CN102838572A - Preparation method of diphenyl ether dianhydride and isomer thereof - Google Patents
Preparation method of diphenyl ether dianhydride and isomer thereof Download PDFInfo
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- CN102838572A CN102838572A CN2012103469445A CN201210346944A CN102838572A CN 102838572 A CN102838572 A CN 102838572A CN 2012103469445 A CN2012103469445 A CN 2012103469445A CN 201210346944 A CN201210346944 A CN 201210346944A CN 102838572 A CN102838572 A CN 102838572A
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- ether dianhydride
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- phenyl ether
- described phenyl
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Abstract
The invention relates to a preparation method of diphenyl ether dianhydride and isomers thereof, which is characterized in that the preparation method comprises the following steps of: adding solvent and monochlorophthalic anhydride into a reactor with a drying and distilling device, increasing temperature for reflux for a certain period under the protection of N2, adding alkali metal salt and catalysts, conducting reflux reaction for a certain period, decreasing the temperature, conducting filtration to obtain crude products, adding cyanophenyl and the crude products prepared through the reaction into the clean reactor with the drying and distilling device, increasing the temperature for reflux for a certain period under the protection of N2, decreasing the temperature, conducting filtration and drying to obtain the diphenyl ether dianhydride and the isomers thereof. The preparation method provided by the invention has the advantages that the synthesis method of the diphenyl ether dianhydride is widened, the preparation process of the diphenyl ether dianhydride is simplified, the environmental pollution is reduced and a new method is provided for the industrial production of the diphenyl ether dianhydride.
Description
Technical field
The present invention relates to a kind of preparation method of dianhydride, especially relate to a kind of preparation method of phenyl ether dianhydride, belong to technical field of composite materials.
Background technology
Polyimide (PI) is because its excellent performance; As: thermostability, electrical insulating property, wear resistance, oilness, size and oxidative stability, chemical proofing, radiation hardness and physical strength are high; Become the aromatic heterocycle polymer material that is widely used in fields such as electromechanics, electric, instrument, petrochemical complex, aerospace; But many aromatic polyimides are because insoluble, not molten; How therefore poor in processability and limited its range of application improve its processing characteristics, and improving its heat resisting temperature is present research topic.Phenyl ether dianhydride type polyimide is compared with traditional full aromatic polyimide, has more high mechanical strength, chemicalstability and good processibility, and phenyl ether dianhydride and isomer thereof then are the important source material of producing the diphenyl ether type polyimide.
US5101006, EP460687 use tetramethyl-phenyl ether oxidation style to prepare phenyl ether dianhydride, US4837404; EP0119576, US4948904 use halobenzoyl anhydride and hydroxyl phthalic anhydride legal system to be equipped with the phenyl ether dianhydride, still; These method yields are low, and byproduct of reaction is many, difficulty and Separation & Purification.
US4933469, CN101402625A, CN1850814A are raw material with the phthalic anhydride, and be through methylamineization, nitrated; Prepare nitro-N-methyl phthalimide, under catalyst action, through condensation, hydrolysis, diphenyl ether tetraformic is prepared in acidifying; After be dehydrated into the phenyl ether dianhydride, this method synthetic line is long, and total recovery is low, in reaction process, produces a large amount of spent acid; Salkali waste uses high amounts of solvents in the reaction process simultaneously, environment is produced greatly pollute, and is unfavorable for suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of phenyl ether dianhydride and isomer thereof, prepared phenyl ether two anhydride process of this method are simple, and cost is low, and product purity is high, are easy to separate, and the produced simultaneously three wastes are few, are beneficial to carry out suitability for industrialized production.
For realizing that the technical scheme that the object of the invention adopted is:
The preparation method of a kind of phenyl ether dianhydride and isomer thereof is characterized in that: in the reactor drum that has drying and water distilling apparatus, add solvent and monochloro for phthalic anhydride, at N
2Temperature rising reflux for some time under the situation of protection adds an alkali metal salt and catalyzer, and back flow reaction for some time, cooling is filtered, and gets crude product, in the clean reactor drum that has drying and water distilling apparatus, adds benzene nitrile and the prepared crude product of above-mentioned reaction, at N
2Temperature rising reflux for some time under the situation of protection, cooling is filtered, and phenyl ether dianhydride and isomer thereof are processed in oven dry.
As preferably, the solvent that the present invention adopted is one or both or the two or more mixture in orthodichlorobenzene, trichlorotoluene zotrichloride, Chlorodracylic acid, cyanobenzene, the N-Methyl pyrrolidone.
