CN102766054A - Industrial synthesizing and purifying method of bis (4-nitrophenyl) carbonate - Google Patents
Industrial synthesizing and purifying method of bis (4-nitrophenyl) carbonate Download PDFInfo
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- CN102766054A CN102766054A CN201210281962XA CN201210281962A CN102766054A CN 102766054 A CN102766054 A CN 102766054A CN 201210281962X A CN201210281962X A CN 201210281962XA CN 201210281962 A CN201210281962 A CN 201210281962A CN 102766054 A CN102766054 A CN 102766054A
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Abstract
The invention discloses an industrial synthesizing and purifying method for safely, stably and reliably synthesizing high-purity bis (4-nitrophenyl) carbonate by a simple process with low energy consumption and low cost. The method comprises the following synthesizing steps: adding dichloromethane and p-nitrophenol serving as raw materials, sodium sulfite serving as an antioxidant, triethylamine sereving as a catalyst, and tap water into a reaction kettle (4) in proportion and stirring for 30min; adding a mixed solution of sodium hydroxide solution with concentration being 34% from a sodium hydroxide solution storage tank (1) and triphosgene- dichloromethane mixed solution from a triphosgene- dichloromethane solution tank (2) into the reaction kettle (4); keeping the temperature in the reaction kettle (4) not higher than 25%, reacting for 2h and then discharging the materials into an oil trap (5) from the reaction kettle (4); and carrying out water washing, distilling, crystallizing and cooling, separating and drying sequentially to finally obtain the high-purity bis (4-nitrophenyl) carbonate product.
Description
Technical field
The present invention relates to a kind of synthetic, method of purification of industry of two (4-oil of mirbane) carbonic ethers.
Background technology
Two (4-oil of mirbane) carbonic ether is solid at normal temperatures, and purity is high, and the phosgene that can be used as the alternative severe toxicity of carbonylation agent comes the carbonate synthesis ester compound, has certain application prospect.
Synthetic and the method for purification of the present domestic no concrete industry of synthesizing two (4-oil of mirbane) carbonic ethers; The present invention provides a kind of safe, reliable, stable technical grade synthetic, method of purification; Two (4-oil of mirbane) carbonate content of finished product can reach more than 99%; Below colourity 20 is deceived once, product yield 99%.
Summary of the invention
The purpose of this invention is to provide that a kind of technology is simple, energy consumption is low, cost is low, safe, stable, the method for two (4-oil of mirbane) carbonic ethers of synthesis of high purity reliably.
Synthetic, the method for purification of the industry of a kind of two (4-oil of mirbane) carbonic ethers of the present invention; Be achieved through following steps: a. synthesis procedure: with raw material methylene dichloride, p-NP, inhibitor S-WAT, catalyst of triethylamine and tap water add in proportion in the reaction kettle and to stir 30 minutes; After be that 34% sodium hydroxide solution and TRIPHOSGENE 99.5--TRIPHOSGENE 99.5 in the dichloromethane solution jar---methylene dichloride mixing solutions adds reaction kettle successively with concentration in the sodium hydroxide solution storage tank; Keep reactor temperature and be no more than 25 ℃, and react after 2 hours the material in the reaction kettle is put into oil trap; B. washing step: tap water is added oil trap the material in the oil trap is washed; C. distillation process: behind the material standing demix after the above-mentioned operation washing, lower floor's organic phase is put into the still kettle distillation remove solvent; D. crystallization, refrigerating work procedure: above-mentioned through distillation remove solvent material in add methylcarbonate solution, and be warming up to 70 ℃, make solution reach supersaturated solution; And naturally cooling; E. separate and drying process: above-mentioned through the material of separating out behind the naturally cooling after whizzer separates, the solid of gained put into oven drying after, promptly get pair (4-oil of mirbane) carbonic ether products; F. solvent recuperation operation: the solvent that steams in the still kettle in the absorption tower by the sodium hydroxide solution washing and recycling in the sodium hydroxide solution storage tank.
Technique scheme, the mol ratio of TRIPHOSGENE 99.5 and p-NP are 1:3～15; Inner liner of reaction kettle enamel; Reactor temperature is controlled at 15～25 ℃; The add-on of catalyst of triethylamine is 0.005～5% of a solution total mass.
Adopt technique scheme,, react so be chosen in the airtight enamelled vessel owing to by-product acid in reaction process; In case solvent evaporates when guaranteeing temperature of reaction, is controlled at 15～25 ℃ with temperature of reaction.
