the bisphenol A into the tetrabromobisphenol A to synthesize the 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane, thereby reducing the reaction steps and the synthesis cost, and simultaneously reducing the waste water yield in the synthesis process because the two-time bromination is reduced to the one-time bromination.
Description
Technical Field
The invention relates to a synthetic preparation method of a brominated flame retardant 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane, belonging to the technical field of preparation of brominated flame retardants by using a chemical synthesis method.
Background
2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane is a novel brominated flame retardant developed in recent years, and the main application of the brominated flame retardant is to replace application of hexabromocyclododecane in flame-retardant expanded polystyrene; at present, domestic patent applications for the preparation process of 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane have been published in CN103193605B and CN 16990032, and the preparation processes adopted by the patent applications can be summarized as follows: 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane is prepared by firstly generating an intermediate 2, 2-bis [ (3, 5-dibromo-4-methallyloxy) phenyl ] propane through an elimination reaction between tetrabromobisphenol A and 3-halogenated methyl propylene and then brominating the intermediate 2, 2-bis [ (3, 5-dibromo-4-methallyloxy) phenyl ] propane by using liquid bromine.
Patents for the preparation of 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropoxy) phenyl ] propane have been reported all using tetrabromobisphenol a as a main raw material, which is usually prepared by bromination of bisphenol a, so that if calculated from bisphenol a as a raw material, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropoxy) phenyl ] propane is prepared through three chemical reactions to obtain the target product.
Disclosure of Invention
The invention prepares 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane by a two-step method, adopts bisphenol A and 3-halogenated methyl propylene as raw materials in the first step, firstly prepares 2, 2-bis [4- (2-methallyloxy) phenyl ] propane by bisphenol A and 3-halogenated methyl propylene, and adds liquid bromine in the second step to obtain a 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane product by addition reaction and substitution reaction.
The reaction equation for the two-step preparation of 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane is as follows:
the used raw materials are as follows: 2, 2-di (4-hydroxyphenyl) propane, 3-chloro-methyl propylene, 3-bromo-methyl propylene, organic solvent including chlorobenzene, dichloroethane, dimeric methane, carbon tetrachloride, chloroform, liquid bromine, sodium sulfite and sodium hydroxide, and catalyst including aluminum trichloride, antimony trichloride and iron powder.
The invention prepares 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane by a two-step method, and comprises the following steps: dissolving bisphenol A in an aqueous solution of sodium hydroxide, wherein the molar ratio of the bisphenol A to the sodium hydroxide is 1: 2-3, controlling the temperature of the system between-5 ℃ and 30 ℃, gradually adding one of 3-chloromethylpropene or 3-bromomethylpropene under stirring, wherein the molar ratio of the 3-chloromethylpropene or the 3-bromomethylpropene to the bisphenol A is 2.0-2.2: 1, reacting for 1-6 hours under stirring, separating an aqueous phase to obtain an organic phase 2, 2-bis [4- (2-methallyloxy) phenyl ] propane, continuously washing with water to be neutral, and separating the aqueous phase.
The second step is that: dissolving 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane in an organic solvent, wherein the organic solvent is one of chlorobenzene, dichloromethane, dichloroethane, carbon tetrachloride and chloroform, controlling the system temperature to be between 10 ℃ below zero and 30 ℃, dropwise adding liquid bromine, the molar ratio of the liquid bromine to the 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane is 2-2.5: 1, after dropwise adding, adding one of aluminum trichloride, antimony trichloride or iron powder serving as a catalyst into the reaction system, the addition amount of the liquid bromine is 1% -5% of the mass of the 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane, controlling the system temperature to be between 10 ℃ below zero and 30 ℃, and continuously dropwise adding the liquid bromine, and the molar ratio of the liquid bromine to the 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane is 4 ℃, (2-methyl allyloxy) phenyl ] propane -5: 1, absorbing hydrogen bromide released in the reaction process by a recovery device to obtain hydrobromic acid, dropwise adding liquid bromine to react, adding sodium sulfite to reduce excessive liquid bromine into hydrogen bromide, adding sodium hydroxide to adjust a reaction system to be neutral, fully washing with water, separating water, and adding methanol or ethanol to an organic phase to separate out a product 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane.