As preferably, the catalyzer that the present invention adopted is one or both or the two or more mixture in triphenyl phosphorus, triple phenoxyl phosphorus, tetraphenylphosphonibromide bromide, Tetrabutyl amonium bromide, chlorination guanidine, six butyl chlorination guanidines, the Hexaethyl chlorination guanidine.
As preferably, an alkali metal salt that the present invention adopted is K
2CO
3, Na
2CO
3, one or both or two or more mixtures among the NaF, KF.
As preferably, the temperature of reaction that the present invention adopted is 60～260 ℃.
As preferably, the monochloro that the present invention adopted is 4-chloro-benzoic anhydride and 3-chloro-benzoic anhydride for two kinds of isomer of phthalic anhydride, and the concrete structure formula is following:
4-chloro-benzoic anhydride 3-chloro-benzoic anhydride
As preferably, monochloro is 1: 0.2～1: 5 for the mol ratio of phthalic anhydride and an alkali metal salt.
As preferably, monochloro is 1: 1～1: 15 for the weight ratio of phthalic anhydride and solvent.
As preferably, catalyst levels is 0.1%～5% of a system gross weight.
The structural formula of the phenyl ether dianhydride that the present invention is prepared is following:
The prepared phenyl ether dianhydride isomer structure formula of the present invention is following:
Above-mentioned three kinds of isomer titles are respectively (1) 3,3 ', 4,4 '-phenyl ether dianhydride, (2) 2,3,3,4 '-phenyl ether dianhydride, (3) 2,2 ', 3,3 '-the phenyl ether dianhydride.
The index of the phenyl ether dianhydride through the present invention preparation is following:
Outward appearance: white or off-white powder
Purity:＞98%
Yield: 60%～85%
Fusing point: 226 ℃～231 ℃
The present invention's beneficial effect compared with prior art is:
The present invention is raw material with monochloro for phthalic anhydride, and through condensation reaction, product is through purifying; Prepare the phenyl ether dianhydride, avoided other synthesis technique circuit long, byproduct of reaction is many; Be difficult to separate, purify; Total recovery is low, and the three wastes that produced in the preparation process are many, environment is produced problems such as pollution greatly.Preparation technology of the present invention is simple, and cost is low, and product purity is high, is easy to separate, and the produced simultaneously three wastes are few, are beneficial to carry out suitability for industrialized production.
Embodiment
Further specify the present invention through embodiment below, but the present invention never only is confined to these embodiment.
Embodiment 1
Have to 500ml and to add trichlorotoluene zotrichloride 200ml in the reactor drum of drying and water distilling apparatus, 4-chloro-benzoic anhydride 35g is at N
2Temperature rising reflux 20min under the situation of protection adds K
2CO
313.5g with triple phenoxyl phosphorus 3.4g, back flow reaction 6 hours, cooling is filtered, and gets crude product 23.85g, and yield is 80%.
To adding 100ml benzene nitrile and the prepared crude product of above-mentioned reaction in clean reactor drum that have drying and water distilling apparatus, at N
2Temperature rising reflux is 1 hour under the situation of protection, is cooled to-10 ℃, filters, and oven dry gets phenyl ether dianhydride and isomer 22.4g thereof.Yield is 75.1%.
Embodiment 2
Have to 500ml and to add orthodichlorobenzene 180ml in the reactor drum of drying and water distilling apparatus, 4-chloro-benzoic anhydride 30.5g is at N
2Temperature rising reflux 35min under the situation of protection adds K
2CO
312.7g with Hexaethyl chlorination guanidine 4.2g, back flow reaction 5.5 hours, cooling is filtered, and gets crude product 21.5g, and yield is 82.7%.
To the mixing solutions and the prepared crude product of above-mentioned reaction that in clean reactor drum, add 120ml benzene nitrile and trichlorotoluene zotrichloride that have drying and water distilling apparatus, at N
2Temperature rising reflux 40min under the situation of protection is cooled to-12 ℃, filters, and oven dry gets phenyl ether dianhydride and isomer 20.8g thereof.Yield is 80.1%.
Embodiment 3
Have to 1000ml and to add orthodichlorobenzene 230ml in the reactor drum of drying and water distilling apparatus, trichlorotoluene zotrichloride 190ml, 4-chloro-benzoic anhydride 92g is at N
2Temperature rising reflux 60min under the situation of protection adds K
2CO
336g and six butyl chlorination guanidine 5.2g, tri-phenyl-phosphorus bromide 2.1g, back flow reaction 7 hours, cooling is filtered, and gets crude product 69.7g, and yield is 89%.
