CN102627567A - Preparation method for 4,4'-dinitryl diphenyl ether - Google Patents
Preparation method for 4,4'-dinitryl diphenyl ether Download PDFInfo
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- CN102627567A CN102627567A CN2012100840166A CN201210084016A CN102627567A CN 102627567 A CN102627567 A CN 102627567A CN 2012100840166 A CN2012100840166 A CN 2012100840166A CN 201210084016 A CN201210084016 A CN 201210084016A CN 102627567 A CN102627567 A CN 102627567A
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Abstract
The invention discloses a preparation method for 4,4'-dinitryl diphenyl ether. The preparation method comprises the steps as follows: adding nitrochlorobenzene, anhydrous carbonic acid alkali metal salt and nitrous acid alkali metal salt into an organic solvent; stirring at a temperature of 70-160 DEG C, and reacting for 4-10 h; filtering a reactant to remove the salts; decompressing and distilling to remove the organic solvent from the reactant, wherein the organic solvent can be recycled; washing residues for 1-5 times by hot water of 85-100 DEG C, and filtering while the residues are hot; and drying the obtained yellow crystals to obtain the 4,4'-dinitryl diphenyl ether. The preparation method has the advantages of no pollution, low production cost, good product quality and high yield.
Description
Technical field
The invention belongs to a kind of 4, the preparation method of 4'-dinitro diphenyl ether.
Background technology
4,4 '-dinitro diphenyl ether (4,4 '-Dinitrodiphenyl ether) be called for short DNDPE, be a kind of fine-chemical intermediate of high added value.Its reduzate 4; 4 '-diaminodiphenyl oxide is the principal monomer of heat-resistant plastics such as synthesis of polyimides, poly maleimide; Polyimide (Polyimide wherein; PI) have high temperature resistant, radioprotective and physical strength advantages of higher, be used for aspects such as film, coating, fiber, porous plastics and photoresist material, be widely used in fields such as aviation, navigation, nuclear power, electronic apparatus industry.DNDPE also is used for the solidifying agent of synthetic epoxy resin, the midbody of dyestuff and the synthesis material of spices etc.Along with each industry is increasingly high to the performance requriements of resin material, the domestic and international market is increasing DNDPE demand and output year by year, and its Technology also more and more comes into one's own, and is therefore significant to the research and development of synthetic DNDPE.
Traditional DNDPE compound method has following 3 kinds: 1) phenyl ether nitrofication process; 2) paradinitrobenzene method; 3) p-Nitrophenyl chloride and p-NP or phenates condensation method.
The phenyl ether nitrofication process: make catalyzer with hydrofluoric acid among the patent US3417146, use the nitric acid nitrating phenyl ether, system temperature is at 0-10 ℃.Behind the 31min, product reclaims with benzene extraction, again water and alkali cleaning.Through detect finding to contain 45% dinitro diphenyl ether in the crystal, wherein 4,4 '-dinitro diphenyl ether only accounts for 50%.This method by product is more, and yield is low, and uses hydrofluoric acid to make reactant and catalyzer, and corrodibility is strong, has brought inconvenience to suitability for industrialized production, and is big for environment pollution.
Make solvent with DMSO (DMSO 99.8MIN.) among paradinitrobenzene method: the patent EP 0495425, paradinitrobenzene and salt of wormwood are heated about 5.8h down at 100 ℃, cooling, washing, getting the DNDPE yield is 88%.This method technology is simple, and yield is higher, but paradinitrobenzene is volatile, and severe toxicity is arranged, and environment is had harm.
P-Nitrophenyl chloride and p-NP or phenates condensation method: p-Nitrophenyl chloride and p-NP or phenates condensation method are the traditional technologys of producing DNDPE; When utilizing p-NP to make raw material; Need be in the presence of sodium hydroxide (potassium) or sodium-chlor (potassium) could with the p-Nitrophenyl chloride condensation, with the then directly condensation of p-nitrophenol salt.
Liu Yuansheng etc. make solvent with oil of mirbane, and with p-Nitrophenyl chloride, p-NP, salt of wormwood and Repone K reaction 15-25h under 200-220 ℃, the optimal yield of DNDPE is 95%.This research is made solvent with oil of mirbane, though the DNDPE yield is high, and p-NP and oil of mirbane strong toxicity, and meet the danger that there is blast in high heat.
More than three kinds of methods have respectively that yield is low, raw material is volatile and severe toxicity is arranged, temperature of reaction is high and operate uneasy congruent drawback.
