CN105646419A - Method for crystallizing and purifying 3-chlorophthalic anhydride - Google Patents
Method for crystallizing and purifying 3-chlorophthalic anhydride Download PDFInfo
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- CN105646419A CN105646419A CN201610169663.5A CN201610169663A CN105646419A CN 105646419 A CN105646419 A CN 105646419A CN 201610169663 A CN201610169663 A CN 201610169663A CN 105646419 A CN105646419 A CN 105646419A
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- benzoic anhydride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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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
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/573—Separation; Purification; Stabilisation; Use of additives
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Abstract
The invention relates to a method for crystallizing and purifying 3-chlorophthalic anhydride. The method comprises the following steps of mixing a chlorophthalic anhydride mixture containing the 3-chlorophthalic anhydride with a mixed solvent under a stirring action, heating to 55 to 65 DEG C, and completely dissolving the mixture; cooling the material to 5 to 15 DEG C in a cooling crystallization manner so as to obtain crystal suspension of the 3-chlorophthalic anhydride; performing filtering, solvent washing and drying treatment on the suspension so as to obtain a 3-chlorophthalic anhydride crystal product. The method disclosed by the invention has the advantages that the purity and yield of the crystallization product are effectively guaranteed by means of selecting the type and composition proportion of the mixed solvent and controlling the crystallization operation conditions at the same time by utilization of the difference of dissolvability of the 3-chlorophthalic anhydride and other chlorophthalic anhydride products in different solvents; the 3-chlorophthalic anhydride crystallization product with the purity of 99.0 percent or higher and the crystallization yield of 70.8 percent or higher can be obtained; the effects of low operation temperature, less energy consumption, strong operability and higher industrial application value are achieved, and the obtained 3-chlorophthalic anhydride product is high in purity and yield.
Description
Technical field
The invention belongs to technical field of chemical separation, in particular to a kind of method of crystallization and purification 3-chloro-benzoic anhydride.
Background technology
Single chloro-benzoic anhydride comprises two kinds of isomerss: 3-chloro-benzoic anhydride and 4-chloro-benzoic anhydride, their English name is respectively 3-chlorophthalicanhydride and 4-chlorophthalicanhydride, fusing point is respectively 123 DEG C and 96 DEG C, and in solid-state under normal temperature, molecular formula is C8H3ClO3, chemical structural formula is as follows respectively:
3-chloro-benzoic anhydride and 4-chloro-benzoic anhydride are all important industrial chemicals, it is applied in the fields such as medicine, dyestuff, agricultural chemicals and engineering materials widely, it is possible to be used for synthesizing the intermediate of the polyimide such as single ether dianhydride, diaether dianhydride, ketone two acid anhydride, biphenyl dianhydride, sulphur ether dianhydride, diphenyl sulfone dianhydride, bisphenol A dianhydride.
The synthetic method of 3-chloro-benzoic anhydride has multiple, and at present, main synthetic method has: mononitro-benzene acid anhydride chlorine for the chlorination process of method, phthalic acid and sodium salt thereof, 3-chloro-o-xylene oxidation style etc. But, in the 3-chloro-benzoic anhydride product obtained by synthesis method, often containing a certain amount of 4-chloro-benzoic anhydride and other chloro-benzoic anhydride mixtures, cause 3-chloro-benzoic anhydride purity in product low, and after only purity reaches certain requirement, 3-chloro-benzoic anhydride product could realize industrial application, therefore just needs to be purified by mixture, obtains 3-chloro-benzoic anhydride sterling.
At present, the method of purification 3-chloro-benzoic anhydride has been studied by more existing documents, Chinese patent CN1186063 utilizes the method for rectification under vacuum to be separated by 3-chloro-benzoic anhydride, its pressure range is 6��100kPa, temperature range is 180��215 DEG C, the purity obtaining 3-chloro-benzoic anhydride solid phase prod is 97.7%, and receipts rate is 49.9%; Solid mixture is heated to 90��150 DEG C by Chinese patent CN103819435 makes its melting, utilize the different melting points of other chloro-benzoic anhydrides such as 3-chloro-benzoic anhydride and 4-chloro-benzoic anhydride, by the mode of fusion-crystallization, 3-chloro-benzoic anhydride is purified, the purity of the 3-chloro-benzoic anhydride crystal product obtained is 99.5%, and receipts rate is 54.8%.It may be seen that the product of rectification method is not high in purity and receipts rate, although the product purity of fusion-crystallization method is higher, but it is not its complicated operation, preparation cycle are long, still high in receipts rate, and these two kinds of separation methods, product is non-crystalline state, all there is the problem that energy consumption is higher. Therefore, it is necessary to develop the 3-chloro-benzoic anhydride method for purifying and separating that a kind of preparation method is simple, process energy consumption is low, product purity height, process receipts rate are high.
