CN104592167A - Method for preparing phenyl glycidyl ether - Google Patents
Method for preparing phenyl glycidyl ether Download PDFInfo
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- CN104592167A CN104592167A CN201410846720.XA CN201410846720A CN104592167A CN 104592167 A CN104592167 A CN 104592167A CN 201410846720 A CN201410846720 A CN 201410846720A CN 104592167 A CN104592167 A CN 104592167A
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- glycidyl ether
- epoxy chloropropane
- phenyl glycidyl
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- ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
- C07D303/23—Oxiranylmethyl ethers of compounds having one hydroxy group bound to a six-membered aromatic ring, the oxiranylmethyl radical not being further substituted, i.e.
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
Abstract
The invention relates to a synthetic method of phenyl glycidyl ether. The method comprises the following steps: carrying out ring-opening reaction; carrying out ring-closure reaction; washing; refining; and recovering excessive epoxy chloropropane in vacuum from a phenyl glycidyl ether coarse to obtain a phenyl glycidyl ether finished product, wherein the recovered epoxy chloropropane is directly reused in next batch. The method comprises the following steps: by taking phenol and epoxy chloropropane as raw materials, firstly, carrying out ring-opening reaction under the action of a ternary compound catalyst comprising N,N-dimethylethanolamine, tetrabutylammonium hydrogen sulfate and quaternary ammonium salt-7 to prepare an intermediate phenyl chlorhydrin; and then carrying out ring-closure reaction with a sodium hydroxide solution to prepare the phenyl glycidyl ether, wherein the recovered epoxy chloropropane can be directly reused. The method provided by the invention has the advantages of simple process, short production cycle, high final product yield, high epoxide number, small color number and the like and is easily industrialized.
Description
Technical field
The present invention relates to a kind of phenyl glycidyl ether, particularly relate to a kind of synthetic method of phenyl glycidyl ether.
Background technology
Containing phenyl ring, ehter bond and epoxy group(ing) in the molecule of phenyl glycidyl ether, structurally containing rigid chain segment, better, cured product is compared with butylglycidyl ether, and heat-drawn wire is significantly improved for thermotolerance and antiseptic property.Be widely used in electronics, electrical equipment, electromechanics, machinery industry, reduce epoxy viscosity, be suitable for embedding, casting, impregnating application art, also can be used in tackiness agent.React can obtain epoxy curing agent with polyamine.
The traditional synthetic method of phenyl glycidyl ether adopts single stage method, namely in the presence of a phase transfer catalyst, is obtained by reacting by phenol, epoxy chloropropane and sodium hydroxide.Its shortcoming is: side reaction is many, and the consumption of sodium hydroxide and epoxy chloropropane is large, and raw material availability is low, and production cost is high; Speed of response is slow, long reaction time, and energy consumption is high, and production efficiency is low; Use volatile solvent, environmental pollution is larger.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of phenyl glycidyl ether, solve the technical problems such as existing synthetic method utilization ratio is low, production cost is high, speed of response is slow, long reaction time, energy consumption are high, production efficiency is low, use volatile solvent, environmental pollution is larger.
A synthetic method for phenyl glycidyl ether, comprises the following steps:
A. ring-opening reaction: with phenol, epoxy chloropropane for raw material, the mass ratio of phenol and epoxy chloropropane is 1:2 ~ 4, adding N, N-dimethylethanolamine, hydrogen sulfate TBuA and polyquaternium-7(dimethyl diallyl ammonium chloride-acrylamide copolymer) ternary complex catalyst, carry out ring-opening reaction under nitrogen protection condition, the temperature of ring-opening reaction is 70 ~ 100 DEG C, obtained intermediate phenyl chloropharin; In described composite catalyst, N, N-dimethylethanolamine consumption is 0.5 ~ 3% of reactant quality, and hydrogen sulfate TBuA consumption is 1 ~ 3% of reactant quality, and polyquaternium-7 consumption is 0.5 ~ 0.9% of reactant;
B. ring-closure reaction: phenyl chloropharin and sodium hydroxide solution are carried out ring-closure reaction under nitrogen protection, the mol ratio of epoxy chloropropane and sodium hydroxide is 1:0.8 ~ 1.5, and the temperature of ring-closure reaction is 40 ~ 70 DEG C, obtained phenyl glycidyl ether work in-process;
C. wash: phenyl glycidyl ether work in-process stratification, salt discharge water, then add soft water and wash, washing once obtains phenyl glycidyl ether crude product;
D. refine: reclaim excessive epoxy chloropropane to phenyl glycidyl ether crude product vacuum, namely obtain phenyl glycidyl ether finished product, the epoxy chloropropane of recovery is directly in next batch reuse.