The method provided by the invention directly adopts bisphenol A, 3-halogenated methyl propylene and liquid bromine as main raw materials to prepare 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane, so that the 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane is synthesized by a three-step method of firstly preparing tetrabromobisphenol A from bisphenol A, the reaction steps are reduced, and the synthesis cost is reduced; meanwhile, when the bisphenol A is taken as a starting point to prepare the 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane, the yield of wastewater in the synthesis process is reduced and the total amount of wastewater required to be treated in the synthesis process is reduced because two brominations are reduced to one bromination.
The specific implementation mode is as follows:
example 1 bisphenol a 0.5 mole was dissolved in an aqueous solution of sodium hydroxide 1.1 mole, and then 3-chloromethylpropene 1.1 mole was gradually added while stirring at a temperature of 20 to 30 c, the reaction was carried out for 5 hours while stirring, the aqueous phase was separated to obtain 2, 2-bis [4- (2-methylalyloxy) phenyl ] propane as an organic phase, the organic phase was further washed with water to neutrality, the aqueous phase was separated, and the yield of the product after drying was 97.3%.
Dissolving 0.5 mole of bis [ (methallyloxy) phenyl ] propane in dichloroethane, controlling the system temperature between-10 ℃ and 0 ℃, dropwise adding 1.05 mole of liquid bromine, after the dropwise adding is finished, adding 3.4g of catalyst aluminum trichloride into the reaction system, controlling the system temperature between-10 ℃ and 0 ℃, continuously dropwise adding 2 moles of liquid bromine, absorbing hydrogen bromide released in the reaction process by a recovery device to obtain hydrobromic acid, after the liquid bromine dropwise adding reaction is finished, adding sodium sulfite, reducing excessive liquid bromine into hydrogen bromide, adding sodium hydroxide to adjust the reaction system to be neutral, fully washing with water and separating water, adding methanol into an organic phase, separating out a target product 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane, the yield of the dried product is 98.5 percent.
Example 2
Dissolving 0.5 mol of bisphenol A in 1.1 mol of aqueous solution of sodium hydroxide, controlling the temperature of the system between 20 ℃ and 30 ℃, gradually adding 1.1 mol of 3-bromomethyl propylene under the stirring condition, stirring for 5 hours for reaction, separating an aqueous phase to obtain an organic phase of 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane, fully washing the organic phase to be neutral, separating the aqueous phase, and drying to obtain the product with the yield of 97.5%.
Dissolving 0.5 mole of 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane in dichloroethane, controlling the system temperature between-10 ℃ and 0 ℃, dropwise adding 1.1 mole of liquid bromine, after the dropwise addition is finished, adding 3.5g of catalyst antimony trichloride into the reaction system, controlling the system temperature between-10 ℃ and 0 ℃, continuously dropwise adding 2 moles of liquid bromine, absorbing the hydrogen bromide released in the reaction process by a recovery device to obtain hydrobromic acid, after the liquid bromine dropwise addition reaction is finished, adding sodium sulfite, reducing the excessive liquid bromine into hydrogen bromide, adding sodium hydroxide to adjust the reaction system to be neutral, fully washing with water and separating water, adding ethanol into an organic phase, separating out a target product 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane, the yield of the dried product is 98.3 percent.
Example 3
Dissolving 0.5 mol of bisphenol A in 1.2 mol of aqueous solution of sodium hydroxide, controlling the temperature of the system between 20 ℃ and 30 ℃, gradually adding 1.2 mol of 3-chloro-methyl-propylene under the stirring condition, stirring for 5 hours for reaction, separating an aqueous phase to obtain an organic phase of 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane, fully washing the organic phase to be neutral, separating the aqueous phase, and drying to obtain the product with the yield of 96%.
