CN101935276A - Synthetic method of p-phthaloyl chloride - Google Patents
Synthetic method of p-phthaloyl chloride Download PDFInfo
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- CN101935276A CN101935276A CN2010102600933A CN201010260093A CN101935276A CN 101935276 A CN101935276 A CN 101935276A CN 2010102600933 A CN2010102600933 A CN 2010102600933A CN 201010260093 A CN201010260093 A CN 201010260093A CN 101935276 A CN101935276 A CN 101935276A
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Abstract
The invention belongs to the technical field of fine chemical industry synthesis and relates to a novel synthetic method of p-phthaloyl chloride by using terephthalic acid and thionyl chloride. The method adopts the terephthalic acid and the thionyl chloride as raw materials, reflux reaction is carried out for 4-12 hours at 70-90DEG C under the existence of a quaternary ammonium salt phase transfer catalyst, then unnecessary thionyl chloride is removed by distilling, reduced pressure distillation is carried out, and then fraction is collected at 115-120 DEG C (399Pa), thus obtaining the pure product p-phthaloyl chloride, the tail gas HCl which is generated in the reaction is absorbed by water, the tail gas SO2 is absorbed by alkali. Compared with a conventional method, the method has the characteristics of having simple making process and high yield rate, saving energy consumption, being beneficial to environmental protection, and the like.
Description
Technical field: the invention belongs to the fine chemistry industry technical field of organic synthesis, relate to a kind of novel method by terephthalic acid, sulfur oxychloride and the synthetic p-phthaloyl chloride of a small amount of phase-transfer catalyst.
Background technology: the method for present industrial production p-phthaloyl chloride has the sulfur oxychloride method and the p-Xylol photocatalysis chlorination method of terephthalic acid, accounts for leading and produce at present with terephthaldehyde's acid system.
The sulfur oxychloride chloride method of terephthalic acid: with the terephthalic acid is raw material, at a spot of catalyst n, under the effect of dinethylformamide (DMF) or pyridine; use the sulfur oxychloride acidylate; reflux 10-12h, a step obtains p-phthaloyl chloride, and yield is 84%.Reaction process such as figure below:
Technological process is: terephthalic acid and sulfur oxychloride are added in the reactor by ratio of components 1: 2.2～3.0 (ω), are catalyzer with pyridine or DMF, heating reflux reaction, and at 80 ℃ of 10～12h that reflux, unnecessary sulfur oxychloride is removed in redistillation.With the products therefrom underpressure distillation, collect 115～120 ℃ of (399Pa) cuts and finished product.
This method is present most widely used operational path, because technology maturation, domestic most of producer adopts this method to produce, the production technique of this method is simple, temperature of reaction is 80 ℃, reaction times is different a little with the kind and the quantity of catalyzer, be generally 8-12 hour, yield is about 85%, but quality product is lower, and purity is not high, and the p-phthaloyl chloride fusing point that makes only has about 80 ℃, can not be directly used in the synthetic of regenerated fiber, often need underpressure distillation can reach set quota for several times.
Summary of the invention: it is simple to the objective of the invention is to propose a kind of preparation technology, and the yield height is saved energy consumption, helps the novel method of the synthetic p-phthaloyl chloride of characteristics such as environment protection.
It is raw material that the present invention mainly adopts terephthalic acid, sulfur oxychloride, in the presence of the quaternary amine phase-transfer catalyst, at 70-90 ℃ of heating reflux reaction 4～12h, unnecessary sulfur oxychloride is removed in redistillation, 115～120 ℃ of (399Pa) cuts are collected in underpressure distillation, promptly get pure product p-phthaloyl chloride, the tail gas HCl water that reaction generates absorbs, tail gas SO
2Employing alkali lye absorbs.
The synthetic p-phthaloyl chloride technology of the inventive method is simple, the product purity height, and 82 ℃-84 ℃ of fusing points can be directly used in the synthetic of regenerated fiber; Do not need repeatedly rectification under vacuum, save energy consumption; And tail gas absorption back synthetic concentration of hydrochloric acid can reach more than 31%, and purity can reach more than 98% after the sulphite crystallization, also can produce certain value added.
