CN105646419B - A kind of method of the chloro-benzoic anhydride of crystallization and purification 3 - Google Patents
A kind of method of the chloro-benzoic anhydride of crystallization and purification 3 Download PDFInfo
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- CN105646419B CN105646419B CN201610169663.5A CN201610169663A CN105646419B CN 105646419 B CN105646419 B CN 105646419B CN 201610169663 A CN201610169663 A CN 201610169663A CN 105646419 B CN105646419 B CN 105646419B
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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
Abstract
The present invention relates to a kind of method of the chloro-benzoic anhydride of crystallization and purification 3.Under stirring action, the chloro-benzoic anhydride mixture containing 3 chloro-benzoic anhydrides is mixed with mixed solvent, 55~65 DEG C is heated to, is completely dissolved mixture；Then material is cooled to 5~15 DEG C by the way of crystallisation by cooling, obtains the crystal suspension of 3 chloro-benzoic anhydrides, filtering, solvent washing, dry, 3 chloro-benzoic anhydride crystal products of acquisition.The present invention is using 3 chloro-benzoic anhydrides and the difference of other solubility of chloro-benzoic anhydride product in different solvents, by selecting mixed solvent species and proportion of composing, while crystallization operation condition is controlled, so that the purity and yield of crystalline product is effectively ensured.Purity more than 99.0%, 3 chloro-benzoic anhydride crystalline products of crystallization yield more than 70.8% can be obtained.The operation temperature of the inventive method is low, less energy consumption, obtains 3 chloro-benzoic anhydride product purities height, high income, workable, with higher industrial application value.
Description
Technical field
The invention belongs to technical field of chemical separation, more particularly to a kind of method of crystallization and purification 3- chloro-benzoic anhydrides.
Background technology
Single chloro-benzoic anhydride includes two kinds of isomers：3- chloro-benzoic anhydrides and 4- chloro-benzoic anhydrides, their English name difference
For 3-chlorophthalic anhydride and 4-chlorophthalic anhydride, fusing point is respectively 123 DEG C and 96
DEG C, it is in solid-state under normal temperature, molecular formula is C8H3ClO3, chemical structural formula is distinguished as follows：
3- chloro-benzoic anhydrides and 4- chloro-benzoic anhydrides are all important industrial chemicals, be widely applied to medicine, dyestuff, agricultural chemicals and
The fields such as engineering material, can be for synthesis monoether dianhydride, diaether dianhydride, ketone dianhydride, biphenyl dianhydride, thioether dianhydride, diphenyl sulphone (DPS)
The intermediate of the polyimides such as dianhydride, bisphenol A dianhydride.
The synthetic method of 3- chloro-benzoic anhydrides has a variety of, at present, and main synthetic method has：Mononitro-benzene acid anhydride chloro method, it is adjacent
The chloridising of phthalic acid and its sodium salt, 3- chloro-o-xylene oxidizing process etc..But, the 3- chlorobenzenes obtained by synthetic method
In anhydride product, often containing a certain amount of 4- chloro-benzoic anhydrides and other chloro-benzoic anhydride mixtures, cause 3- chloro-benzoic anhydrides in product
Purity is low, and only purity is reached after certain require, 3- chloro-benzoic anhydrides product could realize commercial Application, therefore be accomplished by mixed
Compound is purified, to obtain 3- chloro-benzoic anhydride sterlings.
