CN104478696A - Preparation method of terephthaloyl chloride - Google Patents
Preparation method of terephthaloyl chloride Download PDFInfo
- Publication number
- CN104478696A CN104478696A CN201410764744.0A CN201410764744A CN104478696A CN 104478696 A CN104478696 A CN 104478696A CN 201410764744 A CN201410764744 A CN 201410764744A CN 104478696 A CN104478696 A CN 104478696A
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- CN
- China
- Prior art keywords
- preparation
- phthaloyl chloride
- reaction
- trichloromethyl
- crude product
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention belongs to the field of organic chemical synthesis and in particular relates to a preparation method of terephthaloyl chloride. The preparation method comprises the following steps: under irradiation of an LED (light-emitting diode) light source, introducing excessive chlorine to p-xylene to react to obtain a 1,4-bis(trichloromethyl)benzene crude product; enabling the 1,4-bis(trichloromethyl)benzene crude product to react with p-phthalic acid in the presence of a catalyst until no hydrogen chloride is released and carrying out vacuum distillation on an obtained reaction liquid to obtain terephthaloyl chloride. The preparation method has the beneficial effects that the preparation method has the advantages of easily obtained raw materials, low cost, easiness in tail gas treatment, and the like and is suitable for industrial production; the melting point, purity and yield of prepared terephthaloyl chloride are respectively 82-83 DEG C, more than 99.9% and more than 95%; any solvent is not needed to be mixed, the catalyst is recycled, and the high purity of the product is kept.
Description
Technical field
The invention belongs to organic chemical synthesis field, be specifically related to a kind of preparation method of p-phthaloyl chloride.
Background technology
P-phthaloyl chloride is important Organic Chemicals, is the raw material of the polymkeric substance such as polymeric amide, polyester.It is the monomer of synthesis special fibre, aramid fiber, polyamide fibre toughener can be made, aramid fiber is a kind of high-performance synthon, there is superstrength, high temperature resistant, acid and alkali-resistance, the advantage such as lightweight, toughness and intensity respectively can 2 times and 6 times of superior matter steel, in aircraft, rocket, guided missile and shellproof equipment.
P-phthaloyl chloride take terephthalic acid as the synthesis technique of raw material, different according to chloride reagent, is mainly divided into sulfur oxychloride method, phosphorus pentachloride method, phosphorus trichloride method photoreactive gas method.Sulfur oxychloride method take sulfur oxychloride as chlorizating agent, and terephthalic acid is raw material, and DMF or pyridine are catalyst preparing p-phthaloyl chloride.The method due to DMF unstable, SOCl
2reaction generates (chlorine methylene radical) alkyl dimethyl ammonium chloride, and cause not easily separation purity low, after need carrying out repeatedly underpressure distillation, product purity just can reach more than 99%.Chlorizating agent in phosphorus pentachloride method is solid phosphorus pentachloride, reinforced more difficult comparatively speaking, adds phosphorus pentachloride and easily absorbs water, generate the accuracy that hydrogenchloride affects ingredient proportion, and terephthalic acid itself is also solid, both not easily mix, operation inconvenience.The temperature of reaction that phosphorus trichloride method needs is higher, and time length, process conditions more complicated, add the purification of by product phosphorus oxychloride, both etching apparatus, turn increase production cost.Phosgenation operational path, need special generation phosgene or buying phosgene, phosgene belongs to hypertoxic product, need in reaction to use solvent, by product is also gas, easily causes phosgene to discharge with by product, to safety and requirement of shelter very high, also to increase solvent recovery unit in addition, production cost is increased considerably.
Summary of the invention
The object of this invention is to provide a kind of preparation method of p-phthaloyl chloride, have that raw material is easy to get, cost is low, tail gas easily processes, advantage to being safe from harm property of environment, be applicable to suitability for industrialized production.
The preparation method of p-phthaloyl chloride of the present invention, step is as follows:
(1) under LED light source irradiates, in p-Xylol, pass into excessive chlorine reaction, obtain Isosorbide-5-Nitrae-two (trichloromethyl) benzene crude product;
(2) get obtained Isosorbide-5-Nitrae-two (trichloromethyl) the benzene crude product of step (1) and terephthalic acid, react under catalyst action, until release without hydrogen chloride gas, gained reaction solution obtains p-phthaloyl chloride through rectification under vacuum.