The advantages such as this synthetic method adopts two-step approach, and the catalyzer of use is N, N-dimethylethanolamine, hydrogen sulfate TBuA and polyquaternium-7 ternary complex catalyst, and technique is simple, and product yield is high, oxirane value is high and look is number little, easily realize industrialization.Range of catalysts of the present invention is suitable consumption, and catalyst levels is very few, and speed of response is slow; And catalyst levels is too much, speed of response increases not obvious, also can cause side reaction, causes washing layering difficulty simultaneously.
In above-mentioned synthetic method, the mass ratio of phenol and epoxy chloropropane is 1:2 ~ 4, and epoxy chloropropane is fewer, and phenol reactant is incomplete, and product yield is low, and epoxy chloropropane is more, and unwanted side reaction can be suppressed to occur, and the oxirane value of product is high.But meanwhile, epoxy chloropropane is excessive more, and the output of unit equipment is fewer, the energy consumption reclaiming epoxy chloropropane is larger.
In above-mentioned synthetic method, the temperature of ring-opening reaction is 70 ~ 100 DEG C, and this temperature is too low, and speed of reaction is then too low; Temperature is too high, and side reaction becomes many.
In above-mentioned synthetic method, the temperature of ring-closure reaction is 40 ~ 70 DEG C, and this temperature is too low, then the bad control of temperature; And temperature is higher, side reaction easily occurs, and causes product look number higher, and oxirane value reduces.
In above-mentioned synthetic method, the mol ratio of epoxy chloropropane and sodium hydroxide is 1:0.8 ~ 1.5, and sodium hydroxide is excessive, is conducive to the carrying out of ring-closure reaction, and the organochlorine of product is low, and oxirane value is high; But the consumption of sodium hydroxide is too high, the pH value of waste water is high, and wastewater treatment difficulty is large.
The present invention is using phenol, epoxy chloropropane and sodium hydroxide as raw material, two-step approach is adopted to prepare phenyl glycidyl ether, the first step is ring-opening reaction, mainly phenol and ring chlorine are at N, react under the effect of N-dimethylethanolamine, hydrogen sulfate TBuA and polyquaternium-7 ternary complex catalyst, obtained intermediate phenyl chloropharin, simultaneously due to the singularity of reaction mechanism, also can generate a certain amount of phenyl glycidyl ether simultaneously; Second step is ring-closure reaction, and intermediate phenyl chloropharin and sodium hydroxide carry out ring-closure reaction, obtain phenyl glycidyl ether by exquisiteness process.The excess epoxy chloropropane reclaimed can direct reuse.
The present invention adopts open loop-closed loop-washing-recovery epoxy chloropropane synthetic route; with phenol, epoxy chloropropane for raw material; use N; N-dimethylethanolamine, hydrogen sulfate TBuA and polyquaternium-7 ternary complex catalyst; adopt excessive, the nitrogen protection of epoxy chloropropane, conservative control temperature simultaneously; product yield and oxirane value can be improved, reduce look number.Excessive epoxy chloropropane adopts the mode of decompression to reclaim, can direct reuse.The present invention has that technique is simple, with short production cycle, the finished product yield is high, oxirane value is high and the advantage such as look is number little, easily realizes industrialization.
Embodiment
Below in conjunction with specific embodiment, implementation method of the present invention is described in further details.
Embodiment 1
Under nitrogen protection condition, turn on agitator, adds 120 parts of phenol in a kettle. respectively, 2.4 parts of N, N-dimethylethanolamines, 14.4 parts of hydrogen sulfate TBuAs, 2.4 parts of polyquaterniums-7.Heat up, when temperature is to after to 75 DEG C, drips 360 parts of epoxy chloropropane, control temperature is at 80 ~ 85 DEG C, and 3h drips complete, and continuation is incubated 1h; Be cooled to 50 DEG C, under nitrogen protection, at the temperature of 55 ~ 60 DEG C, drip 150 parts of 48% liquid caustic soda, 1h finishes, and continues insulation 3h at 55 ~ 60 DEG C of temperature; Leave standstill, salt discharge water, then add 50 parts of soft water washings, lower floor's oil phase reclaims after excessive epoxy chloropropane through underpressure distillation and namely obtains phenyl glycidyl ether 190 parts, main content 98.30%, and oxirane value is 0.655mol/100 part, and APHA look number is No. 10.