At present, some existing documents are studied the method for purifying 3- chloro-benzoic anhydrides, Chinese patent CN1186063 profits
3- chloro-benzoic anhydrides are separated with the method for rectification under vacuum, its pressure limit is 6~100kPa, temperature range is 180~215 DEG C,
The purity for obtaining 3- chloro-benzoic anhydride solid products is 97.7%, and yield is 49.9%；Chinese patent CN103819435 mixes solid
Compound, which is heated to 90~150 DEG C, melts it, and the fusing point using other chloro-benzoic anhydrides such as 3- chloro-benzoic anhydrides and 4- chloro-benzoic anhydrides is poor
It is different, by way of fusion-crystallization, 3- chloro-benzoic anhydrides are purified, the purity of obtained 3- chloro-benzoic anhydride crystal products is
99.5%, yield is 54.8%.As can be seen that the product of rectification method is not high in purity and yield, the production of fused junction crystallization
Although product purity is higher, its complex operation, long preparation period be not still high on yield, and both separation methods, product
For amorphous state, all there is the problem of energy consumption is higher.Therefore, it is necessary to develop, a kind of preparation method is simple, process energy consumption is low, product
The 3- chloro-benzoic anhydride method for purifying and separating that purity is high, process yield is high.
The content of the invention
In order to overcome the problem of existing 3- chloro-benzoic anhydrides purifies and separates technology is present, the invention discloses a kind of crystallization and purification
The method of 3- chloro-benzoic anhydrides, using the difference on 3- chloro-benzoic anhydrides and other chloro-benzoic anhydride product solubilities, passes through crystallisation by cooling
Solution crystallization mode, by 3- chloro-benzoic anhydride purifies and separates.
The technical scheme is that：Under stirring action, by the chloro-benzoic anhydride mixture containing 3- chloro-benzoic anhydrides with mixing
Solvent is mixed, and is heated to 55~65 DEG C, is completely dissolved mixture；Then material is cooled to 5 by the way of crystallisation by cooling
~15 DEG C, obtain the crystal suspension of 3- chloro-benzoic anhydrides, filtering, solvent washing, dry, acquisition 3- chloro-benzoic anhydride crystal products.
3- chloro-benzoic anhydride quality accounts for more than the 60% of mixture gross mass, chloro-benzoic anhydride in described chloro-benzoic anhydride mixture
Residue after the single chloro-benzoic anhydride of reaction synthetic product or purifying of the mixture from upstream.
Described mixed solvent is made up of solvent orange 2 A and solvent B two parts, and wherein solvent orange 2 A is selected from methanol, ethanol, acetic acid first
One kind in ester, ethyl acetate or Isosorbide-5-Nitrae-dioxane, solvent B is selected from carbon tetrachloride, hexamethylene, n-hexane, petroleum ether or uncle
One kind in amylalcohol, solvent orange 2 A and solvent B mass ratio are 1.5~3:1.
The consumption of described chloro-benzoic anhydride mixture is 0.5~1 with the mass ratio of mixed solvent consumption:1.
During described crystallisation by cooling, first with 2~6 DEG C/h rate of temperature fall, material is cooled to 20~35 DEG C, precipitation
Crystal, 0.5~1h of constant temperature, then with 5~10 DEG C/h rate of temperature fall, is cooled to 5~15 DEG C, 0.5~1h of constant temperature.
The one kind of described cleaning solvent in carbon tetrachloride, hexamethylene, petroleum ether, n-hexane or tert-pentyl alcohol, its temperature
Spend for 5~15 DEG C.
Described drying condition is dry 4~6h at 50~60 DEG C.
The method that solution crystal process of the present invention purifies 3- chloro-benzoic anhydrides, utilizes 3- chloro-benzoic anhydrides and other chlorobenzenes
The difference of solubility of the anhydride product in different solvents, by selecting mixed solvent species and proportion of composing, while controlling to crystallize
Operating condition, so that the purity and yield of crystalline product is effectively ensured.Purity more than 99.0%, crystallization yield can be obtained
More than 70.8% 3- chloro-benzoic anhydride crystalline products, or purity more than 99.5%, crystallization yield more than 68.1% 3- chloros
Phthalic anhydride crystalline product.As shown in Figure 1, good product mobility is easy to use for crystal product form.And existing product is by essence
Evaporate method or fusion-crystallization method is made, it is spontaneous cure under fused mass, normal temperature at high temperature, and its product is non-crystal habit, is in
It is big block, it is packaging, inconvenient for use.The operation temperature of the inventive method is low, less energy consumption, obtained 3- chloro-benzoic anhydride product purities
High, high income, it is workable, with higher industrial application value.