LED light source wavelength region described in step (1) is 380-480nm.
The amount of substance of the chlorine described in step (1) is the 120-140% of theoretical amount.
Temperature of reaction described in step (1) is 130-150 DEG C, and the reaction times is 8-10 hour.
The mass ratio of Isosorbide-5-Nitrae-two (trichloromethyl) the benzene crude product described in step (2) and terephthalic acid is 1:0.50-0.56.
Catalyzer described in step (2) is ZnCl
2or FeCl
3, preferred ZnCl
2.
Catalyst levels described in step (2) is the 0.1-0.5% of terephthalic acid quality.
Temperature of reaction described in step (2) is 120-140 DEG C, and the reaction times is 6-8 hour.
Paraphenylene terephthalamide's cl content described in step (2) is greater than 99.9%, and yield is greater than 95%.
Experimental principle:
The LED ultraviolet lamp wavelength region 380-480nm used in the present invention's reaction has that energy is high, low in energy consumption, the life-span is long, the features such as wavelength region is adjustable, and attended operation is simple.Especially, when carrying out chlorination reaction, the size of the required photodissociation energy of reaction can be participated according to chlorine molecule, select suitable LED light source wavelength region.Wavelength is too short, although energy is high, is unfavorable for that chlorination reaction controls, easily side reaction occurs, cause reaction solution color burn, even carbonization, hinder effective wavelength through, carrying out smoothly of inhibited reaction, cause quality product and yield to reduce; Wavelength is long, then energy is low, inoperative to reaction, causes waste.
Use metal chloride catalyst to be conducive to benzene ring side chain and remove hydrogenchloride, promote the generation of reaction, reduce by product and generate.
The present invention compared with prior art, has following beneficial effect:
The present invention has raw material and is easy to get, and cost is low, and tail gas such as easily to process at the advantage, is applicable to suitability for industrialized production.The p-phthaloyl chloride that the present invention obtains, fusing point is 82-83 DEG C, and purity reaches more than 99.9%, and yield is greater than more than 95%.Be mixed into without the need to any solvent in the present invention, catalyst recirculation uses, and maintains the high purity of product.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
(1) getting p-Xylol 100g, is, under 380-390nm LED light source irradiates, pass into chlorine 481.5g in 130 DEG C to it at wavelength, through reaction in 8 hours, and obtained Isosorbide-5-Nitrae-two (trichloromethyl) benzene crude product 289.6g, chromatographic content is 92.0%;
(2) by obtained for step (1) 1,4-bis-(trichloromethyl) benzene crude product and terephthalic acid 144.8g add in reaction flask, under the katalysis of 0.145g zinc chloride, react 8 hours at 120 DEG C, until release without hydrogen chloride gas, gained reaction solution obtains p-phthaloyl chloride 363.71g through rectification under vacuum, and chromatographic content is 99.93%, fusing point 82.3 DEG C, total yield of products is 95.1% (by p-Xylol).
Embodiment 2
(1) getting p-Xylol 100g, is, under 420-430nm LED light source irradiates, pass into chlorine 521.6g in 140 DEG C to it at wavelength, through reaction in 9 hours, and obtained Isosorbide-5-Nitrae-two (trichloromethyl) benzene crude product 290.27g, chromatographic content is 95.17%;
(2) by obtained for step (1) 1,4-bis-(trichloromethyl) benzene crude product and terephthalic acid 153.8g add in reaction flask, under the effect of 0.461g Ferric Chloride, react 7 hours at 130 DEG C, until release without hydrogen chloride gas, gained reaction solution obtains p-phthaloyl chloride 371.40g through rectification under vacuum, and chromatographic content is 99.91%, fusing point 82.2 DEG C, product yield is 97.1% (by p-Xylol).
