CN108530274A - A kind of preparation method of bisphenol a diallyl ether - Google Patents
A kind of preparation method of bisphenol a diallyl ether Download PDFInfo
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- CN108530274A CN108530274A CN201810499482.8A CN201810499482A CN108530274A CN 108530274 A CN108530274 A CN 108530274A CN 201810499482 A CN201810499482 A CN 201810499482A CN 108530274 A CN108530274 A CN 108530274A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
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Abstract
The invention belongs to organic compound synthesis technical fields, and in particular to a kind of preparation method of bisphenol a diallyl ether.A kind of preparation method of bisphenol a diallyl ether of the present invention includes the following steps：（1）Bisphenol-A, solvent are added in reaction kettle, alkali, water absorbing agent are added after stirring and dissolving；（2）Allyl halides are instilled at a certain temperature, and reaction certain time obtains crude product；（3）Crude product obtains finished product after filtering out salt, vacuum distillation removing low-boiling-point substance.A kind of preparation method of bisphenol a diallyl ether of the present invention can effectively control the water content in reaction system, and reaction forward is promoted to carry out, and greatly reduce the step of waste is handled in production, save production cost, be suitble to large-scale production.
Description
Technical field
The invention belongs to organic compound synthesis technical fields, and in particular to a kind of preparation side of bisphenol a diallyl ether
Method.
Background technology
Bisphenol a diallyl ether is a kind of important organic synthesis intermediate, can be weighed under high temperature or catalysts conditions
Row generates diallyl bisphenol.The toughness and temperature tolerance of resin can be improved in diallyl bisphenol, reduces the solidification temperature of resin,
By the resin that diallyl bisphenol is modified there is excellent mechanical property, dielectric properties and heat resistance, great business to open
It makes an offer value.Currently, industrially mainly synthesizing diallyl bisphenol by indexable method with bisphenol a diallyl ether.Therefore, double
The quality of phenol A dual-allyl ethers has a major impact the synthesis of diallyl bisphenol.
Currently, the main preparation process of bisphenol a diallyl ether is that bisphenol-A and alkali soluble are first formed bisphenol-A in solvent
Then salt is added allyl halides and completes reaction, reaction equation is as follows：
；
Wherein, M is Na or K, X Cl, Br or I.
The prior art uses toluene and diallyl ether for solvent, allows allyl alcohol and bisphenol-a reaction under catalysts conditions,
Obtain bisphenol a diallyl ether.This method will produce many by-products, and the product that can be efficiently separated by HPLC just has five
Kind, the yield of bisphenol a diallyl ether also only has 51% under optimal solvent burden ratio.
The prior art is flowed back for 24 hours in acetone using bisphenol-A, allyl bromide, bromoallylene and potassium carbonate, through filtering and concentrating, dichloromethane
Decoloration washs drying, finally obtained colourless bisphenol a diallyl ether.This method reaction time is long, complex technical process.
Currently, domestic not yet cause this enough attention, the patent and document report about bisphenol a diallyl ether are very
It is few.Only find similar patent：Chinese granted patent CN201010531322.0 describes a kind of tetrabromo bisphenol A diene propyl ether
Preparation method, mixed using first alcohol and water, sodium sulfite and carbonic acid hydrazine be then added, adds tetrabromobisphenol A, hydroxide
Sodium stirs to dissolve, and heat temperature raising adds allyl chloride, and tetrabromo bisphenol A diene propyl ether is obtained after insulation reaction.China awards
The method that power patent CN201110212751.6 describes synthesizing tetrabromo bisphenol A diene propyl ether in a kind of water phase, it is double by tetrabromo
Phenol A, sodium hydroxide or potassium hydroxide aqueous solution with chlorallylene is etherified reacts, tetrabromobisphenol A diene third is made in cooling, separation
Base ether.
Based on this, the application is made.