Summary of the invention
The purpose of this invention is to provide a kind of pollution-free, production cost is low, good product quality, yield are high 4,4 '-preparation method of dinitro diphenyl ether.
Preparing method of the present invention is following:
P-Nitrophenyl chloride, Carbon Dioxide an alkali metal salt, nitrite alkali metal-salt are joined in the organic solvent 70-160
oStir under the C temperature, behind the reaction 4-10 h, reaction product is carried out filter operation; Salt is removed, and organic solvent is removed in underpressure distillation from reaction product; Organic solvent is recyclable to be recycled, and residue is with 85-100 ℃ hot water injection 1-5 time, and filtered while hot; Yellow crystal oven dry with obtaining obtains the DNDPE product, and wherein the mol ratio of raw material is:
P-Nitrophenyl chloride: Carbon Dioxide an alkali metal salt=1:0.5-1; P-Nitrophenyl chloride: nitrite alkali metal-salt=1:0.3-1; P-Nitrophenyl chloride: organic solvent=1:1-3;
Aforesaid Carbon Dioxide an alkali metal salt is soda ash light or Anhydrous potassium carbonate.
Aforesaid nitrite alkali metal-salt is Sodium Nitrite or potassium nitrite.
Aforesaid organic solvent is N, dinethylformamide (DMF), DMSO 99.8MIN. (DMSO) or N-Methyl pyrrolidone (NMP).
Embodiment
Embodiment 1:
In the 500 mL there-necked flasks that reflux condensing tube, electric mixer and TM are housed; The p-Nitrophenyl chloride, 26.5 g (0.25 mol) soda ash light, 10.4 g (0.15 mol) Sodium Nitrite and 36.5 g (0.5 mol) DMF that add 79 g (0.5 mol); Stir, be heated to 70
oBehind reaction 4 h, stop heating, stir under the C temperature, carry out filter operation, remove sodium salt; Organic solvent DMF is removed in underpressure distillation from reaction product; Residue is with 500 mL, 85 ℃ hot water injection 1 time, and filtered while hot, and the yellow crystal oven dry with obtaining obtains the DNDPE product, and yield is 48%, product purity 75%.
Embodiment 2:
In the 500 mL there-necked flasks that reflux condensing tube, electric mixer and TM are housed; The p-Nitrophenyl chloride, 53.0 g (0. 5 mol) soda ash light, 34.5 g (0.5 mol) Sodium Nitrite and 109.5 g (1.5 mol) DMF that add 79 g (0.5 mol); Stir, be heated to 160
oBehind reaction 10 h, stop heating, stir under the C temperature, carry out filter operation, remove sodium salt; Organic solvent DMF is removed in underpressure distillation from reaction product; Residue is with 500 mL, 90 ℃ hot water injection 5 times, and filtered while hot, and the yellow crystal oven dry with obtaining obtains the DNDPE product, and yield is 83%, product purity 99.7%.
Embodiment 3:
In the 500 mL there-necked flasks that reflux condensing tube, electric mixer and TM are housed; The p-Nitrophenyl chloride, 37.1 g (0.35 mol) soda ash light, 27.6 g (0.4 mol) Sodium Nitrite and 73.0 g (1.0 mol) DMF that add 79 g (0.5 mol); Stir, be heated to 150
oBehind reaction 6 h, stop heating, stir under the C temperature, carry out filter operation, remove sodium salt; Organic solvent DMF is removed in underpressure distillation from reaction product; Residue is with 500 mL, 95 ℃ hot water injection 4 times, and filtered while hot, and the yellow crystal oven dry with obtaining obtains the DNDPE product, and yield is 98%, product purity 99.5%.
Embodiment 4:
In the 500 mL there-necked flasks that reflux condensing tube, electric mixer and TM are housed; The p-Nitrophenyl chloride, 37.1 g (0.35 mol) soda ash light, 27.6 g (0.4 mol) Sodium Nitrite and 78.0 g (1.0 mol) DMSO that add 79 g (0.5 mol); Stir, be heated to 100
oBehind reaction 6 h, stop heating, stir under the C temperature, carry out filter operation, remove sodium salt; Organic solvent DMSO is removed in underpressure distillation from reaction product; Residue is with 500 mL, 95 ℃ hot water injection 3 times, and filtered while hot, and the yellow crystal oven dry with obtaining obtains the DNDPE product, and yield is 93%, product purity 99.3%.