In p-phthaloyl chloride synthetic, the mol ratio of terephthalic acid and sulfur oxychloride is 1: 2.3～1: 3.0, preferred 1: 2.5～1: 2.9.
The phase-transfer catalyst that can Gong select for use is the one or more combination thing in quaternary amine, quaternary amine alkali, quaternary alkylphosphonium salt, the cyclic crown ether class etc.Preferred quaternary amine, the preferred Dodecyl trimethyl ammonium chloride of quaternary amine, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, benzyl trimethyl ammonium chloride, benzyl tributyl ammonium chloride, tetramethyl ammonium chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, Trimethyllaurylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, benzyl tributyl brometo de amonio, 4 bromide.One or more combination thing in preferred again Tetrabutyl amonium bromide, cetyl trimethylammonium bromide, the octadecyl trimethyl ammonium chloride.
The mass ratio of phase-transfer catalyst and terephthalic acid is 0.002: 1～0.01: 1, preferred 0.004: 1～0.008: 1.
Tail gas HCl, SO that reaction generates
2Adopt water and alkaline solution to absorb respectively, wherein first water absorbs HCl and a small amount of SO
2, absorb SO with alkali lye again
2, wherein absorbing the water yield of HCl and the mass ratio of terephthalic acid is 0.7: 1～7: 1, preferred 0.7: 1～1: 1, absorbs SO
2Alkali adopt a kind of in subcarbonate or supercarbonate or the alkaline earth metal hydroxides etc., preferred sodium hydroxide, potassium hydroxide, yellow soda ash, a kind of in the salt of wormwood, preferred again sodium hydroxide, potassium hydroxide.The concentration of alkali is 10%～30%, preferred 14%～16%.
The present invention compares synthetic technology in the past, and it is simple to have preparation technology, and the yield height is saved energy consumption, helps characteristics such as environment protection.
Explanation the present invention that can be detailed in following examples, but the present invention is not limited to these.
Embodiment: the present invention is described in detail by following example:
Example 1. is the terephthalic acid of 70g, the sulfur oxychloride of 130g, and the phase-transfer catalyst Tetrabutyl amonium bromide of 0.4g adds in the Erlenmeyer flask of band condensing reflux and device for absorbing tail gas, and the water yield that wherein absorbs HCl is 60mL, absorbs SO
2NaOH concentration be 14%, magnetic agitation 8h in 80 ℃ of oil baths, reactant becomes weak yellow liquid by the white casse suspension liquid, the distillation remove unnecessary sulfur oxychloride, underpressure distillation is collected 115～120 ℃ of (399Pa) cuts and is got colourless liquid.Crystallisation by cooling gets clear crystal 83g, product purity 99.9%, and fusing point: 82 ℃～84 ℃, product yield 96.9%.Concentration of hydrochloric acid 31.6% in the tail gas absorption liquid, concentration of sodium sulfite 16.7%.
Example 2. is the terephthalic acid of 70g, the sulfur oxychloride of 130g, and the phase-transfer catalyst Tetrabutyl amonium bromide of 0.5g adds in the Erlenmeyer flask of band condensing reflux and device for absorbing tail gas, and the water yield that wherein absorbs HCl is 100mL, absorbs SO
2NaOH concentration be 16%, magnetic agitation 7.5h in 80 ℃ of oil baths, reactant becomes weak yellow liquid by the white casse suspension liquid, unnecessary sulfur oxychloride is removed in distillation, and underpressure distillation gets colourless liquid, crystallisation by cooling gets clear crystal 81g, product purity 99.9%, fusing point: 82 ℃～84 ℃, product yield 94.6%.Concentration of hydrochloric acid 22.5% in the tail gas absorption liquid, concentration of sodium sulfite 18.6%.
Example 3. is the terephthalic acid of 70g, the sulfur oxychloride of 130g, and the phase-transfer catalyst Tetrabutyl amonium bromide of 0.6g adds in the Erlenmeyer flask of band condensing reflux and device for absorbing tail gas, and the water yield that wherein absorbs HCl is 200mL, absorbs SO
2NaOH concentration be 12%, magnetic agitation 7h in 80 ℃ of oil baths, reactant becomes weak yellow liquid by the white casse suspension liquid, unnecessary sulfur oxychloride is removed in distillation, and underpressure distillation gets colourless liquid, crystallisation by cooling gets clear crystal 80g, product purity 99.9%, fusing point: 82 ℃～84 ℃, product yield 93.5%.Concentration of hydrochloric acid 13.0% in the tail gas absorption liquid, concentration of sodium sulfite 12.5%.