To adding 190ml benzene nitrile and the prepared crude product of above-mentioned reaction in clean reactor drum that have drying and water distilling apparatus, at N
2Temperature rising reflux 35min under the situation of protection is cooled to-15 ℃, filters, and oven dry gets phenyl ether dianhydride and isomer 68g thereof.Yield is 86.8%.
Embodiment 4
Have to 1000ml and to add trichlorotoluene zotrichloride 400ml in the reactor drum of drying and water distilling apparatus, 4-chloro-benzoic anhydride 92g is at N
2Temperature rising reflux 60min under the situation of protection adds Na
2CO
333g, NaF3.5g, chlorination guanidine 4.8g, tri-phenyl-phosphorus bromide 2.8g, back flow reaction 5 hours, cooling is filtered, and gets crude product 58.5g, and yield is 74.6%.
To adding 150ml benzene nitrile and the prepared crude product of above-mentioned reaction in clean reactor drum that have drying and water distilling apparatus, at N
2Temperature rising reflux 60min under the situation of protection is cooled to-10 ℃, filters, and oven dry gets phenyl ether dianhydride and isomer 57g thereof.Yield is 72.7%.
Embodiment 5
Have to 1000ml and to add trichlorotoluene zotrichloride 400ml in the reactor drum of drying and water distilling apparatus, 3-chloro-benzoic anhydride 70g is at N
2Temperature rising reflux 60min under the situation of protection adds K
2CO
330g, NaF3.0g, Hexaethyl chlorination guanidine 5.8g, back flow reaction 5 hours, cooling is filtered, and gets crude product 53.5g, and yield is 89%.
To adding 150ml benzene nitrile and the prepared crude product of above-mentioned reaction in clean reactor drum that have drying and water distilling apparatus, at N
2Temperature rising reflux 60min under the situation of protection is cooled to-15 ℃, filters, and oven dry gets phenyl ether dianhydride and isomer 49g thereof.Yield is 82.3%.
Embodiment 6
Have to 1000ml and to add trichlorotoluene zotrichloride 400ml in the reactor drum of drying and water distilling apparatus, 4-chloro-benzoic anhydride 70g, 3-chloro-benzoic anhydride 70g is at N
2Temperature rising reflux 60min under the situation of protection adds K
2CO
375g, NaF7.0g, Hexaethyl chlorination guanidine 11.6g, triple phenoxyl phosphorus 3.8 back flow reaction 5 hours, cooling is filtered, and gets crude product 98.4g, and yield is 82.6%.
In the clean reactor drum that has drying and water distilling apparatus, add 310ml benzene nitrile and the prepared crude product of above-mentioned reaction, at N
2Temperature rising reflux 60min under the situation of protection is cooled to-12 ℃, filters, and oven dry gets phenyl ether dianhydride and isomer 91g thereof.Yield is 76.4%
The present invention is not limited to the method described in the embodiment; Its description is illustrative; And it is nonrestrictive; Authority of the present invention is limited claim, based on present technique field personnel according to the present invention can change, technology and the product relevant that method such as reorganization obtains with the present invention, all within protection scope of the present invention.
Claims (9)
1. the preparation method of phenyl ether dianhydride and isomer thereof is characterized in that: in the reactor drum that has drying and water distilling apparatus, add solvent and monochloro for phthalic anhydride, at N
2Temperature rising reflux for some time under the situation of protection adds an alkali metal salt and catalyzer, and back flow reaction for some time, cooling is filtered, and gets crude product, in the clean reactor drum that has drying and water distilling apparatus, adds benzene nitrile and the prepared crude product of above-mentioned reaction, at N
2Temperature rising reflux for some time under the situation of protection, cooling is filtered, and phenyl ether dianhydride and isomer thereof are processed in oven dry.
2. by the preparation method of the described phenyl ether dianhydride of claim 1 and isomer thereof, it is characterized in that: the solvent that is adopted is one or both or the two or more mixture in orthodichlorobenzene, trichlorotoluene zotrichloride, Chlorodracylic acid, cyanobenzene, the N-Methyl pyrrolidone.