Dissolving 0.5 mole of 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane in dichloroethane, controlling the system temperature between-10 ℃ and 0 ℃, dropwise adding 1.05 mole of liquid bromine, after the dropwise adding is finished, adding 5.3g of catalyst iron powder into the reaction system, controlling the system temperature between-10 ℃ and 0 ℃, continuously dropwise adding 2.1 mole of liquid bromine, absorbing the hydrogen bromide released in the reaction process by a recovery device to obtain hydrobromic acid, after the dropwise adding reaction of the liquid bromine is finished, adding sodium sulfite, reducing the excessive liquid bromine into hydrogen bromide, adding sodium hydroxide to adjust the reaction system to be neutral, fully washing with water and separating water, adding ethanol into an organic phase, and separating out a target product 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane, the yield of the dried product is 97.2%.
Example 4
Dissolving 0.5 mol of bisphenol A in 1.5 mol of aqueous solution of sodium hydroxide, controlling the temperature of the system between 20 ℃ and 30 ℃, gradually adding 1.05 mol of 3-chloro-methyl-propylene under stirring, stirring for reacting for 6 hours, separating an aqueous phase to obtain an organic phase of 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane, continuously washing with water to be neutral, separating the aqueous phase, and drying to obtain a product yield of 98.5%.
Dissolving 0.5 mole of 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane in chlorobenzene, controlling the system temperature between 10 ℃ and 20 ℃, dropwise adding 1.1 mole of liquid bromine, after the dropwise addition is finished, adding 5g of catalyst iron powder into a reaction system, controlling the system temperature between 10 ℃ and 20 ℃, continuously dropwise adding 2.5 moles of liquid bromine, absorbing hydrogen bromide released in the reaction process by a recovery device to obtain hydrobromic acid, after the dropwise addition reaction of the liquid bromine is finished, adding sodium sulfite, reducing the excessive liquid bromine into hydrogen bromide, adding sodium hydroxide to adjust the reaction system to be neutral, fully washing with water and separating water, adding methanol into an organic phase, separating out a target product 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methyl propoxy) phenyl ] propane, the yield of the product after drying is 99.0%.
Example 5
Dissolving 0.5 mol of bisphenol A in 1.3 mol of aqueous solution of sodium hydroxide, controlling the temperature of the system between 10 ℃ and 20 ℃, gradually adding 1 mol of 3-bromomethyl propylene under the condition of stirring, stirring for 5 hours for reaction, separating an aqueous phase to obtain an organic phase of 2, 2-bis [4- (2-methallyloxy) phenyl ] propane, continuously washing the organic phase to be neutral, separating the aqueous phase, and drying to obtain the product with the yield of 97.8%.
Dissolving 0.5 mole of 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane in dichloromethane, controlling the temperature of the system between 0 ℃ and 10 ℃, dropwise adding 1 mole of liquid bromine, after the dropwise addition is finished, adding 7g of catalyst antimony trichloride into the reaction system, controlling the temperature of the system between 0 ℃ and 10 ℃, continuously dropwise adding 2.3 moles of liquid bromine, absorbing hydrogen bromide released in the reaction process by a recovery device to obtain hydrobromic acid, after the dropwise addition reaction of the liquid bromine is finished, adding sodium sulfite, reducing excessive liquid bromine into hydrogen bromide, adding sodium hydroxide to adjust the reaction system to be neutral, fully washing with water and separating water, adding ethanol into an organic phase, separating out a target product 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane, the yield of the dried product is 98.6 percent.