Invention content
For drawbacks described above present in existing bisphenol a diallyl ether synthetic method, the present invention is reacted in bisphenol-A with alkali
During water absorbing agent is added, overcome reaction in influence and color and luster depth of the water to target product purity problem.The method work
Skill is simple and practicable, and reaction product is easy to detach from system, bisphenol a diallyl ether purity >=92% obtained, color and luster≤20（Platinum-
Cobalt-colorimetric method）, requirement and industrialized application of the high-end product to purity and color and luster can be met.
To achieve the above object, the technical solution that the application takes is as follows：
A kind of preparation method of bisphenol a diallyl ether, includes the following steps：
（1）Bisphenol-A, solvent are added in reaction kettle, alkali, water absorbing agent are added after stirring and dissolving；
（2）Allyl halides are instilled at a certain temperature, and reaction certain time obtains crude product；
（3）By step（3）Obtained crude product obtains finished product after filtering out salt, vacuum distillation removing low-boiling-point substance.
The step（1）In water absorbing agent be calcium oxide, anhydrous magnesium sulfate or dead plaster.
The step（1）The quality of middle water absorbing agent is the 5%-25% of bisphenol-A, solvent and alkali gross mass.
The step（1）In solvent be toluene, dimethylbenzene, glycol dimethyl ether, chloroform, 1,2- dichloroethanes, 1,2-
The lower alcohol that Bromofume, ethyl acetate, DMF, dimethyl sulfoxide (DMSO), tetrahydrofuran or carbon atom number are 1 ~ 4.
The step（1）The quality of middle solvent is 0.5-5 times of bisphenol-A quality.
The step（1）In alkali be potassium hydroxide, one or both of sodium hydroxide mixture.
The step（1）In alkali and bisphenol-A molar ratio be 2-3：1.
The step（2）In allyl halides be allyl chloride, allyl bromide, bromoallylene or allyl iodide；The step（2）
In allyl halides and bisphenol-A molar ratio be 3-5：1.
The step（2）In certain time be 3-16h.
The step（2）In certain temperature be 40-100 DEG C.
The working principle and beneficial effect of the present invention is as follows：
（1）Water content effectively in control reaction system, promotes reaction forward to carry out.In reaction process, there are two sides in the source of water
Generation is brought and reacted to face, raw material into.In the building-up process of bisphenol a diallyl ether, the presence of water can reduce the conversion of reaction
Rate is unfavorable for reaction forward progress.The present invention makes reaction by the way that water absorbing agent, the water that constantly absorption and consumption reaction generate is added
Moisture is consistently lower than 0.5% in system, this is conducive to pull chemical reaction equilibrium to the direction for being conducive to generate target product
It carries out, to improve conversion ratio, reaches the requirement of high-end product.
（2）Reaction condition of the present invention is simple, and controllably, deicer price used is low, is easy to get, and water removal effect is good, reaction product
It is easy to detach from system, greatly reduces the step of waste is handled in production, save production cost, be suitble to large-scale production.
Specific implementation mode
Embodiment 1
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, toluene 260g is added, after bisphenol-A is completely dissolved
Sodium hydroxide 90g and calcium oxide 28.9g is added, stirs evenly, starts that allyl chloride 229.5g is added dropwise, is warming up to 100 DEG C, heat preservation
React 3h.Reaction finishes, and is cooled to room temperature, obtains product crude product；Crude product is after filtering desalination, vacuum distillation removing low-boiling-point substance
Products obtained therefrom purity 92.9%, color and luster 17.
Embodiment 2
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, dimethylbenzene 260g is added, waits for that bisphenol-A is completely dissolved
Potassium hydroxide 123.2g and calcium oxide 30.6g is added afterwards, stirs evenly, starts that allyl chloride 229.5g is added dropwise, is warming up to 100
DEG C, insulation reaction 3h.Reaction finishes, and is cooled to room temperature, obtains product crude product；Crude product is by filtering desalination, vacuum distillation removing
Products obtained therefrom purity 93.9% after low-boiling-point substance, color and luster 16.
