CN104003868A - Preparation and purification method of paraphthaloyl chloride with high purity - Google Patents
Preparation and purification method of paraphthaloyl chloride with high purity Download PDFInfo
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- CN104003868A CN104003868A CN201410224413.8A CN201410224413A CN104003868A CN 104003868 A CN104003868 A CN 104003868A CN 201410224413 A CN201410224413 A CN 201410224413A CN 104003868 A CN104003868 A CN 104003868A
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- terephthalic acid
- sulfur oxychloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/45—Compounds containing sulfur and halogen, with or without oxygen
- C01B17/4561—Compounds containing sulfur, halogen and oxygen only
- C01B17/4584—Thionyl chloride (SOCl2)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/64—Separation; Purification; Stabilisation; Use of additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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Abstract
The invention discloses a preparation and purification method of paraphthaloyl chloride with a high purity, and belongs to the field of organic chemistry. The method comprises the following steps: carrying out a reflux reaction in the presence of a catalyst by taking terephthalic acid and thionyl chloride as raw materials, cooling and precipitating so as to obtain a crude product; filtering the crude product and then purifying the crude product in a melting crystallization or reduced pressure distillation manner; analyzing the contents of phthalic acid, thionyl chloride and catalyst in a filtrate; replenishing a proper amount of the terephthalic acid, thionyl chloride and catalyst according to the analysis result; then carrying out a circular reaction. Compared with the prior art, the method disclosed by the invention has the main advantage that the excess thionyl chloride does not need to be steamed out after the reaction is finished, but the crude product is obtained in a cooling and filtering manner, so that the filtrate is recycled. Thus, the consumption of energy and materials is decreased.
Description
Technical field
The invention belongs to organic chemistry filed, relate in particular to a kind of purification process of preparing of p-phthaloyl chloride.
Background technology
Aramid fiber is one of main tec fiber; with carbon fiber, high-strength and high-modulus weight polyethylene fiber and claim the world three large high-performance fiber; the not indispensable novel material of aerospace, defence and military and high-tech industry still; also become gradually civilian industry and life material; being widely used at aspects such as advanced composite material, life protection articles for use, communications and transportation and Superlights, is the important foundation raw material that is related to national security and the national economic development.It is reported, at present, aramid fiber product accounts for 7%～8% for flak jackets, the helmet etc., and aerospace material, physical culture account for greatly 40% with material; The aspect such as tyre framework material, conveyor materials accounts for greatly 20% left and right, and the aspects such as high-strength rope account for greatly 13%.At aramid fiber production field, contraposition aramid fiber is with fastest developing speed, and production capacity mainly concentrates on Japan and the U.S., Europe.Whole world p-aramid fiber is a market for monopolization relatively, is a market of supplying with restriction demand.The p-aramid fiber of China mainly relies on import, seriously under one's control, and within 2011, China's p-aramid fiber production capacity is about 0.21 ten thousand ton/year, approximately 5000 tons of demands.P-phthaloyl chloride is one of two essential large main raw materials of synthetic aramid fiber, and its output far can not meet market demand, almost whole dependence on import.Therefore p-phthaloyl chloride is urgently developed and is built.
The method of producing at present p-phthaloyl chloride both at home and abroad adopts sulfur oxychloride method mostly, in reaction system, add catalyzer, after reaction finishes, first to steam excessive sulfur oxychloride, and then carry out underpressure distillation or rectifying, or adopt the method for recrystallization to obtain product.Sulfur oxychloride method as what all adopt in CN20091013180, CN201010260093, CN201110101589.The above method need to consume a large amount of energy recovery sulfur oxychlorides, and raw material availability is low, and production cost is high.Be badly in need of at present its technique to improve, reduce energy and supplies consumption, meet suitability for industrialized production demand.
Summary of the invention
The object of the embodiment of the present invention is to provide a kind of preparation and purification process of p-phthaloyl chloride, is intended to solve utilization of materials low, the defects such as energy consumption height, by recycling reactants material, reduce production costs, reach good economic and social benefit, meet suitability for industrialized production demand.
For realizing the object of the invention, the present invention improves existing technique, reaction finishes directly cooling thick product to be separated out to filtration afterwards, analyze the content of measuring terephthalic acid, sulfur oxychloride and catalyzer in filtrate, add a certain amount of terephthalic acid, sulfur oxychloride and catalyzer according to result and carry out circulating reaction.The thick product obtaining is through underpressure distillation or fusion-crystallization, and a step can reach more than 99.9% purity, has reduced like this energy and supplies consumption, reaches good economic and social benefit.
