CN109336746A - A kind of preparation method of methyl eight bromo ether - Google Patents
A kind of preparation method of methyl eight bromo ether Download PDFInfo
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- CN109336746A CN109336746A CN201811398873.7A CN201811398873A CN109336746A CN 109336746 A CN109336746 A CN 109336746A CN 201811398873 A CN201811398873 A CN 201811398873A CN 109336746 A CN109336746 A CN 109336746A
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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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Abstract
The invention discloses a kind of preparation methods of methyl eight bromo ether, belong to the production technical field of fire retardant methyl eight bromo ether, comprising the following steps: tetrabromobisphenol A is added to the water dissolution, the molar ratio of water and tetrabromobisphenol A is 2-8:1, adjusts pH value with sodium hydroxide, the range of the pH value is 8-10, and carry out first time heat preservation, then, methylallyl chloride organic solution is added dropwise, phase transfer catalyst is added, it carries out keeping the temperature for second after completion of dropwise addition, then it is cooled to room temperature, is layered, takes organic layer；Bromating agent is added to dissolution in organic solvent and obtains bromination agent solution, above-mentioned organic layer is added after catalyst, bromination agent solution progress bromination reaction is added dropwise, third time heat preservation is carried out under conditions of temperature is 25-55 DEG C, sodium sulfite aqueous solution reaction is then added, it is washed with water after reaction, static layering takes lower organic layer to be added in the aqueous solution of emulsifier, is distilled, remove organic solvent, suction filtration obtains material, and product is prepared in drying.
Description
Technical field
The present invention relates to the production technical fields of fire retardant methyl eight bromo ether, and in particular to a kind of preparation of methyl eight bromo ether
Method.
Background technique
Methyl eight bromo ether is one of bromide fire retardant product, and it is more to can be widely applied to polyethylene, polypropylene, polystyrene etc.
Kind of polyolefin and its copolymer it is fire-retardant.Currently, the scientific research of bromide fire retardant new process is also deeply being held in countries in the world
In continuous development.Methyl eight bromo ether meets RoHS standard requirements, is as one of efficient bromide fire retardant product, production and use
The product of environmentally friendly fire retardant and bromide fire retardant upgrading, will develop into the leading production in bromide fire retardant market
Product.
Existing production technology still has some defects: using bromine for bromating agent, bromine is the smoke of high corrosion
Liquid and air pollutants, process safety is low, needs special equipment to store and safety measure, while can discharge by-product
Hydrobromic acid；Technique is more complex, and products obtained therefrom methyl eight bromo ether purity is not high, second-rate.
Summary of the invention
The present invention provides a kind of preparation method of methyl eight bromo ether, using hydrobromic acid and solid brominated sodium as catalyst,
It is reacted using new bromating agent, instead of traditional bromine production technology, safe operation, reaction is mild, and reaction condition temperature
With technological operation simplicity, and reduce bromine as brominating agent degree height, lead to the possibility of chain rupture and methyl bromide
Property, effectively reduce the generation of by-product.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of preparation method of methyl eight bromo ether, comprising the following steps:
(1) tetrabromobisphenol A is added to the water dissolution, the molar ratio of water and tetrabromobisphenol A is 2-8:1, uses sodium hydroxide
PH value is adjusted, the range of the pH value is 8-10, and carries out first time heat preservation, then, methylallyl chloride organic solution is added dropwise,
Phase transfer catalyst is added, second is carried out after completion of dropwise addition and is kept the temperature, room temperature is then cooled to, is layered, takes organic layer；
(2) bromating agent is added to dissolution in organic solvent and obtains bromination agent solution, catalyst is added in above-mentioned organic layer
The molar ratio of dropwise addition bromination agent solution progress bromination reaction afterwards, the bromating agent and tetrabromobisphenol A is 2-4:1, is 25- in temperature
Third time heat preservation is carried out under conditions of 55 DEG C, and sodium sulfite aqueous solution reaction is then added, is washed with water after reaction, static point
Layer takes lower organic layer to be added in the aqueous solution of emulsifier, is distilled, and removes organic solvent, and suction filtration obtains material, dries,
Product is prepared.