Example 4. is the terephthalic acid of 70g, the sulfur oxychloride of 130g, and the phase-transfer catalyst Tetrabutyl amonium bromide of 0.4g adds in the Erlenmeyer flask of band condensing reflux and device for absorbing tail gas, and the water yield that wherein absorbs HCl is 100mL, absorbs SO
2NaOH concentration be 23%, magnetic agitation 8h in 80 ℃ of oil baths, reactant becomes weak yellow liquid by the white casse suspension liquid, unnecessary sulfur oxychloride is removed in distillation, and underpressure distillation gets colourless liquid, crystallisation by cooling gets clear crystal 82.8g, product purity 99.9%, fusing point: 82 ℃～84 ℃, product yield 96.7%.Concentration of hydrochloric acid 20.8% in the tail gas absorption liquid, concentration of sodium sulfite 12.9%.
Example 5. is the terephthalic acid of 70g, the sulfur oxychloride of 147g, and the phase-transfer catalyst Tetrabutyl amonium bromide of 0.6g adds in the Erlenmeyer flask of band condensing reflux and device for absorbing tail gas, and the water yield that wherein absorbs HCl is 200mL, absorbs SO
2NaOH concentration be 12%, magnetic agitation 8h in 80 ℃ of oil baths, reactant becomes weak yellow liquid by the white casse suspension liquid, unnecessary sulfur oxychloride is removed in distillation, and underpressure distillation gets colourless liquid, crystallisation by cooling gets clear crystal 80.0g, product purity 99.9%, fusing point: 82 ℃～84 ℃, product yield 93.4%.Concentration of hydrochloric acid 12.9% in the tail gas absorption liquid, concentration of sodium sulfite 12.6%.
Example 6. is the terephthalic acid of 70g, the sulfur oxychloride of 138g, and the phase-transfer catalyst cetyl trimethylammonium bromide of 0.6g adds in the Erlenmeyer flask of band condensing reflux and device for absorbing tail gas, and the water yield that wherein absorbs HCl is 200mL, absorbs SO
2NaOH concentration be 15%, magnetic agitation 9h in 80 ℃ of oil baths, reactant becomes weak yellow liquid by the white casse suspension liquid, unnecessary sulfur oxychloride is removed in distillation, and underpressure distillation gets colourless liquid, crystallisation by cooling gets clear crystal 78.0g, product purity 99.9%, fusing point: 82 ℃～84 ℃, product yield 91.1%.Concentration of hydrochloric acid 11.9% in the tail gas absorption liquid, concentration of sodium sulfite 18.7%.
Example 7. is the terephthalic acid of 70g, the sulfur oxychloride of 130g, and the phase-transfer catalyst octadecyl trimethyl ammonium chloride of 0.5g adds in the Erlenmeyer flask of band condensing reflux and device for absorbing tail gas, and the water yield that wherein absorbs HCl is 200mL, absorbs SO
2NaOH concentration be 15%, magnetic agitation 10h in 80 ℃ of oil baths, reactant becomes weak yellow liquid by the white casse suspension liquid, unnecessary sulfur oxychloride is removed in distillation, and underpressure distillation gets colourless liquid, crystallisation by cooling gets clear crystal 77.5g, product purity 99.9%, fusing point: 82 ℃～84 ℃, product yield 90.5%.Concentration of hydrochloric acid 12.4% in the tail gas absorption liquid, concentration of sodium sulfite 18.0%.
Claims (9)
1. p-phthaloyl chloride synthetic method, it is characterized in that with terephthalic acid, sulfur oxychloride be raw material, in the presence of the quaternary amine phase-transfer catalyst, at 70-90 ℃ of heating reflux reaction 4～12h, unnecessary sulfur oxychloride is removed in redistillation, 115～120 ℃, 399Pa cut are collected in underpressure distillation, promptly get pure product p-phthaloyl chloride; The mol ratio of terephthalic acid and sulfur oxychloride is 1: 2.3～1: 3.0, and the mass ratio of phase-transfer catalyst and terephthalic acid is 0.002: 1～0.01: 1.