Embodiment 3
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, glycol dimethyl ether 450g is added, waits for that bisphenol-A is complete
Sodium hydroxide 80g and dead plaster 100g is added after fully dissolved, stirs evenly, starts that allyl chloride 382.5g, heating is added dropwise
To 85 DEG C, insulation reaction 16h.Reaction finishes, and is cooled to room temperature, obtains product crude product；Crude product is by filtering desalination, vacuum distillation
Products obtained therefrom purity 92.3% after removing low-boiling-point substance, color and luster 19.
Embodiment 4
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, chloroform 170g is added, after bisphenol-A is completely dissolved
Potassium hydroxide 112g and dead plaster 100g is added, stirs evenly, starts that allyl bromide, bromoallylene 363g is added dropwise, is warming up to 70 DEG C, protect
Temperature reaction 16h.Reaction finishes, and is cooled to room temperature, obtains product crude product；Crude product is by filtering desalination, vacuum distillation removing low boiling
Products obtained therefrom purity 92.1% after object, color and luster 20.
Embodiment 5
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, acetone 400g is added, after bisphenol-A is completely dissolved
Sodium hydroxide 80g, potassium hydroxide 56g and calcium oxide 100g is added, stirs evenly, starts that allyl chloride 382.5g, heating is added dropwise
To 60 DEG C, insulation reaction 4h.Reaction finishes, and is cooled to room temperature, obtains product crude product；Crude product is by filtering desalination, vacuum distillation
Products obtained therefrom purity 94.4% after removing low-boiling-point substance, color and luster 10.
Embodiment 6
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, 1,2- dichloroethanes 400g are added, wait for that bisphenol-A is complete
Potassium hydroxide 168g and calcium oxide 100g is added after fully dissolved, stirs evenly, starts that allyl chloride 382.5g is added dropwise, is warming up to 60
DEG C, insulation reaction 4h.Reaction finishes, and is cooled to room temperature, obtains product crude product；Crude product is by filtering desalination, vacuum distillation removing
Products obtained therefrom purity 92.4% after low-boiling-point substance, color and luster 15.
Embodiment 7
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, 1,2- Bromofume 400g are added, wait for that bisphenol-A is complete
Potassium hydroxide 168g and calcium oxide 100g is added after fully dissolved, stirs evenly, starts that allyl chloride 382.5g is added dropwise, is warming up to
60 DEG C, insulation reaction 4h.Reaction finishes, and is cooled to room temperature, obtains product crude product；Crude product is de- by filtering desalination, vacuum distillation
Except products obtained therefrom purity 93.8% after low-boiling-point substance, color and luster 14.
Embodiment 8
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, ethyl acetate 400g is added, waits for that bisphenol-A is completely molten
Potassium hydroxide 168g and anhydrous magnesium sulfate 100g is added after solution, stirs evenly, starts that allyl iodide 840g is added dropwise, is warming up to 80
DEG C, insulation reaction 4h.Reaction finishes, and is cooled to room temperature, obtains product crude product；Crude product is by filtering desalination, vacuum distillation removing
Products obtained therefrom purity 92.8% after low-boiling-point substance, color and luster 17.
Embodiment 9
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, DMF 114g are added, after bisphenol-A is completely dissolved
Sodium hydroxide 120g and calcium oxide 115.5g is added, stirs evenly, starts that allyl chloride 267.7g is added dropwise, is warming up to 80 DEG C, protect
Temperature reaction 4h.Reaction finishes, and is cooled to room temperature, obtains product crude product；Crude product is by filtering desalination, vacuum distillation removing low-boiling-point substance
Products obtained therefrom purity 94.7% afterwards, color and luster 12.
Embodiment 10
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, dimethyl sulfoxide (DMSO) 500g is added, waits for that bisphenol-A is complete
Sodium hydroxide 120g and anhydrous magnesium sulfate 100g is added after dissolving, stirs evenly, starts that allyl chloride 229.5g is added dropwise, is warming up to
80 DEG C, insulation reaction 4h.Reaction finishes, and is cooled to room temperature, obtains product crude product；Crude product is de- by filtering desalination, vacuum distillation
Except products obtained therefrom purity 92.0% after low-boiling-point substance, color and luster 19.