Brief description of the drawings
3- chloro-benzoic anhydride crystal products prepared by Fig. 1 present invention.
Embodiment
Embodiment 1：
Take 30.0g chloro-benzoic anhydride mixture solid raw materials, wherein 3- chloro-benzoic anhydrides mass content 60%, be added to 40.0g
Under the in the mixed solvent of methyl acetate and 20.0g hexamethylenes, stirring action, 57 DEG C are heated to until solid is completely dissolved；
Solution temperature is declined according to 2 DEG C/h speed, crystal occurs at 20 DEG C, constant temperature growing the grain 30min, then proceed to drop with 5 DEG C/h
Warm speed crystallisation by cooling, until 5 DEG C of terminal of cooling, continues constant temperature growing the grain 30min.Then suspension is filtered, with 10 DEG C of rings
Hexane washs filter cake, and 6h is dried at 50 DEG C, the crystal product of 3- chloro-benzoic anhydrides is finally given.Process yield 70.9%, high pressure
Liquid chromatographic detection product purity is 99.2%.
Embodiment 2：
Take 30.0g chloro-benzoic anhydride mixture solid raw materials, wherein 3- chloro-benzoic anhydrides mass content 98%, be added to 45.0g
Under the in the mixed solvent of ethyl acetate and 15.0g n-hexanes, stirring action, 60 DEG C are heated to, until solid is completely dissolved；
Solution temperature is declined according to 6 DEG C/h speed, crystal occurs at 35 DEG C, constant temperature growing the grain 1h, then proceed to cool with 10 DEG C/h
Speed crystallisation by cooling, until 5 DEG C of terminal of cooling, continues constant temperature growing the grain 1h.Then suspension is filtered, washed with 5 DEG C of petroleum ether
Filter cake is washed, 5h is dried at 50 DEG C, the crystal product of 3- chloro-benzoic anhydrides is finally given.Process yield 69.6%, high pressure liquid phase color
Spectrum detection product purity is 99.3%.
Embodiment 3：
Take 30.0g chloro-benzoic anhydride mixture solid raw materials, wherein 3- chloro-benzoic anhydrides mass content 80%, be added to
Under the in the mixed solvent of 30.0g1,4- dioxane and 20.0g tert-pentyl alcohols, stirring action, 65 DEG C are heated to, until solid
It is completely dissolved；Solution temperature is set to decline according to 4 DEG C/h speed, crystal occurs at 28 DEG C, constant temperature growing the grain 1h is then proceeded to 5
DEG C/h rate of temperature fall crystallisation by cooling, until 15 DEG C of terminal of cooling, continues constant temperature growing the grain 1h.Then suspension is filtered, with 15 DEG C
N-hexane washing filter cake, at 60 DEG C dry 4h, finally give the crystal product of 3- chloro-benzoic anhydrides.Process yield 72.1%,
High pressure liquid chromatography detection product purity is 99.2%.
Embodiment 4：
Take 30.0g chloro-benzoic anhydride mixture solid raw materials, wherein 3- chloro-benzoic anhydrides mass content 65%, be added to 30.0g
Under the in the mixed solvent of ethanol and 10.0g petroleum ethers, stirring action, 55 DEG C are heated to, until solid is completely dissolved；Make molten
Liquid temperature degree declines according to 4 DEG C/h speed, and crystal occurs at 30 DEG C, constant temperature growing the grain 40min, then proceedes to cool with 7.5 DEG C/h
Speed crystallisation by cooling, until 10 DEG C of terminal of cooling, continues constant temperature growing the grain 50min.Then suspension is filtered, with 10 DEG C of tetrachloros
Change carbon washing filter cake, 5h is dried at 55 DEG C, the crystal product of 3- chloro-benzoic anhydrides is finally given.Process yield 70.6%, high pressure
Liquid chromatographic detection product purity is 99.1%.