Summary of the invention
In order to overcome existing 3-chloro-benzoic anhydride purifies and separates technology Problems existing, the present invention discloses a kind of method of crystallization and purification 3-chloro-benzoic anhydride, utilize the difference on 3-chloro-benzoic anhydride and other chloro-benzoic anhydride product solubilities, by the solution crystallization mode of crystallisation by cooling, by 3-chloro-benzoic anhydride purifies and separates.
The technical scheme of the present invention is: under stirring action, is mixed with mixed solvent by the chloro-benzoic anhydride mixture containing 3-chloro-benzoic anhydride, is heated to 55��65 DEG C, mixture is dissolved completely; Then adopt the mode of crystallisation by cooling that material is cooled to 5��15 DEG C, obtain the crystal suspension liquid of 3-chloro-benzoic anhydride, filtration, solvent wash, drying, obtain 3-chloro-benzoic anhydride crystal product.
In described chloro-benzoic anhydride mixture, 3-chloro-benzoic anhydride quality accounts for more than the 60% of mixture total mass, the residuum of chloro-benzoic anhydride mixture after the Reactive Synthesis product or purifying list chloro-benzoic anhydride of upstream.
Described mixed solvent is made up of solvent orange 2 A and solvent B two portions, wherein solvent orange 2 A is selected from methyl alcohol, ethanol, methyl acetate, ethyl acetate or 1, one in 4-dioxane, the one that solvent B is selected from tetracol phenixin, hexanaphthene, normal hexane, sherwood oil or tertiary amyl alcohol, the mass ratio of solvent orange 2 A and solvent B is 1.5��3:1.
The consumption of described chloro-benzoic anhydride mixture and the mass ratio of mixed solvent consumption are 0.5��1:1.
In described crystallisation by cooling process, first with the rate of temperature fall of 2��6 DEG C/h, material is cooled to 20��35 DEG C, crystallize out, constant temperature 0.5��1h, then with the rate of temperature fall of 5��10 DEG C/h, it is cooled to 5��15 DEG C, constant temperature 0.5��1h.
The one that described cleaning solvent is selected from tetracol phenixin, hexanaphthene, sherwood oil, normal hexane or tertiary amyl alcohol, its temperature is 5��15 DEG C.
Described drying conditions is dry 4��6h at 50��60 DEG C.
The method of solution crystal process purification 3-chloro-benzoic anhydride of the present invention, utilize the difference of solubleness in different solvents of 3-chloro-benzoic anhydride and other chloro-benzoic anhydride products, by selecting mixed solvent kind and proportion of composing, simultaneously crystallization control operational condition, thus effectively ensure purity and the receipts rate of crystalline product. The 3-chloro-benzoic anhydride crystalline product of purity more than 99.0%, crystallization yield more than 70.8% can be obtained, or the 3-chloro-benzoic anhydride crystalline product of purity more than 99.5%, crystallization yield more than 68.1%. Crystal product form as shown in Figure 1, good product mobility, it may also be useful to convenient. And existing product obtains by rectification method or fusion-crystallization method, it is at high temperature melts, spontaneous cure under normal temperature, and its product is non-crystal habit, in big block, and packaging, use inconvenience. The service temperature of the inventive method is low, less energy consumption, the 3-chloro-benzoic anhydride product purity height that obtains, receipts rate height, workable, has higher industrial application value.
Accompanying drawing explanation
3-chloro-benzoic anhydride crystal product prepared by Fig. 1 the present invention.
Embodiment
Embodiment 1:
Get 30.0g chloro-benzoic anhydride mixture solid raw material, wherein 3-chloro-benzoic anhydride mass content 60%, join in the mixed solvent of 40.0g methyl acetate and 20.0g hexanaphthene, under stirring action, be heated to 57 DEG C until solid dissolves completely;Solution temperature is declined according to the speed of 2 DEG C/h, and when 20 DEG C, crystal occurs, constant temperature supports brilliant 30min, then continues with 5 DEG C/h rate of temperature fall crystallisation by cooling, until cooling 5 DEG C, terminal, continues constant temperature and supports brilliant 30min. Then by suspension filtered, with the hexanaphthene washing leaching cakes of 10 DEG C, at 50 DEG C, dry 6h, finally obtains the crystal product of 3-chloro-benzoic anhydride. Process receipts rate 70.9%, high pressure liquid chromatography testing product purity is 99.2%.