Embodiment 2
Under nitrogen protection condition, turn on agitator, adds 120 parts of phenol in a kettle. respectively, 14.4 parts of N, N-dimethylethanolamines, 4.8 parts of hydrogen sulfate TBuAs, 4.3 parts of polyquaterniums-7.Heat up, when temperature is to after to 75 DEG C, drips 360 parts of epoxy chloropropane, control temperature is at 80 ~ 85 DEG C, and 3h drips complete, and continuation is incubated 1h; Be cooled to 50 DEG C, under nitrogen protection, at the temperature of 55 ~ 60 DEG C, drip 150 parts of 48% liquid caustic soda, 1h finishes, and continues insulation 3h at 55 ~ 60 DEG C of temperature; Leave standstill, salt discharge water, then add 50 parts of soft water washings, lower floor's oil phase reclaims after excessive epoxy chloropropane through underpressure distillation and namely obtains phenyl glycidyl ether 190 parts, main content 97.61%, and oxirane value is 0.650mol/100 part, and APHA look number is No. 10.
Embodiment 3
Under nitrogen protection condition, turn on agitator, adds 120 parts of phenol in a kettle. respectively, 7.2 parts of N, N-dimethylethanolamines, 7.2 parts of hydrogen sulfate TBuAs, 2.5 parts of polyquaterniums-7.Heat up, when temperature is to after to 75 DEG C, drips 240 parts of epoxy chloropropane, control temperature is at 80 ~ 85 DEG C, and 3h drips complete, and continuation is incubated 1h; Be cooled to 50 DEG C, under nitrogen protection, at the temperature of 55 ~ 60 DEG C, drip 150 parts of 48% liquid caustic soda, 1h finishes, and continues insulation 3h at 55 ~ 60 DEG C of temperature; Leave standstill, salt discharge water, then add 50 parts of soft water washings, lower floor's oil phase reclaims after excessive epoxy chloropropane through underpressure distillation and namely obtains phenyl glycidyl ether 190 parts, main content 98.4%%, and oxirane value is 0.656mol/100 part, and look number is No. 10.
Embodiment 4
Under nitrogen protection condition, turn on agitator, adds 120 parts of phenol in a kettle. respectively, 6 parts of N, N-dimethylethanolamines, 18 parts of hydrogen sulfate TBuAs, 3 parts of polyquaterniums-7.Heat up, when temperature is to after to 75 DEG C, drips 480 parts of epoxy chloropropane, control temperature is at 80 ~ 85 DEG C, and 3h drips complete, and continuation is incubated 1h; Be cooled to 50 DEG C, under nitrogen protection, at the temperature of 55 ~ 60 DEG C, drip 150 parts of 48% liquid caustic soda, 1h finishes, and continues insulation 3h at 55 ~ 60 DEG C of temperature; Leave standstill, salt discharge water, then add 50 parts of soft water washings, lower floor's oil phase reclaims after excessive epoxy chloropropane through underpressure distillation and namely obtains phenyl glycidyl ether 190 parts, main content 97.76%, and oxirane value is 0.651mol/100 part, and APHA look number is No. 10.
Embodiment 5
Under nitrogen protection condition, turn on agitator, adds 120 parts of phenol in a kettle. respectively, 12 parts of N, N-dimethylethanolamines, 6 parts of hydrogen sulfate TBuAs, 3.6 parts of polyquaterniums-7.Heat up, when temperature is to after to 75 DEG C, drips 360 parts of epoxy chloropropane, control temperature is at 80 ~ 85 DEG C, and 3h drips complete, and continuation is incubated 1h; Be cooled to 50 DEG C, under nitrogen protection, at the temperature of 55 ~ 60 DEG C, drip 150 parts of 48% liquid caustic soda, 1h finishes, and continues insulation 3h at 55 ~ 60 DEG C of temperature; Leave standstill, salt discharge water, then add 50 parts of soft water washings, lower floor's oil phase reclaims after excessive epoxy chloropropane through underpressure distillation and namely obtains phenyl glycidyl ether 190 parts, main content 97.91%, and oxirane value is 0.652mol/100 part, and APHA look number is No. 10.