Embodiment 3
(1) getting p-Xylol 100g, is, under 470-480nm LED light source irradiates, pass into chlorine 561.7g in 150 DEG C to it at wavelength, through reaction in 10 hours, and obtained Isosorbide-5-Nitrae-two (trichloromethyl) benzene crude product 290.34g, chromatographic content is 96.0%;
(2) by obtained for step (1) 1,4-bis-(trichloromethyl) benzene crude product and terephthalic acid 162.6g add in reaction flask, under zinc chloride 0.813g katalysis, react 6 hours at 140 DEG C, until release without hydrogen chloride gas, gained reaction solution obtains p-phthaloyl chloride 375.57g through rectification under vacuum, and chromatographic content is 99.94%, fusing point 82.5 DEG C, total yield of products is 98.2% (by p-Xylol).
Claims (8)
1. a preparation method for p-phthaloyl chloride, is characterized in that step is as follows:
(1) under LED light source irradiates, in p-Xylol, pass into excessive chlorine reaction, obtain Isosorbide-5-Nitrae-two (trichloromethyl) benzene crude product;
(2) get obtained Isosorbide-5-Nitrae-two (trichloromethyl) the benzene crude product of step (1) and terephthalic acid, react under catalyst action, until release without hydrogen chloride gas, gained reaction solution obtains p-phthaloyl chloride through rectification under vacuum.
2. the preparation method of p-phthaloyl chloride according to claim 1, is characterized in that the LED light source wavelength region described in step (1) is 380-480nm.
3. the preparation method of p-phthaloyl chloride according to claim 1, is characterized in that the amount of substance of the chlorine described in step (1) is the 120-140% of theoretical amount.
4. the preparation method of p-phthaloyl chloride according to claim 1, it is characterized in that the temperature of reaction described in step (1) is 130-150 DEG C, the reaction times is 8-10 hour.
5. the preparation method of p-phthaloyl chloride according to claim 1, is characterized in that the mass ratio of Isosorbide-5-Nitrae-two (trichloromethyl) the benzene crude product described in step (2) and terephthalic acid is 1:0.50-0.56.
6. the preparation method of p-phthaloyl chloride according to claim 1, is characterized in that the catalyzer described in step (2) is ZnCl
2or FeCl
3.
7. the preparation method of p-phthaloyl chloride according to claim 1, is characterized in that the catalyst levels described in step (2) is the 0.1-0.5% of terephthalic acid quality.
8. the preparation method of p-phthaloyl chloride according to claim 1, it is characterized in that the temperature of reaction described in step (2) is 120-140 DEG C, the reaction times is 6-8 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764744.0A CN104478696A (en) | 2014-12-12 | 2014-12-12 | Preparation method of terephthaloyl chloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764744.0A CN104478696A (en) | 2014-12-12 | 2014-12-12 | Preparation method of terephthaloyl chloride |
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|---|---|
| CN104478696A true CN104478696A (en) | 2015-04-01 |
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|---|---|---|---|
| CN201410764744.0A Pending CN104478696A (en) | 2014-12-12 | 2014-12-12 | Preparation method of terephthaloyl chloride |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4029560A (en) * | 1975-04-01 | 1977-06-14 | Mitsubishi Gas Chemical Company, Inc. | Process for producing α,α,α,α',α',α'-hexachloroxylene |
| US4165337A (en) * | 1976-10-25 | 1979-08-21 | Mitsubishi Gas Chemical Company, Inc. | Process for producing phthaloyl dichlorides of high purity |
| CN1948245A (en) * | 2006-04-14 | 2007-04-18 | 浙江巍华化工有限公司 | Method of producing chlorobenzyl by photochlorination |
-
2014
- 2014-12-12 CN CN201410764744.0A patent/CN104478696A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4029560A (en) * | 1975-04-01 | 1977-06-14 | Mitsubishi Gas Chemical Company, Inc. | Process for producing α,α,α,α',α',α'-hexachloroxylene |
| US4165337A (en) * | 1976-10-25 | 1979-08-21 | Mitsubishi Gas Chemical Company, Inc. | Process for producing phthaloyl dichlorides of high purity |
| CN1948245A (en) * | 2006-04-14 | 2007-04-18 | 浙江巍华化工有限公司 | Method of producing chlorobenzyl by photochlorination |
Non-Patent Citations (1)
| Title |
|---|
| 魏文珑等: "邻、间、对苯二甲酰氯的合成工艺", 《山西化工》, vol. 29, no. 1, 28 February 2009 (2009-02-28), pages 20 - 24 * |
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