Embodiment 2:
Get 30.0g chloro-benzoic anhydride mixture solid raw material, wherein 3-chloro-benzoic anhydride mass content 98%, join in the mixed solvent of 45.0g ethyl acetate and 15.0g normal hexane, under stirring action, be heated to 60 DEG C, until solid dissolves completely; Solution temperature is declined according to the speed of 6 DEG C/h, and when 35 DEG C, crystal occurs, constant temperature supports brilliant 1h, then continues with 10 DEG C/h rate of temperature fall crystallisation by cooling, until cooling 5 DEG C, terminal, continues constant temperature and supports brilliant 1h. Then by suspension filtered, with the petroleum ether filter cakes of 5 DEG C, at 50 DEG C, dry 5h, finally obtains the crystal product of 3-chloro-benzoic anhydride. Process receipts rate 69.6%, high pressure liquid chromatography testing product purity is 99.3%.
Embodiment 3:
Get 30.0g chloro-benzoic anhydride mixture solid raw material, wherein 3-chloro-benzoic anhydride mass content 80%, join in the mixed solvent of 30.0g1,4-dioxane and 20.0g tertiary amyl alcohol, under stirring action, be heated to 65 DEG C, until solid dissolves completely; Solution temperature is declined according to the speed of 4 DEG C/h, and when 28 DEG C, crystal occurs, constant temperature supports brilliant 1h, then continues with 5 DEG C/h rate of temperature fall crystallisation by cooling, until cooling 15 DEG C, terminal, continues constant temperature and supports brilliant 1h. Then by suspension filtered, with the n-hexane filter cakes of 15 DEG C, at 60 DEG C, dry 4h, finally obtains the crystal product of 3-chloro-benzoic anhydride. Process receipts rate 72.1%, high pressure liquid chromatography testing product purity is 99.2%.
Embodiment 4:
Get 30.0g chloro-benzoic anhydride mixture solid raw material, wherein 3-chloro-benzoic anhydride mass content 65%, join in the mixed solvent of 30.0g ethanol and 10.0g sherwood oil, under stirring action, be heated to 55 DEG C, until solid dissolves completely; Solution temperature is declined according to the speed of 4 DEG C/h, and when 30 DEG C, crystal occurs, constant temperature supports brilliant 40min, then continues with 7.5 DEG C/h rate of temperature fall crystallisation by cooling, until cooling 10 DEG C, terminal, continues constant temperature and supports brilliant 50min. Then by suspension filtered, with the tetracol phenixin washing leaching cakes of 10 DEG C, at 55 DEG C, dry 5h, finally obtains the crystal product of 3-chloro-benzoic anhydride. Process receipts rate 70.6%, high pressure liquid chromatography testing product purity is 99.1%.
Embodiment 5:
Get 30.0g chloro-benzoic anhydride mixture solid raw material, wherein 3-chloro-benzoic anhydride mass content 70%, join in the mixed solvent of 20.0g methyl alcohol and 10.0g tetracol phenixin, under stirring action, be heated to 58 DEG C, until solid dissolves completely; Solution temperature is declined according to the speed of 6 DEG C/h, and when 20 DEG C, crystal occurs, constant temperature supports brilliant 45min, then continues with 5 DEG C/h rate of temperature fall crystallisation by cooling, until cooling 15 DEG C, terminal, continues constant temperature and supports brilliant 45min. Then by suspension filtered, with the tertiary amyl alcohol washing leaching cakes of 5 DEG C, at 60 DEG C, dry 6h, finally obtains the crystal product of 3-chloro-benzoic anhydride. Process receipts rate 69.2%, high pressure liquid chromatography testing product purity is 99.5%.
The present invention is open and the method for crystallization and purification 3-chloro-benzoic anhydride that proposes, and those skilled in the art are by using for reference content herein, and the links such as suitable feed change, processing parameter realize.The method of the present invention and product are described by better examples of implementation, person skilled obviously can not depart from content of the present invention, spirit and scope, method as herein described and product are changed or suitably change with combination, realize the technology of the present invention. Special needs to be pointed out is, all mutually similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Claims (7)
1. a method for crystallization and purification 3-chloro-benzoic anhydride, is characterized in that: under stirring action, is mixed with mixed solvent by the chloro-benzoic anhydride mixture containing 3-chloro-benzoic anhydride, is heated to 55��65 DEG C, mixture is dissolved completely; Then adopt the mode of crystallisation by cooling that material is cooled to 5��15 DEG C, obtain the crystal suspension liquid of 3-chloro-benzoic anhydride, filtration, solvent wash, drying, obtain 3-chloro-benzoic anhydride crystal product.
2. the method for claim 1, it is characterized in that described mixed solvent is made up of solvent orange 2 A and solvent B two portions, wherein solvent orange 2 A is selected from methyl alcohol, ethanol, methyl acetate, ethyl acetate or 1, one in 4-dioxane, the one that solvent B is selected from tetracol phenixin, hexanaphthene, normal hexane, sherwood oil or tertiary amyl alcohol, the mass ratio of solvent orange 2 A and solvent B is 1.5��3:1.
