CN102766054B - 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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- CN102766054B CN102766054B CN201210281962.XA CN201210281962A CN102766054B CN 102766054 B CN102766054 B CN 102766054B CN 201210281962 A CN201210281962 A CN 201210281962A CN 102766054 B CN102766054 B CN 102766054B
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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 industry that the present invention relates to a kind of two (4-oil of mirbane) carbonic ethers is synthesized, method of purification.
Background technology
Two (4-oil of mirbane) carbonic ether is solid at normal temperatures, and purity is high, can be used as the alternative hypertoxic phosgene of carbonylation agent and carrys out carbonate synthesis ester compound, has certain application prospect.
The current domestic industrial synthesizing progress method without concrete synthetic two (4-oil of mirbane) carbonic ethers, the invention provides that a kind of safe, reliable, stable technical grade is synthetic, method of purification, two (4-oil of mirbane) carbonate content of finished product can reach more than 99%, colourity 20 black once below, product yield 99%.
Summary of the invention
The object of this invention is to provide that a kind of technique 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.
The industry of a kind of two (4-oil of mirbane) carbonic ethers of the present invention is synthesized, method of purification, be achieved by following steps: a. synthesis procedure: by raw material methylene dichloride, p-NP, antioxidant S-WAT, catalyst of triethylamine and tap water add in proportion in reactor and stir 30 minutes; After successively by the sodium hydroxide solution that in sodium hydroxide solution storage tank, concentration is 34% and triphosgene---triphosgene in dichloromethane solution tank---methylene dichloride mixing solutions adds reactor; Maintain reactor temperature and be no more than 25 DEG C, and react after 2 hours the material in reactor is put into oil trap; B. washing step: add oil trap to wash the material in oil trap in tap water; C. distillation process: after the material stratification after above-mentioned operation washing, lower floor's organic phase is put into still kettle and distill desolvation; D. crystallization, refrigerating work procedure: above-mentioned through distillation desolvation material in add methylcarbonate solution, and be warming up to 70 DEG C, make solution reach supersaturated solution; And naturally cooling; E. separate and drying process: above-mentioned material of separating out after naturally cooling, after whizzer separates, is put into the solid of gained after oven drying, obtain two (4-oil of mirbane) carbonic ether products; F. solvent recuperation operation: the solvent steaming in still kettle in absorption tower by the sodium hydroxide solution washing and recycling in sodium hydroxide solution storage tank.
Technique scheme, the mol ratio of triphosgene and p-NP is 1:3～15; Inner liner of reaction kettle enamel; Reactor temperature is controlled at 15～25 DEG C; The add-on of catalyst of triethylamine is 0.005～5% of solution total mass.
Adopt technique scheme, due to by-product acid in reaction process, react therefore be chosen in airtight enamelled vessel; In case solvent evaporates, in ensureing temperature of reaction, is controlled at 15～25 DEG C by temperature of reaction.
In sum, the invention has the beneficial effects as follows: owing to adopting raw material methylene dichloride, p-NP, water of condensation in antioxidant S-WAT, catalyst of triethylamine and condenser is in reaction kettle for reaction, by reaction gained material through washing, distillation, crystallization, cooling, separates and drying process obtains highly purified two (4-oil of mirbane) carbonic ether product, adopts this kind of method technique simple; In this reaction process, temperature of reaction only need be controlled at 15～25 DEG C, and energy consumption is low; Consider by-product acid in reaction process, can cause corrosion to equipment, reactor adopts liner enamel, therefore can ensure this technical scheme safety, stable, reliable; Owing to being provided with solvent recuperation operation in reaction process, solvent can being recycled, and then reduced production cost.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
In figure: 1 sodium hydroxide solution storage tank, 2 triphosgene---dichloromethane solution tank, 3 condensers, 4 reactors, 5 oil traps, 6 crude product grooves, 7 still kettles, 8 dichloromethane solution tanks, 9 whizzers, 10 baking ovens, 11 absorption towers, 12 sodium hydroxide solution storage tanks
Embodiment
Below in conjunction with accompanying drawing 1, the present invention will be further described:
Embodiment mono-:
In 1L reactor 4, successively add 500ml methylene dichloride, 56.3g p-NP, 20ml water, 1.5g S-WAT, 0.2ml triethylamine, stir 30 minutes; Take 21g triphosgene and be dissolved in 60ml methylene dichloride, be made into triphosgene---dichloromethane solution; Be 34% sodium hydroxide solution and triphosgene---the dichloromethane solution for preparing to slowly dripping respectively 38ml concentration in reactor 4; Control reaction process temperature, be no more than 25 DEG C, be stirred to the pH value end of synthesis that no longer declines.Add oil trap 5 to wash the material in oil trap in tap water; After stratification, lower floor's organic phase is put into still kettle 7 and distill desolvation; In the solution of distillation, adding 70 DEG C of methylcarbonates to dissolve Solid Double (4-oil of mirbane) carbonic ether, make it reach supersaturated solution, entering baking oven 10 through the separating obtained solid of whizzer 9, to obtain purity after dry be 99.51%, and colourity is 10 black two (4-oil of mirbane) carbonic ether products once.