Preferably, the molar ratio of the methylallyl chloride and tetrabromobisphenol A is 1.8-2.5:1.
Preferably, the phase transfer catalyst is tetrabutylammonium bromide, any one in tetraethylammonium bromide, the phase
The molar ratio of transfer catalyst and tetrabromobisphenol A is 0.5-1:5.
Preferably, the bromating agent is tribromo tetrabutylammonium bromide, tribromo tetraethylammonium bromide, pyridine bromide, dibromo sea
Any one because in, the organic solvent are methylene chloride, ethyl acetate, any one in dichloroethanes, carbon tetrachloride,
The mass ratio of the bromating agent and organic solvent is 1-10:1.
Preferably, the catalyst is the mixture of hydrobromic acid and sodium bromide, and the molar ratio of hydrobromic acid and sodium bromide is
The mass ratio of 1.5:1, the catalyst and organic layer described in step (1) is 0.5:10.
Preferably, the condition of the first time heat preservation is 100 DEG C, 0.5-1h, it is therefore an objective to remove the oxygen in water.
Preferably, the condition of second of heat preservation is 60 DEG C, 1-2h, carries out substitution reaction.
Preferably, the time of the third time heat preservation is 35 DEG C, 1-3h.
Preferably, the mass fraction of the sodium sulfite aqueous solution is 5-10%.
Preferably, the emulsifier be OP-10, fatty alcohol ether phosphate, any one or more in phenolic ether phosphate,
The dosage of the emulsifier is the 1-3wt% of water consumption, and the use of the emulsifier in the aqueous solution of emulsifier is added in the organic layer
Amount is the 0.5wt% of organic layer dosage.
Beneficial effects of the present invention are shown:
Using hydrobromic acid and solid brominated sodium as catalyst, bromination reaction is carried out using bromating agent, reacts the mild of change,
Graft reaction is carried out using phase transfer catalyst, improves conversion ratio, and avoid using toxicity height, corrosivity, volatility
Big bromine, easy to operate, safety；It is distilled using emulsifier, improves the degree of scatter of product, the solvent in technique can
With recycling and reusing, bromination reaction temperature is low, and reaction condition is mild, easily controllable, and production energy consumption is low, and each step is without harshness
Reaction condition, easy to industrialized production, product yield is high, good product quality.
Specific embodiment
In order to facilitate the understanding of those skilled in the art, the present invention is further illustrated combined with specific embodiments below:
Embodiment 1:
A kind of preparation method of methyl eight bromo ether, comprising the following steps:
(1) tetrabromobisphenol A is added to the water dissolution, the molar ratio of water and tetrabromobisphenol A is 2:1, with sodium hydroxide tune
PH value is saved, the pH value is 8, and carries out first time heat preservation, then, methylallyl chloride organic solution is added dropwise, phase transfer is added
Catalyst, carries out keeping the temperature for second after completion of dropwise addition, is then cooled to room temperature, is layered, takes organic layer；
(2) bromating agent is added to dissolution in organic solvent and obtains bromination agent solution, catalyst is added in above-mentioned organic layer
The molar ratio of dropwise addition bromination agent solution progress bromination reaction afterwards, the bromating agent and tetrabromobisphenol A is 2:1, is 25-55 in temperature
Third time heat preservation is carried out under conditions of DEG C, and sodium sulfite aqueous solution reaction is then added, is washed with water after reaction, static layering,
It takes lower organic layer to be added in the aqueous solution of emulsifier, is distilled, remove organic solvent, suction filtration obtains material, dries, preparation
Obtain product.