Claims (3)
1. A method for producing a flame retardant, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane, characterized in that 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane is produced by a two-step process, the first step is a process for producing 2, 2-bis [4- (2-methylallyloxy) phenyl ] propane by reacting bisphenol A with 3-halogenomethylpropene using bisphenol A and 3-halogenomethylpropene as raw materials, and the second step is a process for producing: dissolving 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane in an organic solvent, wherein the organic solvent is one of chlorobenzene, dichloromethane, dichloroethane, carbon tetrachloride and chloroform, the system temperature is controlled to be between 10 ℃ below zero and 30 ℃, liquid bromine is dropwise added, the molar ratio of the liquid bromine to the 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane is 2-2.5: 1, after dropwise addition is finished, one of aluminum trichloride, antimony trichloride or iron powder serving as a catalyst is added into a reaction system, the addition amount is 1-5% of the mass of the 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane, the system temperature is controlled to be between 10 ℃ below zero and 30 ℃, the liquid bromine is continuously dropwise added, the molar ratio of the liquid bromine to the 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane is 4-5: 1, absorbing hydrogen bromide released in the reaction process by a recovery device to obtain hydrobromic acid, adding sodium sulfite after the dropwise addition reaction of liquid bromine is completed, reducing excessive liquid bromine into hydrogen bromide, adding sodium hydroxide to adjust a reaction system to be neutral, fully washing with water, separating water, and adding methanol or ethanol into an organic phase to separate out a product 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane.
2. A process for producing a flame retardant, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane, characterized by a two-step production route of 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane:
(2) the method comprises the following steps: dissolving 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane in an organic solvent, wherein the organic solvent is one of chlorobenzene, dichloromethane, dichloroethane, carbon tetrachloride and chloroform, the system temperature is controlled to be between 10 ℃ below zero and 30 ℃, liquid bromine is dropwise added, the molar ratio of the liquid bromine to the 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane is 2-2.5: 1, after dropwise addition is finished, one of aluminum trichloride, antimony trichloride or iron powder serving as a catalyst is added into a reaction system, the addition amount is 1-5% of the mass of the 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane, the system temperature is controlled to be between 10 ℃ below zero and 30 ℃, the liquid bromine is continuously dropwise added, the molar ratio of the liquid bromine to the 2, 2-bis [4- (2-methyl allyloxy) phenyl ] propane is 4-5: 1, absorbing hydrogen bromide released in the reaction process by a recovery device to obtain hydrobromic acid, adding sodium sulfite after the dropwise addition reaction of liquid bromine is completed, reducing excessive liquid bromine into hydrogen bromide, adding sodium hydroxide to adjust a reaction system to be neutral, fully washing with water, separating water, and adding methanol or ethanol into an organic phase to separate out a product 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane.
3. The method for producing 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane flame retardant according to claim 1, characterized by the first step of the two-step process: dissolving bisphenol A in an aqueous solution of sodium hydroxide, wherein the molar ratio of bisphenol A to sodium hydroxide is 1: 2-3, then controlling the temperature of the system between-5 ℃ and 30 ℃, gradually adding one of 3-chloromethylpropene or 3-bromomethylpropene under stirring, wherein the molar ratio of 3-chloromethylpropene or 3-bromomethylpropene to bisphenol A is 2.0-2.2: 1, stirring for reacting for 1-6 hours, separating an aqueous phase, obtaining an organic phase of 2, 2-bis [4- (2-methallyloxy) phenyl ] propane, continuously washing with water to be neutral, and separating the aqueous phase.
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| CN110483257B (en) * | 2019-09-17 | 2020-06-23 | 江苏欣舟化工科技有限公司 | Synthesis method of 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane |
| CN110981767B (en) * | 2019-12-16 | 2021-10-26 | 山东旭锐新材有限公司 | Preparation method of octabromo S ether flame retardant |
| CN115819194A (en) * | 2023-01-17 | 2023-03-21 | 山东润科化工股份有限公司 | Synthesis method of 1,3, 5-tribromo-2- (2, 3-dibromo-2-methylpropyloxy) benzene |
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