Embodiment 5:
In the 500 mL there-necked flasks that reflux condensing tube, electric mixer and TM are housed; The p-Nitrophenyl chloride, 37.1 g (0.35 mol) soda ash light, 27.6 g (0.4 mol) Sodium Nitrite and 99.0 g (1.0 mol) NMP that add 79 g (0.5 mol); Stir, be heated to 120
oBehind reaction 6 h, stop heating, stir under the C temperature, carry out filter operation, remove sodium salt; Organic solvent NMP is removed in underpressure distillation from reaction product; Residue is with 500 mL, 90 ℃ hot water injection 4 times, and filtered while hot, and the yellow crystal oven dry with obtaining obtains the DNDPE product, and yield is 95%, product purity 99.5%.
Embodiment 6:
In the 500 mL there-necked flasks that reflux condensing tube, electric mixer and TM are housed; The p-Nitrophenyl chloride, 34.5 g (0.25 mol) Anhydrous potassium carbonate, 12.8 g (0.15 mol) potassium nitrite and 36.5 g (0.5 mol) DMF that add 79 g (0.5 mol); Stir, be heated to 80
oBehind reaction 4 h, stop heating, stir under the C temperature, carry out filter operation, remove sodium salt; Organic solvent DMF is removed in underpressure distillation from reaction product; Residue is with 500 mL, 95 ℃ hot water injection 1 time, and filtered while hot, and the yellow crystal oven dry with obtaining obtains the DNDPE product, and yield is 47.5%, product purity 76%.
Embodiment 7:
In the 500 mL there-necked flasks that reflux condensing tube, electric mixer and TM are housed; The p-Nitrophenyl chloride, 48.3 g (0.35 mol) Anhydrous potassium carbonate, 34.0 g (0.4 mol) potassium nitrite and 73.0 g (1.0 mol) DMF that add 79 g (0.5 mol); Stir, be heated to 150
oBehind reaction 6 h, stop heating, stir under the C temperature, carry out filter operation, remove sodium salt; Organic solvent DMF is removed in underpressure distillation from reaction product; Residue is with 500 mL, 100 ℃ hot water injection 4 times, and filtered while hot, and the yellow crystal oven dry with obtaining obtains the DNDPE product, and yield is 96%, product purity 99.5%.
Embodiment 8:
In the 500 mL there-necked flasks that reflux condensing tube, electric mixer and TM are housed; The p-Nitrophenyl chloride, 69.0 g (0. 5 mol) Anhydrous potassium carbonate, 42.5 g (0.5 mol) potassium nitrite and 109.5 g (1.5 mol) DMF that add 79 g (0.5 mol); Stir, be heated to 160
oBehind reaction 10 h, stop heating, stir under the C temperature, carry out filter operation, remove sodium salt; Organic solvent DMF is removed in underpressure distillation from reaction product; Residue is with 500 mL, 100 ℃ hot water injection 5 times, and filtered while hot, and the yellow crystal oven dry with obtaining obtains the DNDPE product, and yield is 81.8%, product purity 99.7%.
Embodiment 9:
In the 500 mL there-necked flasks that reflux condensing tube, electric mixer and TM are housed; The p-Nitrophenyl chloride, 48.3 g (0.35 mol) Anhydrous potassium carbonate, 34.0 g (0.4 mol) potassium nitrite and 78.0 g (1.0 mol) DMSO that add 79 g (0.5 mol); Stir, be heated to 120
oBehind reaction 6 h, stop heating, stir under the C temperature, carry out filter operation, remove sodium salt; Organic solvent DMSO is removed in underpressure distillation from reaction product; Residue is with 500 mL, 95 ℃ hot water injection 4 times, and filtered while hot, and the yellow crystal oven dry with obtaining obtains the DNDPE product, and yield is 92.6%, product purity 99.2%.
Embodiment 10:
In the 500 mL there-necked flasks that reflux condensing tube, electric mixer and TM are housed; The p-Nitrophenyl chloride, 48.3 g (0.35 mol) Anhydrous potassium carbonate, 34.0 g (0.4 mol) potassium nitrite and 99.0 g (1.0 mol) NMP that add 79 g (0.5 mol); Stir, be heated to 130
oBehind reaction 6 h, stop heating, stir under the C temperature, carry out filter operation, remove sodium salt; Organic solvent NMP is removed in underpressure distillation from reaction product; Residue is with 500 mL, 95 ℃ hot water injection 5 times, and filtered while hot, and the yellow crystal oven dry with obtaining obtains the DNDPE product, and yield is 93.7%, product purity 99.5%.