The molar ratio of the methylallyl chloride and tetrabromobisphenol A is 1.8:1.The phase transfer catalyst is tetrabutyl bromine
The molar ratio of change ammonium, the phase transfer catalyst and tetrabromobisphenol A is 0.5:5.The bromating agent is tribromo tetrabutylammonium bromide,
The organic solvent is methylene chloride, and the mass ratio of the bromating agent and organic solvent is 1:1.The catalyst be hydrobromic acid with
The molar ratio of the mixture of sodium bromide, hydrobromic acid and sodium bromide is 1.5:1, and the mass ratio of the catalyst and organic layer is 0.5:
10.The condition of the first time heat preservation is 100 DEG C, 0.5-1h, it is therefore an objective to remove the oxygen in water.The item of second of heat preservation
Part is 60 DEG C, 1-2h, carries out substitution reaction.The time of the third time heat preservation is 35 DEG C, 1-3h.The sodium sulfite aqueous solution
Mass fraction be 5%.The emulsifier is OP-10, and the dosage of the emulsifier is the 1wt% of water consumption, the emulsifier
Dosage be organic layer dosage 0.5wt%.
The present embodiment products obtained therefrom methyl eight bromo ether is white powder, and purity 99.0%, thermal decomposition temperature is 325 DEG C.
Embodiment 2:
A kind of preparation method of methyl eight bromo ether, comprising the following steps:
(1) tetrabromobisphenol A is added to the water dissolution, the molar ratio of water and tetrabromobisphenol A is 5:1, with sodium hydroxide tune
PH value is saved, the pH value is 9, and carries out first time heat preservation, then, methylallyl chloride organic solution is added dropwise, phase transfer is added
Catalyst, carries out keeping the temperature for second after completion of dropwise addition, is then cooled to room temperature, is layered, takes organic layer；
(2) bromating agent is added to dissolution in organic solvent and obtains bromination agent solution, catalyst is added in above-mentioned organic layer
The molar ratio of dropwise addition bromination agent solution progress bromination reaction afterwards, the bromating agent and tetrabromobisphenol A is 3:1, is 25-55 in temperature
Third time heat preservation is carried out under conditions of DEG C, and sodium sulfite aqueous solution reaction is then added, is washed with water after reaction, static layering,
It takes lower organic layer to be added in the aqueous solution of emulsifier, is distilled, remove organic solvent, suction filtration obtains material, dries, preparation
Obtain product.
The molar ratio of the methylallyl chloride and tetrabromobisphenol A is 2:1.The phase transfer catalyst is tetraethyl bromination
The molar ratio of ammonium, the phase transfer catalyst and tetrabromobisphenol A is 0.7:5.The bromating agent is pyridine bromide, described organic molten
Agent is carbon tetrachloride, and the mass ratio of the bromating agent and organic solvent is 5:1.The catalyst is the mixed of hydrobromic acid and sodium bromide
Close object, the molar ratio of hydrobromic acid and sodium bromide is 1.5:1, and the mass ratio of the catalyst and organic layer is 0.5:10.Described
The condition once kept the temperature is 100 DEG C, 0.5-1h, it is therefore an objective to remove the oxygen in water.The condition of second heat preservation is 60 DEG C,
1-2h carries out substitution reaction.The time of the third time heat preservation is 35 DEG C, 1-3h.The quality of the sodium sulfite aqueous solution point
Number is 7%.The emulsifier is fatty alcohol ether phosphate, and the dosage of the emulsifier is the 2wt% of water consumption, the emulsifier
Dosage be organic layer dosage 0.5wt%.
The present embodiment products obtained therefrom methyl eight bromo ether is white powder, and purity 98.6%, thermal decomposition temperature is 330 DEG C.