Concrete steps are as follows: taking terephthalic acid as raw material; under catalyst action; use sulfur oxychloride acidylate; 79-89 DEG C of reflux; the cooling crude product of separating out, filters, and analyzes the content of measuring terephthalic acid, sulfur oxychloride and catalyzer in filtrate; according to result, add terephthalic acid, sulfur oxychloride and catalyzer according to reactant ratio and carry out circulating reaction.The thick product filtering out obtains product through fusion-crystallization or underpressure distillation purification.Reaction process is as follows:
Described catalyzer be 1-hexyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-hexyl-3-Methylimidazole hexafluorophosphate or DMF, pyridine, tetraethylammonium bromide, benzyltriethylammoinium chloride, cetyl trimethylammonium bromide, tetra-n-butyl ammonium bromide one of them.Preferred: 1-hexyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-hexyl-3-Methylimidazole hexafluorophosphate or pyridine.
Sweating temperature when described fusion-crystallization is 65-78 DEG C, emits sweat, then is warming up to 85-90 DEG C and emits product.
Described underpressure distillation vacuum tightness is at 133-1330Pa, and it is 105-130 DEG C that cut receives temperature.
Catalyzer usage quantity is the 3%-7% of terephthalic acid quality.Sulfur oxychloride consumption is 2-4 times of terephthalic acid quality.
The tail gas HCl, the SO that generate for reaction
2, utilize cryogenic condensation device first to separate SO
2, reclaim and prepare sulfur oxychloride; HCl gas water absorbs or for the preparation of polyvinyl chloride.
Compared with prior art, main advantage is in the present invention: reaction finishes rear direct cold filtration and obtains thick product, and recycling raw materials and catalyzer, be different from existing method: steam excessive sulfur oxychloride, save energy and material consumption.Improve product purity by fusion-crystallization, not only economy but also environmental protection.Product yield is brought up to 90%-95%, and purity reaches more than 99.9%, more convenient to operate, is applicable to suitability for industrialized production.The p-phthaloyl chloride of being prepared by the method reaches the required every polymerization index of p-aramid fiber, can better meet the needs of p-aramid fiber.
Embodiment
For better the present invention will be described, for embodiment the present invention following detailed description, but the present invention is not limited to these.
Embodiment 1.
To reflux condensing tube is housed, temperature is taken into account in the there-necked flask of device for absorbing tail gas, add successively terephthalic acid 50 g, sulfur oxychloride 90 mL, 1-hexyl-3-methyl imidazolium tetrafluoroborate 3.0 g, tail gas absorbs with NaOH alkaline solution, starts induction stirring, is heated to 79
oc 10 h that reflux, reactant becomes shallow yellow transparent solution from white opacity suspension, finishes reaction, the cooling product of separating out.Filter, terephthalic acid, sulfur oxychloride and catalyst content in analyzing and testing filtrate, add accordingly according to reaction volume, carries out circulating reaction.The crude product filtering out is added in melting crystallizer to 65-72
oc program 4 h that heat up, emit sweat, and temperature is risen to 85
oc, emits product.Obtain white products 55.2 g, product purity 99.9%, fusing point: 82.5-83.0
oc, yield 90.3%.
The tail gas HCl, the SO that generate for reaction
2, utilize cryogenic condensation device first to separate SO
2, reclaim and prepare sulfur oxychloride; HCl gas water absorbs or for the preparation of polyvinyl chloride.
Embodiment 2.
To reflux condensing tube is housed, temperature is taken into account in the there-necked flask of device for absorbing tail gas, add successively terephthalic acid 50 g, sulfur oxychloride 80 mL, 1-hexyl-3-Methylimidazole hexafluorophosphate 4.5 g, tail gas absorbs with NaOH alkaline solution, starts induction stirring, is heated to 89
oc 4 h that reflux, reactant becomes shallow yellow transparent solution from white opacity suspension, finishes reaction, the cooling product of separating out.Filter, terephthalic acid, sulfur oxychloride and catalyst content in analyzing and testing filtrate, add accordingly according to reaction volume, carries out circulating reaction.The crude product filtering out is added in melting crystallizer to 72-78
oc program intensification 4h, emits sweat, and temperature is risen to 90
oc, emits product.Obtain white products 56.1 g, product purity 99.9%, fusing point: 82.0-82.5
oc, yield 91.8%.