Comparative example 1
Under nitrogen protection condition, turn on agitator, adds 120 parts of phenol in a kettle. respectively, 12 parts of N, N-dimethylethanolamines.Heat up, when temperature is to after to 75 DEG C, drips 360 parts of epoxy chloropropane, control temperature is at 80 ~ 85 DEG C, and 3h drips complete, and continuation is incubated 1h; Be cooled to 50 DEG C, under nitrogen protection condition, at the temperature of 55 ~ 60 DEG C, drip 150 parts of 48% liquid caustic soda, 1h finishes, and continues insulation 3h at 55 ~ 60 DEG C of temperature; Leave standstill, salt discharge water, then add 50 parts of soft water washings, lower floor's oil phase reclaims after excessive epoxy chloropropane through underpressure distillation and namely obtains phenyl glycidyl ether 190 parts, main content 87.6%, and oxirane value is 0.5860mol/100 part, and APHA look number is No. 20.
Comparative example 2
Turn on agitator, adds 120 parts of phenol in a kettle. respectively, 12 parts of hydrogen sulfate TBuAs.Heat up, when temperature is to after to 75 DEG C, drips 360 parts of epoxy chloropropane, control temperature is at 80 ~ 85 DEG C, and 3h drips complete, and continuation is incubated 1h; Be cooled to 50 DEG C, under nitrogen protection, at the temperature of 55 ~ 60 DEG C, drip 150 parts of 48% liquid caustic soda, 1h finishes, and continues insulation 3h at 55 ~ 60 DEG C of temperature; Leave standstill, salt discharge water, then add 50 parts of soft water washings, lower floor's oil phase reclaims after excessive epoxy chloropropane through underpressure distillation and namely obtains phenyl glycidyl ether 190 parts, main content 89.1%, and oxirane value is 0.5993mol/100 part, and APHA look number is No. 30.
Comparative example 3
Turn on agitator, adds 120 parts of phenol in a kettle. respectively, 12 parts of polyquaterniums-7.Heat up, when temperature is to after to 90 DEG C, drips 360 parts of epoxy chloropropane, control temperature is at 95 ~ 100 DEG C, and 3h drips complete, and continuation is incubated 1h; Be cooled to 50 DEG C, under nitrogen protection, at the temperature of 55 ~ 60 DEG C, drip 150 parts of 48% liquid caustic soda, 1h finishes, and continues insulation 3h at 55 ~ 60 DEG C of temperature; Leave standstill, salt discharge water, then add 50 parts of soft water washings, lower floor's oil phase reclaims after excessive epoxy chloropropane through underpressure distillation and namely obtains phenyl glycidyl ether 190 parts, main content 90.56%, and oxirane value is 0.606mol/100 part, and APHA look number is No. 30.
Comparative example 4
Turn on agitator, adds 120 parts of phenol in a kettle. respectively, 12 parts of N, N-dimethylethanolamines, 6 parts of hydrogen sulfate TBuAs, 3.6 parts of polyquaterniums-7.Heat up, when temperature is to after to 95 DEG C, drips 360 parts of epoxy chloropropane, control temperature is at 100 ~ 105 DEG C, and 3h drips complete, and continuation is incubated 1h; Be cooled to 50 DEG C, at the temperature of 75 ~ 80 DEG C, drip 150 parts of 48% liquid caustic soda, 1h finishes, and continues insulation 3h at 75 ~ 80 DEG C of temperature; Leave standstill, salt discharge water, then add 50 parts of soft water washings, lower floor's oil phase reclaims after excessive epoxy chloropropane through underpressure distillation and namely obtains phenyl glycidyl ether 178 parts, main content 79%, and oxirane value is 0.5260mol/100 part, and APHA look number is No. 40.
Comparative example 5
Turn on agitator, adds 120 parts of phenol in a kettle. respectively, 12 parts of benzyltriethylammoinium chlorides, 150 part of 48% liquid caustic soda, heats up, and when temperature is to after to 60 DEG C, drips 120 parts of epoxy chloropropane, control temperature is at 70 ~ 75 DEG C, and 3h drips complete, and continuation is incubated 1h; Leave standstill, salt discharge water, then add 50 parts of soft water washings, lower floor's oil phase reclaims after excessive epoxy chloropropane through underpressure distillation and namely obtains phenyl glycidyl ether 178 parts, main content 69%, and oxirane value is 0.4595mol/100 part, and APHA look number is No. 70.