Embodiment 3:
A kind of preparation method of methyl eight bromo ether, comprising the following steps:
(1) tetrabromobisphenol A is added to the water dissolution, the molar ratio of water and tetrabromobisphenol A is 8:1, with sodium hydroxide tune
PH value is saved, the pH value is 10, and carries out first time heat preservation, then, methylallyl chloride organic solution is added dropwise, phase transfer is added
Catalyst, carries out keeping the temperature for second after completion of dropwise addition, is then cooled to room temperature, is layered, takes organic layer；
(2) bromating agent is added to dissolution in organic solvent and obtains bromination agent solution, catalyst is added in above-mentioned organic layer
The molar ratio of dropwise addition bromination agent solution progress bromination reaction afterwards, the bromating agent and tetrabromobisphenol A is 4:1, is 25-55 in temperature
Third time heat preservation is carried out under conditions of DEG C, and sodium sulfite aqueous solution reaction is then added, is washed with water after reaction, static layering,
It takes lower organic layer to be added in the aqueous solution of emulsifier, is distilled, remove organic solvent, suction filtration obtains material, dries, preparation
Obtain product.
The molar ratio of the methylallyl chloride and tetrabromobisphenol A is 2.5:1.The phase transfer catalyst is tetrabutyl bromine
The molar ratio of change ammonium, the phase transfer catalyst and tetrabromobisphenol A is 1:5.The bromating agent is C5H6Br2N2O2, described organic molten
Agent is ethyl acetate, and the mass ratio of the bromating agent and organic solvent is 10:1.The catalyst is hydrobromic acid and sodium bromide
The molar ratio of mixture, hydrobromic acid and sodium bromide is 1.5:1, and the mass ratio of the catalyst and organic layer is 0.5:10.It is described
The condition of heat preservation is 100 DEG C, 0.5-1h for the first time, it is therefore an objective to remove the oxygen in water.The condition of second of heat preservation is 60
DEG C, 1-2h, carry out substitution reaction.The time of the third time heat preservation is 35 DEG C, 1-3h.The quality of the sodium sulfite aqueous solution
Score is 5-10%.The emulsifier is phenolic ether phosphate, and the dosage of the emulsifier is the 3wt% of water consumption, the emulsification
The dosage of agent is the 0.5wt% of organic layer dosage.
The present embodiment products obtained therefrom methyl eight bromo ether is white powder, and purity 99.2%, thermal decomposition temperature is 342 DEG C.
Above content is only to structure example of the invention and explanation, affiliated those skilled in the art
It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention
Structure or beyond the scope defined by this claim, be within the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of methyl eight bromo ether, which comprises the following steps:
(1) tetrabromobisphenol A is added to the water dissolution, the molar ratio of water and tetrabromobisphenol A is 2-8:1, is adjusted with sodium hydroxide
The range of pH value, the pH value is 8-10, and carries out first time heat preservation, then, methylallyl chloride organic solution is added dropwise, is added
Phase transfer catalyst, carries out keeping the temperature for second after completion of dropwise addition, is then cooled to room temperature, is layered, takes organic layer；
(2) bromating agent is added to dissolution in organic solvent and obtains bromination agent solution, dripped after catalyst is added in above-mentioned organic layer
Bromination agent solution is added to carry out bromination reaction, the molar ratio of the bromating agent and tetrabromobisphenol A is 2-4:1, is 25-55 DEG C in temperature
Under conditions of carry out third time heat preservation, then be added sodium sulfite aqueous solution reaction, be washed with water after reaction, static layering takes
Lower organic layer is added in the aqueous solution of emulsifier, is distilled, and organic solvent is removed, and suction filtration obtains material, dries, is prepared into
To product.
2. a kind of preparation method of methyl eight bromo ether according to claim 1, which is characterized in that the methylallyl chloride
Molar ratio with tetrabromobisphenol A is 1.8-2.5:1.