Embodiment bis-:
In 50L reactor 4, successively add 25L methylene dichloride, 2.8kg p-NP, 2L water, 15g S-WAT, 12ml triethylamine, stir 30 minutes; Take again 1.1kg triphosgene and be dissolved in 3L methylene dichloride, be made into triphosgene---dichloromethane solution; Be 34% sodium hydroxide solution and triphosgene---the dichloromethane solution for preparing to slowly dripping respectively 2L concentration in reactor 4; Whole process temperature control is no more than 25 DEG C, and after stirring 2h, pH value is stable, end of synthesis.Add oil trap 5 to wash the material in oil trap in tap water; After stratification, lower floor's organic phase is put into still kettle 7 and distill desolvation; In the solution of distillation, adding 70 DEG C of methylcarbonates to dissolve Solid Double (4-oil of mirbane) carbonic ether, make it reach supersaturated solution, entering baking oven 10 through the separating obtained solid of whizzer 9, to obtain purity after dry be 99.36%, black two (4-oil of mirbane) the carbonic ether products once of colourity 10.
Embodiment tri-:
In 3000L reactor 4, successively add 1500L, 165kg p-NP, 120L water, 0.9kg S-WAT, 0.8L triethylamine, stir 30 minutes, then take 1.1kg triphosgene and be dissolved in 3L methylene dichloride, is made into triphosgene---dichloromethane solution; To in reactor 4 respectively with 0.12m
3/ h flow adds 34% sodium hydroxide solution, with 0.18 m
3/ h flow adds triphosgene---dichloromethane solution; After stirring reaction 2h, survey the stable no longer decline of pH value, stop stirring; Add oil trap 5 to wash the material in oil trap in tap water; After stratification, lower floor's organic phase is put into still kettle 7 and distill desolvation; In the solution of distillation, adding 70 DEG C of methylcarbonates to dissolve Solid Double (4-oil of mirbane) carbonic ether, make it reach supersaturated solution, entering baking oven 10 through the separating obtained solid of whizzer 9, to obtain purity after dry be 99.12%, and colourity is 20 black two (4-oil of mirbane) carbonic ether products once.
Claims (1)
1. synthetic, the method for purification of the industry of two (4-oil of mirbane) carbonic ethers, it is characterized in that: in 3000L reactor 4, successively add 1500L methylene dichloride, 165kg p-NP, 120L water, 0.9kg S-WAT, 0.8L triethylamine, stir 30 minutes, take again 1.1kg triphosgene and be dissolved in 3L methylene dichloride, be made into triphosgene---dichloromethane solution; To in reactor 4 respectively with 0.12m
3it is 34% sodium hydroxide solution that/h flow adds mass concentration, with 0.18 m
3/ h flow adds triphosgene---dichloromethane solution; After stirring reaction 2h, survey the stable no longer decline of pH value, stop stirring; Add oil trap 5 to wash the material in oil trap in tap water; After stratification, lower floor's organic phase is put into still kettle 7 and distill desolvation; In the solution of distillation, adding 70 DEG C of methylcarbonates to dissolve Solid Double (4-oil of mirbane) carbonic ether, make it reach supersaturated solution, entering baking oven 10 through the separating obtained solid of whizzer 9, to obtain purity after dry be 99.12%, and colourity is 20 black two (4-oil of mirbane) carbonic ether products once.
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| CN201210281962.XA CN102766054B (en) | 2012-08-09 | 2012-08-09 | Industrial synthesizing and purifying method of bis (4-nitrophenyl) carbonate |
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| CN201210281962.XA CN102766054B (en) | 2012-08-09 | 2012-08-09 | Industrial synthesizing and purifying method of bis (4-nitrophenyl) carbonate |
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| CN102766054A CN102766054A (en) | 2012-11-07 |
| CN102766054B true CN102766054B (en) | 2014-12-03 |
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| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11140029A (en) * | 1997-11-07 | 1999-05-25 | Mitsubishi Chemical Corp | Production of diaryl carbonate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (3)
| Title |
|---|
| 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.》.2010,(第49期),第3049-3052页. * |
| 三光气合成碳酸二(4-硝基苯基)酯工艺研究;王磊等;《合肥工业大学学报》;20091231;第32卷(第12期);第1916-1919页 * |
| 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》.2009,第32卷(第12期),第1916-1919页. * |
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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. |