2. method according to claim 1, the mol ratio that it is characterized in that terephthalic acid and sulfur oxychloride is 1: 2.5～1: 2.9.
3. method according to claim 1 is characterized in that the quaternary amine phase-transfer catalyst is for being selected from Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, benzyl trimethyl ammonium chloride, benzyl tributyl ammonium chloride, tetramethyl ammonium chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, Trimethyllaurylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, the octadecyl trimethylammonium bromide, benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, benzyl tributyl brometo de amonio, one or several mixtures in the 4 bromide.
4. according to claim 1 or 3 described methods, the mass ratio that it is characterized in that phase-transfer catalyst and terephthalic acid is 0.004: 1～0.008: 1.
5. method according to claim 1 is characterized in that reacting tail gas HCl, the SO of generation
2, first water absorbs HCl, absorbs SO with alkali lye again
2
6. method according to claim 1 or 5 is characterized in that absorbing the water yield of HCl and the mass ratio of terephthalic acid is 0.7: 1～7: 1.
7. method according to claim 1 or 5 is characterized in that absorbing the water yield of HCl and the mass ratio of terephthalic acid is 0.7: 1～1: 1.
8. method according to claim 1 or 5 is characterized in that absorbing SO
2Alkali lye be selected from a kind of in subcarbonate or supercarbonate or the alkaline earth metal hydroxides, the concentration expressed in percentage by weight of alkali lye is 10%～30%.
9. method according to claim 1 or 5 is characterized in that absorbing SO
2Alkali lye be selected from sodium hydroxide, potassium hydroxide, yellow soda ash, a kind of in the salt of wormwood, the concentration expressed in percentage by weight of alkali lye is 14%～16%.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225895A (en) * | 2011-04-22 | 2011-10-26 | 仪征华纳生物科技有限公司 | Preparation method of terephthaloyl chloride |
| CN102796004A (en) * | 2012-08-28 | 2012-11-28 | 山东凯盛新材料股份有限公司 | Synthesis method for paranitrobenzoyl chloride |
| CN102976988A (en) * | 2012-12-24 | 2013-03-20 | 三门峡奥科化工有限公司 | Synthesis technique of 2-thionaphthol |
| CN103641710A (en) * | 2013-12-04 | 2014-03-19 | 山东凯盛新材料股份有限公司 | Synthesis method for trimesoyl 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 |
| CN103724188A (en) * | 2013-12-18 | 2014-04-16 | 河南能源化工集团研究院有限公司 | Method for preparing paraphthaloyl chloride |
| CN104003868A (en) * | 2014-05-26 | 2014-08-27 | 中国平煤神马能源化工集团有限责任公司技术中心 | Preparation and purification method of paraphthaloyl chloride with high purity |
| CN104138703A (en) * | 2014-08-06 | 2014-11-12 | 山东凯盛新材料有限公司 | Waste gas treatment process and device in isophthaloyl dichloride/paraphthaloyl chloride production |
| CN104447299A (en) * | 2014-12-12 | 2015-03-25 | 山东凯盛新材料有限公司 | M-phthaloyl chloride production process and production device thereof |
| CN105348077A (en) * | 2015-12-14 | 2016-02-24 | 山东凯盛新材料有限公司 | Preparation method of p-phthaloyl chloride |
| CN105348078A (en) * | 2015-12-14 | 2016-02-24 | 山东凯盛新材料有限公司 | Recover method of thionyl chloride in continuous preparation process of p-phthaloyl chloride |
| CN107789855A (en) * | 2017-11-30 | 2018-03-13 | 山东凯盛新材料股份有限公司 | Acyl chlorides rectification under vacuum waste water reclaiming device and method |
| CN109393611A (en) * | 2018-10-25 | 2019-03-01 | 广州市雅娜琪服装有限公司 | A kind of resistant nanometer garment material and preparation method thereof |