The tail gas HCl, the SO that generate for reaction
2, utilize cryogenic condensation device first to separate SO
2, reclaim and prepare sulfur oxychloride; HCl gas water absorbs or for the preparation of polyvinyl chloride.
Embodiment 3.
To reflux condensing tube is housed, temperature is taken into account in the there-necked flask of device for absorbing tail gas, add successively terephthalic acid 50 g, sulfur oxychloride 80 mL, 1-butyl-3-methyl imidazolium tetrafluoroborate 3.5 g, tail gas absorbs with NaOH alkaline solution, starts induction stirring, is heated to 80
oc 10 h that reflux, reactant becomes shallow yellow transparent solution from white opacity suspension, finishes reaction, the cooling product of separating out.Filter, terephthalic acid, sulfur oxychloride and catalyst content in analyzing and testing filtrate, add accordingly according to reaction volume, carries out circulating reaction.By the crude product underpressure distillation filtering out, vacuum tightness is 133 Pa, and the cut at receiving 105-110 DEG C, obtains white products 58.0 g, product purity 99.9%, fusing point: 82.5-83.0
oc, yield 94.9%.
The tail gas HCl, the SO that generate for reaction
2, utilize cryogenic condensation device first to separate SO
2, reclaim and prepare sulfur oxychloride; HCl gas water absorbs or for the preparation of polyvinyl chloride.
Embodiment 4.
To reflux condensing tube is housed, temperature is taken into account in the there-necked flask of device for absorbing tail gas, adds successively terephthalic acid 50 g, sulfur oxychloride 80 mL, benzyltriethylammoinium chloride 4.0 g, tail gas absorbs with NaOH alkaline solution, starts induction stirring, is heated to 85
oc 7 h that reflux, reactant becomes shallow yellow transparent solution from white opacity suspension, finishes reaction, the cooling product of separating out.Filter, filtrate is detected terephthalic acid, sulfur oxychloride and the catalyst content in filtrate by analysis, adds accordingly according to reaction volume, carries out circulating reaction.By the crude product underpressure distillation filtering out, vacuum tightness is 1330 Pa, and the cut at receiving 125-130 DEG C, obtains white products 57.5 g, product purity 99.9%, fusing point: 82.0-82.5
oc, yield 94.1%.
The tail gas HCl, the SO that generate for reaction
2, utilize cryogenic condensation device first to separate SO
2, reclaim and prepare sulfur oxychloride; HCl gas water absorbs or for the preparation of polyvinyl chloride.
Embodiment 5.
To reflux condensing tube is housed, temperature is taken into account in the there-necked flask of device for absorbing tail gas, adds successively terephthalic acid 50 g, sulfur oxychloride 85 mL, pyridine 1.2 mL, tail gas absorbs with NaOH alkaline solution, starts induction stirring, is heated to 85
oc 6 h that reflux, reactant becomes shallow yellow transparent solution from white opacity suspension, finishes reaction, the cooling product of separating out.Filter, terephthalic acid, sulfur oxychloride and catalyst content in analyzing and testing filtrate, add accordingly according to reaction volume, carries out circulating reaction.By the crude product underpressure distillation filtering out, vacuum tightness is 550 Pa, and the cut at receiving 115-120 DEG C, obtains white products 57.7 g, product purity 99.9%, fusing point: 82.0-82.5
oc, yield 94.4%.
The tail gas HCl, the SO that generate for reaction
2, utilize cryogenic condensation device first to separate SO
2, reclaim and prepare sulfur oxychloride; HCl gas water absorbs or for the preparation of polyvinyl chloride.
The p-phthaloyl chloride technical indicator that the embodiment of the present invention makes is as following table:
| Outward appearance | White crystal |
| Fusing point | 82-83 oC |
| Content | ≥99.9% |
Claims (5)
1. the preparation of p-phthaloyl chloride and method of purification, is characterized in that, made by following processing step:
Taking terephthalic acid as raw material, under catalyst action, use sulfur oxychloride acidylate, 79-89 DEG C of reflux, the cooling crude product of separating out, filters, and analyzes the content of measuring terephthalic acid, sulfur oxychloride and catalyzer in filtrate, according to result, add terephthalic acid, sulfur oxychloride and catalyzer according to reactant ratio and carry out circulating reaction; The thick product filtering out obtains product through fusion-crystallization or underpressure distillation purification;
Described catalyzer be 1-hexyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-hexyl-3-Methylimidazole hexafluorophosphate or DMF, pyridine, tetraethylammonium bromide, benzyltriethylammoinium chloride, cetyl trimethylammonium bromide, tetra-n-butyl ammonium bromide one of them;
Sweating temperature when described fusion-crystallization is 65-78 DEG C, emits sweat, then is warming up to 85-90 DEG C and emits product;
Described underpressure distillation vacuum tightness is at 133-1330Pa, and it is 105-130 DEG C that cut receives temperature.