Following table is that the index of various embodiments of the present invention and comparative example contrasts:
Claims (1)
1. a synthetic method for phenyl glycidyl ether, is characterized in that comprising the following steps:
A. ring-opening reaction: with phenol, epoxy chloropropane for raw material, the mass ratio of phenol and epoxy chloropropane is 1:2 ~ 4, at N, ring-opening reaction is carried out under the effect of N-dimethylethanolamine, hydrogen sulfate TBuA and polyquaternium-7 ternary complex catalyst, the temperature of ring-opening reaction is 70 ~ 100 DEG C, obtained intermediate phenyl chloropharin; In described composite catalyst, N, N-dimethylethanolamine consumption is 0.5 ~ 3% of reactant quality, and hydrogen sulfate TBuA consumption is 1 ~ 3% of reactant quality, and polyquaternium-7 consumption is 0.5 ~ 0.9% of reactant;
B. ring-closure reaction: phenyl chloropharin and sodium hydroxide solution are carried out ring-closure reaction under nitrogen protection, the mol ratio of epoxy chloropropane and sodium hydroxide is 1:0.8 ~ 1.5, and the temperature of ring-closure reaction is 40 ~ 70 DEG C, obtained phenyl glycidyl ether work in-process;
C. wash: phenyl glycidyl ether work in-process stratification, salt discharge water, then add soft water and wash, washing once obtains phenyl glycidyl ether crude product;
D. refine: reclaim excessive epoxy chloropropane to phenyl glycidyl ether crude product vacuum, namely obtain phenyl glycidyl ether finished product, the epoxy chloropropane of recovery is directly in next batch reuse.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299341A (en) * | 2018-01-04 | 2018-07-20 | 南京林业大学 | A kind of castor oil-base epoxy resin and preparation method thereof |
| CN110452190A (en) * | 2019-08-12 | 2019-11-15 | 南京林业大学 | A kind of castor oil-base polyglycidyl ether and preparation method thereof containing phenyl ring |
| CN113773199A (en) * | 2020-06-09 | 2021-12-10 | 中国石油化工股份有限公司 | Composition containing phenol polyether ester and preparation method and application thereof |
| US11414626B2 (en) | 2018-11-30 | 2022-08-16 | Ecolab Usa Inc. | Surfactant compositions and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4722983A (en) * | 1985-12-13 | 1988-02-02 | Ciba-Geigy Corporation | Process for the preparation of glycidyl compounds |
| US20040024254A1 (en) * | 2002-07-31 | 2004-02-05 | Keisuke Yaegashi | Process for preparation of optically active halogeno hydroxypropyl compound and glycidyl compound |
| CN103739571A (en) * | 2013-10-30 | 2014-04-23 | 中昊(大连)化工研究设计院有限公司 | Synthesis method of phenyl glycidyl ether |
-
2014
- 2014-12-31 CN CN201410846720.XA patent/CN104592167B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4722983A (en) * | 1985-12-13 | 1988-02-02 | Ciba-Geigy Corporation | Process for the preparation of glycidyl compounds |
| US20040024254A1 (en) * | 2002-07-31 | 2004-02-05 | Keisuke Yaegashi | Process for preparation of optically active halogeno hydroxypropyl compound and glycidyl compound |
| CN103739571A (en) * | 2013-10-30 | 2014-04-23 | 中昊(大连)化工研究设计院有限公司 | Synthesis method of phenyl glycidyl ether |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299341A (en) * | 2018-01-04 | 2018-07-20 | 南京林业大学 | A kind of castor oil-base epoxy resin and preparation method thereof |
| US11414626B2 (en) | 2018-11-30 | 2022-08-16 | Ecolab Usa Inc. | Surfactant compositions and use thereof |
| US11807830B2 (en) | 2018-11-30 | 2023-11-07 | Ecolab Usa Inc. | Surfactant compositions and use thereof |
| CN110452190A (en) * | 2019-08-12 | 2019-11-15 | 南京林业大学 | A kind of castor oil-base polyglycidyl ether and preparation method thereof containing phenyl ring |
| CN113773199A (en) * | 2020-06-09 | 2021-12-10 | 中国石油化工股份有限公司 | Composition containing phenol polyether ester and preparation method and application thereof |
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