Embodiment 11
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, tetrahydrofuran 250g is added, waits for that bisphenol-A is completely molten
Sodium hydroxide 120g and anhydrous magnesium sulfate 100g is added after solution, stirs evenly, starts that allyl chloride 229.5g is added dropwise, is warming up to
40 DEG C, insulation reaction 16h.Reaction finishes, and is cooled to room temperature, obtains product crude product；Crude product is de- by filtering desalination, vacuum distillation
Except products obtained therefrom purity 94.0% after low-boiling-point substance, color and luster 14.
Embodiment 12
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, tert-butyl alcohol 684g is added, waits for that bisphenol-A is completely dissolved
Sodium hydroxide 100g and calcium oxide 100g is added afterwards, stirs evenly, starts that allyl chloride 267g is added dropwise, is warming up to 80 DEG C, heat preservation
React 6h.Reaction finishes, and is cooled to room temperature, obtains product crude product；Crude product is after filtering desalination, vacuum distillation removing low-boiling-point substance
Products obtained therefrom purity 95.3%, color and luster 6.
Embodiment 13
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, tert-butyl alcohol 1140g is added（Supplement the embodiment with
It supports that the quality of solvent is 5 times of bisphenol-A, the table of comparisons can be not added with）, sodium hydroxide 100g is added after bisphenol-A is completely dissolved
It with calcium oxide 100g, stirs evenly, starts that allyl chloride 267g is added dropwise, be warming up to 80 DEG C, insulation reaction 6h.Reaction finishes, drop
It warms to room temperature, obtains product crude product；Crude product products obtained therefrom purity 95.3% after filtering desalination, vacuum distillation removing low-boiling-point substance,
Color and luster 6.
Comparative example 1
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, acetone 400g is added, after bisphenol-A is completely dissolved
Sodium hydroxide 80g, potassium hydroxide 56g is added, stirs evenly, starts to be added dropwise allyl chloride 382.5g, 1h is added dropwise, is warming up to
60 DEG C, insulation reaction 4h.Reaction finishes, and is cooled to room temperature, obtains product crude product；Crude product is de- by filtering desalination, vacuum distillation
Except products obtained therefrom purity 77.1% after low-boiling-point substance, color and luster 121.
Comparative example 2
Bisphenol-A 228g is added in 1000ml four-hole boiling flasks, opens stirring, tert-butyl alcohol 684g is added, waits for that bisphenol-A is completely dissolved
Sodium hydroxide 100g is added afterwards, stirs evenly, starts that allyl chloride 267g is added dropwise, is warming up to 60 DEG C, insulation reaction 6h.Reaction
It finishes, is cooled to room temperature, obtain product crude product；Crude product products obtained therefrom after filtering desalination, vacuum distillation removing low-boiling-point substance is pure
Degree 76.4%, color and luster 96.
As can be seen that can obtain higher purity and more shallow color and luster using by inventive method, purity >=92%, color and luster≤
20, meet high-end product requirement.
The quality controls table of product under 1 different technology conditions of table
In commercial Application, maximum difficult point is the balance between product purity and color and luster, usually when product purity is higher,
Color and luster is also higher, influences quality, color and luster and the application performance of downstream product, when color and luster is relatively low, product purity also declines, can not
Meet the requirement in terms of product reactivity, the application realizes the requirement of high-purity and low color, assign by the way that water absorbing agent is added
The higher reactivity of product and condition index are given.
Claims (10)
1. a kind of preparation method of bisphenol a diallyl ether, it is characterised in that include the following steps：
（1）Bisphenol-A, solvent are added in reaction kettle, alkali, water absorbing agent are added after stirring and dissolving；
（2）Allyl halides are instilled at a certain temperature, and reaction certain time obtains crude product；
（3）By step（3）Obtained crude product obtains finished product after filtering out salt, vacuum distillation removing low-boiling-point substance.