| CN111039780A (en) * | 2019-12-31 | 2020-04-21 | 宁夏丰华生物科技有限公司 | Process for producing aramid polymerized monomer by thionyl chloride method |
| CN112724013A (en) * | 2020-12-29 | 2021-04-30 | 山东凯盛新材料股份有限公司 | Preparation method of isophthaloyl dichloride |
| CN112876351A (en) * | 2020-12-29 | 2021-06-01 | 山东凯盛新材料股份有限公司 | Preparation method of paraphthaloyl chloride |
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Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225895A (en) * | 2011-04-22 | 2011-10-26 | 仪征华纳生物科技有限公司 | Preparation method of terephthaloyl chloride |
| CN102796004A (en) * | 2012-08-28 | 2012-11-28 | 山东凯盛新材料股份有限公司 | Synthesis method for paranitrobenzoyl chloride |
| CN102976988B (en) * | 2012-12-24 | 2014-06-18 | 三门峡奥科化工有限公司 | Synthesis technique of 2-thionaphthol |
| CN102976988A (en) * | 2012-12-24 | 2013-03-20 | 三门峡奥科化工有限公司 | Synthesis technique of 2-thionaphthol |
| CN103641710A (en) * | 2013-12-04 | 2014-03-19 | 山东凯盛新材料股份有限公司 | Synthesis method for trimesoyl chloride |
| CN103724188B (en) * | 2013-12-18 | 2015-07-01 | 河南能源化工集团研究院有限公司 | Method for preparing paraphthaloyl chloride |
| CN103724188A (en) * | 2013-12-18 | 2014-04-16 | 河南能源化工集团研究院有限公司 | Method for preparing paraphthaloyl 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 |
| CN104003868A (en) * | 2014-05-26 | 2014-08-27 | 中国平煤神马能源化工集团有限责任公司技术中心 | Preparation and purification method of paraphthaloyl chloride with high purity |
| CN104138703B (en) * | 2014-08-06 | 2016-01-20 | 山东凯盛新材料有限公司 | Between/paraphthaloyl chloride produce in waste gas treatment process and device |
| CN104138703A (en) * | 2014-08-06 | 2014-11-12 | 山东凯盛新材料有限公司 | Waste gas treatment process and device in isophthaloyl dichloride/paraphthaloyl chloride production |
| CN104447299B (en) * | 2014-12-12 | 2016-06-01 | 山东凯盛新材料有限公司 | M-phthaloyl chloride production technique and production equipment thereof |
| CN104447299A (en) * | 2014-12-12 | 2015-03-25 | 山东凯盛新材料有限公司 | M-phthaloyl chloride production process and production device thereof |
| CN105348077A (en) * | 2015-12-14 | 2016-02-24 | 山东凯盛新材料有限公司 | Preparation method of p-phthaloyl chloride |
| CN105348078A (en) * | 2015-12-14 | 2016-02-24 | 山东凯盛新材料有限公司 | Recover method of thionyl chloride in continuous preparation process of p-phthaloyl chloride |
| CN107789855A (en) * | 2017-11-30 | 2018-03-13 | 山东凯盛新材料股份有限公司 | Acyl chlorides rectification under vacuum waste water reclaiming device and method |
| CN107789855B (en) * | 2017-11-30 | 2020-04-14 | 山东凯盛新材料股份有限公司 | Acyl chloride vacuum rectification wastewater recovery device and method |
| CN109393611A (en) * | 2018-10-25 | 2019-03-01 | 广州市雅娜琪服装有限公司 | A kind of resistant nanometer garment material and preparation method thereof |
| CN109393611B (en) * | 2018-10-25 | 2020-12-18 | 江阴市伊芙特制衣有限公司 | Stain-resistant nano garment fabric and preparation method thereof |
| CN111039780A (en) * | 2019-12-31 | 2020-04-21 | 宁夏丰华生物科技有限公司 | Process for producing aramid polymerized monomer by thionyl chloride method |
| CN112724013A (en) * | 2020-12-29 | 2021-04-30 | 山东凯盛新材料股份有限公司 | Preparation method of isophthaloyl dichloride |
| CN112876351A (en) * | 2020-12-29 | 2021-06-01 | 山东凯盛新材料股份有限公司 | Preparation method of paraphthaloyl chloride |
| CN112724013B (en) * | 2020-12-29 | 2022-11-22 | 山东凯盛新材料股份有限公司 | Preparation method of isophthaloyl dichloride |
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