In sum; The invention has the beneficial effects as follows: owing to adopt raw material methylene dichloride, p-NP, the water of condensation in inhibitor S-WAT, catalyst of triethylamine and the condensing surface is in reaction kettle for reaction, with the material of reaction gained through washing; Distillation; Crystallization, cooling separate and drying process promptly gets highly purified two (4-oil of mirbane) carbonic ether product, adopt this kind method technology simple; In this reaction process, temperature of reaction only need be controlled at 15～25 ℃, and energy consumption is low; Consider by-product acid in reaction process, can cause corrosion to equipment, reaction kettle adopts liner enamel, so can guarantee this technical scheme safety, stable, reliable; Owing to be provided with the solvent recuperation operation in reaction process, make solvent to recycle, and then reduced production cost.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Among the figure: 1 sodium hydroxide solution storage tank, 2 TRIPHOSGENE 99.5s---dichloromethane solution jar, 3 condensing surfaces, 4 reaction kettles; 5 oil traps, 6 bullion grooves, 7 still kettles, 8 dichloromethane solution jars; 9 whizzers, 10 baking ovens, 11 absorption towers, 12 sodium hydroxide solution storage tanks
Embodiment
1 couple of the present invention further specifies below in conjunction with accompanying drawing:
Embodiment one:
In 1L reaction kettle 4, successively add 500ml methylene dichloride, 56.3g p-NP, 20ml water, 1.5g S-WAT, 0.2ml triethylamine, stirred 30 minutes; Take by weighing the 21g TRIPHOSGENE 99.5 and be dissolved in the 60ml methylene dichloride, be made into TRIPHOSGENE 99.5---dichloromethane solution; In reaction kettle 4, slowly drip 38ml concentration respectively and be 34% sodium hydroxide solution and the TRIPHOSGENE 99.5---dichloromethane solution for preparing; Control reaction process temperature is no more than 25 ℃, is stirred to the pH value end of synthesis that no longer descends.The material that tap water is added in 5 pairs of oil traps of oil trap washs; Behind the standing demix, lower floor's organic phase is put into still kettle 7 distillations remove solvent; In distillatory solution, adding 70 ℃ of methylcarbonate dissolving Solid Double (4-oil of mirbane) carbonic ethers; Make it reach supersaturated solution; After whizzer 9 separating obtained solids get into baking oven 10 dryings, promptly getting purity is 99.51%, and colourity is 10 black two (4-oil of mirbane) carbonic ether products once.
Embodiment two:
In 50L reaction kettle 4, successively add 25L methylene dichloride, 2.8kg p-NP, 2L water, 15g S-WAT, 12ml triethylamine, stirred 30 minutes; Take by weighing the 1.1kg TRIPHOSGENE 99.5 again and be dissolved in the 3L methylene dichloride, be made into TRIPHOSGENE 99.5---dichloromethane solution; In reaction kettle 4, slowly drip 2L concentration respectively and be 34% sodium hydroxide solution and the TRIPHOSGENE 99.5---dichloromethane solution for preparing; Whole process temperature control is no more than 25 ℃, and pH value is stable behind the stirring 2h, end of synthesis.The material that tap water is added in 5 pairs of oil traps of oil trap washs; Behind the standing demix, lower floor's organic phase is put into still kettle 7 distillations remove solvent; In distillatory solution, adding 70 ℃ of methylcarbonate dissolving Solid Double (4-oil of mirbane) carbonic ethers; Make it reach supersaturated solution; After whizzer 9 separating obtained solids get into baking oven 10 dryings, promptly getting purity is 99.36%, colourity 10 black two (4-oil of mirbane) carbonic ether products once.
Embodiment three:
In 3000L reaction kettle 4, successively add 1500L, 165kg p-NP, 120L water, 0.9kg S-WAT, 0.8L triethylamine stirred 30 minutes, took by weighing the 1.1kg TRIPHOSGENE 99.5 again and were dissolved in the 3L methylene dichloride, were made into TRIPHOSGENE 99.5---dichloromethane solution; In reaction kettle 4 respectively with 0.12m
3/ h flow adds 34% sodium hydroxide solution, with 0.18 m
3/ h flow adds TRIPHOSGENE 99.5---dichloromethane solution; Survey the stable no longer decline of pH value behind the stirring reaction 2h, stop to stir; The material that tap water is added in 5 pairs of oil traps of oil trap washs; Behind the standing demix, lower floor's organic phase is put into still kettle 7 distillations remove solvent; In distillatory solution, adding 70 ℃ of methylcarbonate dissolving Solid Double (4-oil of mirbane) carbonic ethers; Make it reach supersaturated solution; After whizzer 9 separating obtained solids get into baking oven 10 dryings, promptly getting purity is 99.12%, and colourity is 20 black two (4-oil of mirbane) carbonic ether products once.