3. by the preparation method of the described phenyl ether dianhydride of claim 1 and isomer thereof, it is characterized in that: the catalyzer that is adopted is one or both or the two or more mixture in triphenyl phosphorus, triple phenoxyl phosphorus, tetraphenylphosphonibromide bromide, Tetrabutyl amonium bromide, chlorination guanidine, six butyl chlorination guanidines, the Hexaethyl chlorination guanidine.
4. by the preparation method of described phenyl ether dianhydride of claim 1 and isomer thereof, it is characterized in that: an alkali metal salt that is adopted is K
2CO
3, Na
2CO
3, one or both or two or more mixtures among the NaF, KF.
5. by the preparation method of described phenyl ether dianhydride of claim 1 and isomer thereof, it is characterized in that: the temperature of reaction that is adopted is 60～260 ℃.
6. by the preparation method of described phenyl ether dianhydride of claim 1 and isomer thereof, it is characterized in that: monochloro is 4-chloro-benzoic anhydride and 3-chloro-benzoic anhydride for two kinds of isomer of phthalic anhydride.
7. by the preparation method of described phenyl ether dianhydride of claim 1 and isomer thereof, it is characterized in that: monochloro is 1: 0.2～1: 5 for the mol ratio of phthalic anhydride and an alkali metal salt.
8. by the preparation method of described phenyl ether dianhydride of claim 1 and isomer thereof, it is characterized in that: monochloro is 1: 1～1: 15 for the weight ratio of phthalic anhydride and solvent.
9. by the preparation method of described phenyl ether dianhydride of claim 1 and isomer thereof, it is characterized in that: catalyst levels is 0.1%～5% of a system gross weight.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130227A (en) * | 2014-07-31 | 2014-11-05 | 景立秋 | Preparation method for diphenyl ether dianhydride |
| CN106279085A (en) * | 2016-08-17 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of preparation method mixing isomery bis ether tetracarboxylic acid dianhydride |
| CN108250168A (en) * | 2017-12-25 | 2018-07-06 | 上海固创化工新材料有限公司 | A kind of preparation method of diphenyl ether tetraformic dianhydride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0264624A1 (en) * | 1986-10-03 | 1988-04-27 | Occidental Chemical Corporation | Process for the preparation of oxy-diphthalic anhydrides |
| US5153335A (en) * | 1990-06-08 | 1992-10-06 | Occidental Chemical Corporation | Process for the preparation of oxydiphthalic anhydride and acyloxyphthalic anhydrides |
| CN1324794A (en) * | 2000-05-19 | 2001-12-05 | 黑龙江省石油化学研究院 | Prepn. of diphenyl ether tetraformic dianhydride |
-
2012
- 2012-09-07 CN CN2012103469445A patent/CN102838572A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0264624A1 (en) * | 1986-10-03 | 1988-04-27 | Occidental Chemical Corporation | Process for the preparation of oxy-diphthalic anhydrides |
| US5153335A (en) * | 1990-06-08 | 1992-10-06 | Occidental Chemical Corporation | Process for the preparation of oxydiphthalic anhydride and acyloxyphthalic anhydrides |
| CN1324794A (en) * | 2000-05-19 | 2001-12-05 | 黑龙江省石油化学研究院 | Prepn. of diphenyl ether tetraformic dianhydride |
Non-Patent Citations (3)
| Title |
|---|
| 张春荣等: "3,3",4,4"-二苯醚四甲酸二酐合成进展", 《黑龙江科学》 * |
| 王正平等: "二苯醚四甲酸二酐合成方法的研究", 《精细化工原料与中间体》 * |
| 黎庆: "氯代苯酐制3,3"4,4"-二苯醚四甲酸酐及设备", 《化学与黏合》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130227A (en) * | 2014-07-31 | 2014-11-05 | 景立秋 | Preparation method for diphenyl ether dianhydride |
| CN104130227B (en) * | 2014-07-31 | 2016-01-20 | 景立秋 | A kind of preparation method of diphenyl ether dianhydride |
| CN106279085A (en) * | 2016-08-17 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of preparation method mixing isomery bis ether tetracarboxylic acid dianhydride |
| CN106279085B (en) * | 2016-08-17 | 2018-07-10 | 万华化学集团股份有限公司 | A kind of preparation method for mixing isomery bis ether tetracarboxylic acid dianhydride |
| CN108250168A (en) * | 2017-12-25 | 2018-07-06 | 上海固创化工新材料有限公司 | A kind of preparation method of diphenyl ether tetraformic dianhydride |
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Application publication date: 20121226 |