2. the preparation of p-phthaloyl chloride according to claim 1 and method of purification, it is characterized in that, catalyzer is preferred: 1-hexyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-hexyl-3-Methylimidazole hexafluorophosphate or pyridine.
3. the preparation of p-phthaloyl chloride according to claim 1 and method of purification, is characterized in that, catalyzer usage quantity is the 3%-7% of terephthalic acid quality.
4. the preparation of p-phthaloyl chloride according to claim 1 and method of purification, is characterized in that, sulfur oxychloride consumption is 2-4 times of terephthalic acid quality.
5. preparation and the method for purification of the p-phthaloyl chloride described in one of them according to claim 1-4, is characterized in that, the tail gas HCl, the SO that generate for reaction
2, utilize cryogenic condensation device first to separate SO
2, reclaim and prepare sulfur oxychloride; HCl gas water absorbs or for the preparation of polyvinyl chloride.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230703A (en) * | 2014-09-30 | 2014-12-24 | 烟台裕祥精细化工有限公司 | Method for synthesizing high-purity benzoyl chloride |
| CN105348087A (en) * | 2015-12-14 | 2016-02-24 | 山东凯盛新材料有限公司 | Continuous production process of parachlorobenzoyl chloride |
| CN105481681A (en) * | 2015-12-14 | 2016-04-13 | 山东凯盛新材料有限公司 | Preparation method of o-phthaloyl chloride |
| CN108017536A (en) * | 2017-11-29 | 2018-05-11 | 连云港市三联化工有限公司 | A kind of process for improving thionyl chloride utilization rate |
| CN108516930A (en) * | 2018-05-18 | 2018-09-11 | 宁夏大学 | A kind of synthetic method of 4- fluorine phthalic acid |
| CN109912404A (en) * | 2019-03-15 | 2019-06-21 | 方圆化工有限公司 | The purification process and equipment of trichloromethyl substituted benzene or corresponding carboxylic acid halides |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560146A (en) * | 2009-04-08 | 2009-10-21 | 淄博达隆制药科技有限公司 | Preparation method of paraphthaloyl chloride with high purity |
| CN101935276A (en) * | 2010-08-20 | 2011-01-05 | 南化集团研究院 | Synthetic method of p-phthaloyl chloride |
| CN103694113A (en) * | 2013-12-18 | 2014-04-02 | 河南能源化工集团研究院有限公司 | Method for preparing paraphthaloyl chloride |
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2014
- 2014-05-26 CN CN201410224413.8A patent/CN104003868B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560146A (en) * | 2009-04-08 | 2009-10-21 | 淄博达隆制药科技有限公司 | Preparation method of paraphthaloyl chloride with high purity |
| CN101935276A (en) * | 2010-08-20 | 2011-01-05 | 南化集团研究院 | Synthetic method of p-phthaloyl chloride |
| CN103694113A (en) * | 2013-12-18 | 2014-04-02 | 河南能源化工集团研究院有限公司 | Method for preparing paraphthaloyl chloride |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230703A (en) * | 2014-09-30 | 2014-12-24 | 烟台裕祥精细化工有限公司 | Method for synthesizing high-purity benzoyl chloride |
| CN105348087A (en) * | 2015-12-14 | 2016-02-24 | 山东凯盛新材料有限公司 | Continuous production process of parachlorobenzoyl chloride |
| CN105481681A (en) * | 2015-12-14 | 2016-04-13 | 山东凯盛新材料有限公司 | Preparation method of o-phthaloyl chloride |
| CN108017536A (en) * | 2017-11-29 | 2018-05-11 | 连云港市三联化工有限公司 | A kind of process for improving thionyl chloride utilization rate |
| CN108516930A (en) * | 2018-05-18 | 2018-09-11 | 宁夏大学 | A kind of synthetic method of 4- fluorine phthalic acid |
| CN109912404A (en) * | 2019-03-15 | 2019-06-21 | 方圆化工有限公司 | The purification process and equipment of trichloromethyl substituted benzene or corresponding carboxylic acid halides |
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| CN104003868B (en) | 2015-07-29 |
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