Claims (5)
1. synthetic, the method for purification of the industry of two (4-oil of mirbane) carbonic ethers is characterized in that adopting following steps:
A. synthesis procedure: with raw material methylene dichloride, p-NP, inhibitor S-WAT, catalyst of triethylamine and tap water add in proportion in the reaction kettle (4) and stirred 30 minutes; After be that 34% sodium hydroxide solution and TRIPHOSGENE 99.5--TRIPHOSGENE 99.5 in the dichloromethane solution jar (2)---methylene dichloride mixing solutions adds reaction kettle (4) with concentration in the sodium hydroxide solution storage tank (1) successively; Keep the interior temperature of reaction kettle (4) and be no more than 25 ℃, and react after 2 hours the material in the reaction kettle (4) is put into oil trap (5);
B. washing step: tap water is added oil trap (5) material in the oil trap is washed;
C. distillation process: behind the material standing demix after the above-mentioned operation washing, lower floor's organic phase is put into still kettle (7) distill and remove solvent;
D. crystallization, refrigerating work procedure: above-mentioned through distillation remove solvent material in add methylcarbonate solution, and be warming up to 70 ℃, make solution reach supersaturated solution; And naturally cooling;
E. separate and drying process: above-mentioned material through naturally cooling after whizzer (9) separates, the solid of gained put into baking oven (10) drying after, promptly get pair (4-oil of mirbane) carbonic ether products;
F. solvent recuperation operation: the solvent that steams in the still kettle (7) in absorption tower (11) by the sodium hydroxide solution washing and recycling in the sodium hydroxide solution storage tank (12).
2. the industry of a kind of two (4-oil of mirbane) carbonic ethers according to claim 1 is synthetic, method of purification, and it is characterized in that: the mol ratio of TRIPHOSGENE 99.5 and p-NP is 1:3～15.
3. the industry of a kind of two (4-oil of mirbane) carbonic ethers according to claim 1 is synthetic, method of purification, it is characterized in that: reaction kettle (4) liner enamel.
4. the industry of a kind of two (4-oil of mirbane) carbonic ethers according to claim 1 is synthetic, method of purification, and it is characterized in that: the interior temperature of reaction kettle (4) is controlled at 15～25 ℃.
5. the industry of a kind of two (4-oil of mirbane) carbonic ethers according to claim 1 is synthetic, method of purification, and it is characterized in that: the add-on of catalyst of triethylamine is 0.005～5% of a solution total mass.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713441A (en) * | 2019-10-25 | 2020-01-21 | 湖南兴同化学科技有限公司 | Synthesis method of oxadiazon intermediate 2, 4-dichloro-5-nitrophenol |
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| SU213811A1 (en) * | Научно исследовательский институт химических полимеров | METHOD OF OBTAINING DI- | ||
| JPH11140029A (en) * | 1997-11-07 | 1999-05-25 | Mitsubishi Chemical Corp | Production of diaryl carbonate |
| CN101074193A (en) * | 2006-05-19 | 2007-11-21 | 赵云 | Production of diphenyl carbonate by triphosgene or solid phosgene |
| CN101177481A (en) * | 2007-12-04 | 2008-05-14 | 山东默锐化学有限公司 | Preparation method for synthesizing brominated polycarbonate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU213811A1 (en) * | Научно исследовательский институт химических полимеров | METHOD OF OBTAINING DI- | ||
| JPH11140029A (en) * | 1997-11-07 | 1999-05-25 | Mitsubishi Chemical Corp | Production of diaryl carbonate |
| CN101074193A (en) * | 2006-05-19 | 2007-11-21 | 赵云 | Production of diphenyl carbonate by triphosgene or solid phosgene |
| CN101177481A (en) * | 2007-12-04 | 2008-05-14 | 山东默锐化学有限公司 | Preparation method for synthesizing brominated polycarbonate |
Non-Patent Citations (2)
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| DAVID CRICH，CHANDRASEKHAR NAVULURI: "Stereoselective Synthesis of a-Keto-deoxy-d-glycero-d-galactononulosonic Acid Glycosides by Means of the 4,5-O-Carbonate Protecting Group", 《ANGEW.CHEM.INT.ED.》, no. 49, 23 March 2010 (2010-03-23), pages 3049 - 3052 * |
| 王磊等: "三光气合成碳酸二(4-硝基苯基)酯工艺研究", 《合肥工业大学学报》, vol. 32, no. 12, 31 December 2009 (2009-12-31), pages 1916 - 1919 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713441A (en) * | 2019-10-25 | 2020-01-21 | 湖南兴同化学科技有限公司 | Synthesis method of oxadiazon intermediate 2, 4-dichloro-5-nitrophenol |
| CN110713441B (en) * | 2019-10-25 | 2023-03-10 | 湖南兴同化学科技有限公司 | Synthetic method of oxadiazon intermediate 2, 4-dichloro-5-nitrophenol |
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Address after: 244000 Anhui city of Tongling Province Lake Road six Tongling nonferrous circular economy industrial park Patentee after: TONGLING JINTAI CHEMICAL INDUSTRIAL CO., LTD. Address before: 244000 Anhui city of Tongling Province Lake Road six Tongling nonferrous circular economy industrial park Patentee before: Tongling Jintai Chemical Industrial Co., Ltd. |