3. a kind of preparation method of methyl eight bromo ether according to claim 1, which is characterized in that the phase transfer catalyst
For any one in tetrabutylammonium bromide, tetraethylammonium bromide, the molar ratio of the phase transfer catalyst and tetrabromobisphenol A is
0.5-1:5。
4. a kind of preparation method of methyl eight bromo ether according to claim 1, which is characterized in that the bromating agent is tribromo
Tetrabutylammonium bromide, tribromo tetraethylammonium bromide, pyridine bromide, any one in C5H6Br2N2O2, the organic solvent is two
Chloromethanes, ethyl acetate, any one in dichloroethanes, carbon tetrachloride, the mass ratio of the bromating agent and organic solvent is
1-10:1。
5. a kind of preparation method of methyl eight bromo ether according to claim 1, which is characterized in that the catalyst is hydrogen bromine
The molar ratio of acid and the mixture of sodium bromide, hydrobromic acid and sodium bromide is 1.5:1, and the mass ratio of the catalyst and organic layer is
0.5:10。
6. a kind of preparation method of methyl eight bromo ether according to claim 1, which is characterized in that the first time heat preservation
Condition is 100 DEG C, 0.5-1h.
7. a kind of preparation method of methyl eight bromo ether according to claim 1, which is characterized in that second of heat preservation
Condition is 60 DEG C, 1-2h.
8. a kind of preparation method of methyl eight bromo ether according to claim 1, which is characterized in that the third time heat preservation
Time is 35 DEG C, 1-3h.
9. a kind of preparation method of methyl eight bromo ether according to claim 1, which is characterized in that the sodium sulfite is water-soluble
The mass fraction of liquid is 5-10%.
10. a kind of preparation method of methyl eight bromo ether according to claim 1, which is characterized in that the emulsifier is OP-
10, fatty alcohol ether phosphate, any one or more in phenolic ether phosphate, the dosage of the emulsifier is the 1- of water consumption
3wt%, the dosage of the emulsifier are the 0.5wt% of organic layer dosage.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796315A (en) * | 2019-02-22 | 2019-05-24 | 山东兄弟科技股份有限公司 | A kind of preparation method of high heat stability sex flame retardant methyl eight bromo 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 |
| CN112830868A (en) * | 2021-02-02 | 2021-05-25 | 山东迈特新材料科技有限公司 | Preparation method of high-purity methyl octabromoether |
| CN114195621A (en) * | 2021-12-14 | 2022-03-18 | 山东省海洋化工科学研究院 | Preparation method of methyl octabromoether |
| CN114573427A (en) * | 2022-05-05 | 2022-06-03 | 山东东信阻燃科技有限公司 | Preparation method for synthesizing flame retardant methyl octabromoether by two-step method |
| CN114805039A (en) * | 2022-04-13 | 2022-07-29 | 山东海王化工股份有限公司 | Production process of high-melting-point flame retardant methyl octabromoether |
-
2018
- 2018-11-22 CN CN201811398873.7A patent/CN109336746A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796315A (en) * | 2019-02-22 | 2019-05-24 | 山东兄弟科技股份有限公司 | A kind of preparation method of high heat stability sex flame retardant methyl eight bromo 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 |
| CN112830868A (en) * | 2021-02-02 | 2021-05-25 | 山东迈特新材料科技有限公司 | Preparation method of high-purity methyl octabromoether |
| CN112830868B (en) * | 2021-02-02 | 2023-02-17 | 山东迈特新材料科技有限公司 | Preparation method of methyl octabromoether |
| CN114195621A (en) * | 2021-12-14 | 2022-03-18 | 山东省海洋化工科学研究院 | Preparation method of methyl octabromoether |
| CN114195621B (en) * | 2021-12-14 | 2023-12-22 | 山东省海洋化工科学研究院 | Preparation method of methyl octabromoether |
| CN114805039A (en) * | 2022-04-13 | 2022-07-29 | 山东海王化工股份有限公司 | Production process of high-melting-point flame retardant methyl octabromoether |
| CN114573427A (en) * | 2022-05-05 | 2022-06-03 | 山东东信阻燃科技有限公司 | Preparation method for synthesizing flame retardant methyl octabromoether by two-step method |
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