2. a kind of preparation method of bisphenol a diallyl ether as described in claim 1, it is characterised in that：The step（1）In
Water absorbing agent be calcium oxide, anhydrous magnesium sulfate or dead plaster.
3. a kind of preparation method of bisphenol a diallyl ether as described in claim 1, it is characterised in that：The step（1）In
The quality of water absorbing agent is the 5%-25% of bisphenol-A, solvent and alkali gross mass.
4. a kind of preparation method of bisphenol a diallyl ether as described in claim 1, it is characterised in that：The step（1）In
Solvent be toluene, dimethylbenzene, glycol dimethyl ether, chloroform, 1,2- dichloroethanes, 1,2- Bromofumes, ethyl acetate, DMF,
The lower alcohol that dimethyl sulfoxide (DMSO), tetrahydrofuran or carbon atom number are 1 ~ 4.
5. a kind of preparation method of bisphenol a diallyl ether as described in claim 1, it is characterised in that：The step（1）In
The quality of solvent is 0.5-5 times of bisphenol-A quality.
6. a kind of preparation method of bisphenol a diallyl ether as described in claim 1, it is characterised in that：The step（1）In
Alkali be potassium hydroxide, one or both of sodium hydroxide mixture.
7. a kind of preparation method of bisphenol a diallyl ether as described in claim 1, it is characterised in that：The step（1）In
Alkali and bisphenol-A molar ratio be 2-3：1.
8. a kind of preparation method of bisphenol a diallyl ether as described in claim 1, it is characterised in that：The step（2）In
Allyl halides be allyl chloride, allyl bromide, bromoallylene or allyl iodide；The step（2）In allyl halides and bis-phenol
The molar ratio of A is 3-5：1.
9. a kind of preparation method of bisphenol a diallyl ether as described in claim 1, it is characterised in that：The step（2）In
Certain time be 3-16h.
10. a kind of preparation method of bisphenol a diallyl ether as described in claim 1, it is characterised in that：The step（2）
In certain temperature be 40-100 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109574813A (en) * | 2018-12-07 | 2019-04-05 | 浙江皇马新材料科技有限公司 | A kind of synthetic method of bisphenol a diallyl ether |
| CN112125787A (en) * | 2020-10-15 | 2020-12-25 | 莱州市百辰绝缘材料有限公司 | Process for synthesizing diallyl phenol ether compound by azeotropic dehydration |
| CN114671762A (en) * | 2022-03-01 | 2022-06-28 | 长春市兆兴新材料技术有限责任公司 | Fluorine-containing biphenyl dimethacrylate crosslinking agent and preparation method thereof |
| CN114752038A (en) * | 2022-03-16 | 2022-07-15 | 黄山天马新材料科技有限公司 | Halogen-free flame-retardant epoxy resin and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574813A (en) * | 2018-12-07 | 2019-04-05 | 浙江皇马新材料科技有限公司 | A kind of synthetic method of bisphenol a diallyl ether |
| CN109574813B (en) * | 2018-12-07 | 2022-05-17 | 浙江皇马科技股份有限公司 | Synthesis method of bisphenol A diallyl ether |
| CN112125787A (en) * | 2020-10-15 | 2020-12-25 | 莱州市百辰绝缘材料有限公司 | Process for synthesizing diallyl phenol ether compound by azeotropic dehydration |
| CN114671762A (en) * | 2022-03-01 | 2022-06-28 | 长春市兆兴新材料技术有限责任公司 | Fluorine-containing biphenyl dimethacrylate crosslinking agent and preparation method thereof |
| CN114671762B (en) * | 2022-03-01 | 2024-03-19 | 长春市兆兴新材料技术有限责任公司 | Fluorine-containing bi-xylylene methacrylate cross-linking agent and preparation method thereof |
| CN114752038A (en) * | 2022-03-16 | 2022-07-15 | 黄山天马新材料科技有限公司 | Halogen-free flame-retardant epoxy resin and preparation method thereof |
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| CN108530274B (en) | 2021-08-13 |
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