Embodiment 5：
Take 30.0g chloro-benzoic anhydride mixture solid raw materials, wherein 3- chloro-benzoic anhydrides mass content 70%, be added to 20.0g
Under the in the mixed solvent of methanol and 10.0g carbon tetrachloride, stirring action, 58 DEG C are heated to, until solid is completely dissolved；Make
Solution temperature declines according to 6 DEG C/h speed, and crystal occurs at 20 DEG C, constant temperature growing the grain 45min, then proceedes to cool with 5 DEG C/h
Speed crystallisation by cooling, until 15 DEG C of terminal of cooling, continues constant temperature growing the grain 45min.Then suspension is filtered, with 5 DEG C of uncles penta
Alcohol washs filter cake, and 6h is dried at 60 DEG C, the crystal product of 3- chloro-benzoic anhydrides is finally given.Process yield 69.2%, high pressure liquid
Phase chromatogram detection product purity is 99.5%.
The method for the crystallization and purification 3- chloro-benzoic anhydrides that the present invention is disclosed and proposed, those skilled in the art can be by using for reference this
Literary content, the link such as appropriate feed change, technological parameter is realized.The method of the present invention is entered by preferred embodiment with product
Gone description, person skilled substantially can not departing from present invention, in spirit and scope to method described herein and
Product is modified or suitably change is with combining, to realize the technology of the present invention.In particular, it is all similar to replace
Change and change apparent to those skilled in the art, they be considered as being included in spirit of the invention, scope and
In content.
Claims (4)
1. a kind of method of crystallization and purification 3- chloro-benzoic anhydrides, it is characterized in that：Under stirring action, by the chloro containing 3- chloro-benzoic anhydrides
Phthalic anhydride mixture is mixed with mixed solvent, is heated to 55~65 DEG C, is completely dissolved mixture；Then the side of crystallisation by cooling is used
Material is cooled to 5~15 DEG C by formula, obtains the crystal suspension of 3- chloro-benzoic anhydrides, filtering, solvent washing, dry, acquisition 3- chlorine
For phthalic anhydride crystal product；Described mixed solvent is made up of solvent orange 2 A and solvent B two parts, wherein solvent orange 2 A be selected from methanol, ethanol,
One kind in methyl acetate, ethyl acetate or Isosorbide-5-Nitrae-dioxane, solvent B is selected from carbon tetrachloride, hexamethylene, n-hexane, oil
One kind in ether or tert-pentyl alcohol, solvent orange 2 A and solvent B mass ratio are 1.5~3:1；During described crystallisation by cooling, first with 2
~6 DEG C/h rate of temperature fall, 20~35 DEG C are cooled to by material, separate out crystal, 0.5~1h of constant temperature, then with 5~10 DEG C/h's
Rate of temperature fall, is cooled to 5~15 DEG C, 0.5~1h of constant temperature；3- chloro-benzoic anhydride quality accounts for mixing in described chloro-benzoic anhydride mixture
More than the 60% of thing gross mass.
2. the method as described in claim 1, it is characterized in that the consumption of described chloro-benzoic anhydride mixture and mixed solvent consumption
Mass ratio be 0.5~1:1.
3. the method as described in claim 1, it is characterized in that described cleaning solvent be selected from carbon tetrachloride, hexamethylene, petroleum ether,
One kind in n-hexane or tert-pentyl alcohol, its temperature is 5~15 DEG C.
4. the method as described in claim 1, it is characterized in that described drying condition is dry 4~6h at 50~60 DEG C.
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| CN1109013C (en) * | 1996-12-25 | 2003-05-21 | 中国科学院长春应用化学研究所 | Separation of isomers of chloro-benzoic anhydride |
| CN1090171C (en) * | 1999-11-11 | 2002-09-04 | 黑龙江省石油化学研究院 | Process for preparation of monochlorobenzoyl oxide by liquid phase air oxidation |
| CN1160346C (en) * | 2001-04-02 | 2004-08-04 | 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 |
| CN1189463C (en) * | 2003-06-11 | 2005-02-16 | 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 |
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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 |