3. the method for claim 1, is characterized in that the mass ratio of the consumption of described chloro-benzoic anhydride mixture and mixed solvent consumption is 0.5��1:1.
4. the method for claim 1, is characterized in that in described crystallisation by cooling process, first with the rate of temperature fall of 2��6 DEG C/h, material is cooled to 20��35 DEG C, crystallize out, constant temperature 0.5��1h, then with the rate of temperature fall of 5��10 DEG C/h, it is cooled to 5��15 DEG C, constant temperature 0.5��1h.
5. the method for claim 1, is characterized in that the one that described cleaning solvent is selected from tetracol phenixin, hexanaphthene, sherwood oil, normal hexane or tertiary amyl alcohol, and its temperature is 5��15 DEG C.
6. the method for claim 1, is characterized in that described drying conditions is dry 4��6h at 50��60 DEG C.
7. the method for claim 1, is characterized in that in described chloro-benzoic anhydride mixture, 3-chloro-benzoic anhydride quality accounts for more than the 60% of mixture total mass.
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| CN201610169663.5A CN105646419B (en) | 2016-03-23 | 2016-03-23 | A kind of method of the chloro-benzoic anhydride of crystallization and purification 3 |
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| CN201610169663.5A CN105646419B (en) | 2016-03-23 | 2016-03-23 | A kind of method of the chloro-benzoic anhydride of crystallization and purification 3 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107344929A (en) * | 2017-06-26 | 2017-11-14 | 北京旭阳科技有限公司 | From the method for phthalic anhydride Light ends separation and recovery phthalic anhydride |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186063A (en) * | 1996-12-25 | 1998-07-01 | 中国科学院长春应用化学研究所 | Separation of isomers of chloro-benzoic anhydride |
| CN1295999A (en) * | 1999-11-11 | 2001-05-23 | 黑龙江省石油化学研究院 | Process for preparation of monochlorobenzoyl oxide by liquid phase air oxidation |
| CN1318543A (en) * | 2001-04-02 | 2001-10-24 | 中国科学院长春应用化学研究所 | Pre-rectification treatment of crude chlorobenzoic anhydride and chlorophthalic acid product |
| CN1460677A (en) * | 2003-06-11 | 2003-12-10 | 黑龙江省石油化学研究院 | Method for preparing monochlorophthalic anhydride by means of chloration of phthalic anhydride |
| US20060004223A1 (en) * | 2004-06-30 | 2006-01-05 | General Electric Company | Method of making halophthalic acids and halophthalic anhydrides |
| CN103819435A (en) * | 2014-02-17 | 2014-05-28 | 扬州大学 | Method for separating 3-chlorophthalic anhydride from monochlorophthalic anhydride isomer mixture |
-
2016
- 2016-03-23 CN CN201610169663.5A patent/CN105646419B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186063A (en) * | 1996-12-25 | 1998-07-01 | 中国科学院长春应用化学研究所 | Separation of isomers of chloro-benzoic anhydride |
| CN1295999A (en) * | 1999-11-11 | 2001-05-23 | 黑龙江省石油化学研究院 | Process for preparation of monochlorobenzoyl oxide by liquid phase air oxidation |
| CN1318543A (en) * | 2001-04-02 | 2001-10-24 | 中国科学院长春应用化学研究所 | Pre-rectification treatment of crude chlorobenzoic anhydride and chlorophthalic acid product |
| CN1460677A (en) * | 2003-06-11 | 2003-12-10 | 黑龙江省石油化学研究院 | Method for preparing monochlorophthalic anhydride by means of chloration of phthalic anhydride |
| US20060004223A1 (en) * | 2004-06-30 | 2006-01-05 | General Electric Company | Method of making halophthalic acids and halophthalic anhydrides |
| CN103819435A (en) * | 2014-02-17 | 2014-05-28 | 扬州大学 | Method for separating 3-chlorophthalic anhydride from monochlorophthalic anhydride isomer mixture |
Non-Patent Citations (1)
| Title |
|---|
| 谢威扬等: "氯代苯酐的合成", 《化工进展》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107344929A (en) * | 2017-06-26 | 2017-11-14 | 北京旭阳科技有限公司 | From the method for phthalic anhydride Light ends separation and recovery phthalic anhydride |
| CN107344929B (en) * | 2017-06-26 | 2021-02-19 | 北京旭阳科技有限公司 | Method for separating and recovering phthalic anhydride from phthalic anhydride light component |
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| CN105646419B (en) | 2017-11-03 |
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Address after: 300350 District, Jinnan District, Tianjin Haihe Education Park, 135 beautiful road, Beiyang campus of Tianjin University Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92, Tianjin University Patentee before: Tianjin University |