Claims (4)
1. one kind 4, the preparation method of 4'-dinitro diphenyl ether is characterized in that comprising the steps:
P-Nitrophenyl chloride, Carbon Dioxide an alkali metal salt, nitrite alkali metal-salt are joined in the organic solvent 70-160
oStir under the C temperature, behind the reaction 4-10 h, reaction product is carried out filter operation, salt is removed; Organic solvent is removed in underpressure distillation from reaction product, organic solvent is recyclable to be recycled; Residue is with 85-100 ℃ hot water injection 1-5 time, and filtered while hot, with the yellow crystal oven dry that obtains; Obtain 4,4'-dinitro diphenyl ether product, wherein the mol ratio of raw material is:
P-Nitrophenyl chloride: Carbon Dioxide an alkali metal salt=1:0.5-1; P-Nitrophenyl chloride: nitrite alkali metal-salt=1:0.3-1; P-Nitrophenyl chloride: organic solvent=1:1-3.
2. as claimed in claim 1 a kind of 4, the preparation method of 4'-dinitro diphenyl ether is characterized in that described Carbon Dioxide an alkali metal salt is soda ash light or Anhydrous potassium carbonate.
3. as claimed in claim 1 a kind of 4, the preparation method of 4'-dinitro diphenyl ether is characterized in that described nitrite alkali metal-salt is Sodium Nitrite or potassium nitrite.
4. as claimed in claim 1 a kind of 4, the preparation method of 4'-dinitro diphenyl ether is characterized in that described organic solvent is N, dinethylformamide, DMSO 99.8MIN. or N-Methyl pyrrolidone.
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| CN2012100840166A CN102627567A (en) | 2012-03-27 | 2012-03-27 | Preparation method for 4,4'-dinitryl diphenyl ether |
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| CN2012100840166A CN102627567A (en) | 2012-03-27 | 2012-03-27 | Preparation method for 4,4'-dinitryl diphenyl ether |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776427A (en) * | 2019-11-23 | 2020-02-11 | 南通汇顺化工有限公司 | Method for preparing 4, 4' -dinitrodiphenyl ether |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5455536A (en) * | 1977-10-04 | 1979-05-02 | Mitsui Toatsu Chem Inc | Preparation o dinitrobiphenyl ethers |
| JPS5569542A (en) * | 1978-11-16 | 1980-05-26 | Mitsui Toatsu Chem Inc | Preparation of dinitrodiphenyl ether |
| JPS5632439A (en) * | 1979-08-28 | 1981-04-01 | Mitsui Toatsu Chem Inc | Production of dinitrodiphenyl ether |
| CN1762976A (en) * | 2005-09-08 | 2006-04-26 | 华东理工大学 | 4,4-dinitrodiphenyl ethers synthesis method |
-
2012
- 2012-03-27 CN CN2012100840166A patent/CN102627567A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5455536A (en) * | 1977-10-04 | 1979-05-02 | Mitsui Toatsu Chem Inc | Preparation o dinitrobiphenyl ethers |
| JPS5569542A (en) * | 1978-11-16 | 1980-05-26 | Mitsui Toatsu Chem Inc | Preparation of dinitrodiphenyl ether |
| JPS5632439A (en) * | 1979-08-28 | 1981-04-01 | Mitsui Toatsu Chem Inc | Production of dinitrodiphenyl ether |
| CN1762976A (en) * | 2005-09-08 | 2006-04-26 | 华东理工大学 | 4,4-dinitrodiphenyl ethers synthesis method |
Non-Patent Citations (2)
| Title |
|---|
| ZHANG, ZHIQIANG 等: "Investigation on the new synthetic reactions and mechanisms of substituted diphenyl ethers", 《CHINESE CHEMICAL LETTERS》 * |
| 朱维群 等: "4,4"-二氨基二苯醚合成新工艺", 《天津化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776427A (en) * | 2019-11-23 | 2020-02-11 | 南通汇顺化工有限公司 | Method for preparing 4, 4' -dinitrodiphenyl ether |
| CN110776427B (en) * | 2019-11-23 | 2022-03-29 | 南通汇顺化工有限公司 | Method for preparing 4, 4' -dinitrodiphenyl ether |
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Application publication date: 20120808 |