CN112574148B - Preparation method of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) - Google Patents
Preparation method of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) Download PDFInfo
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- CN112574148B CN112574148B CN202011532951.5A CN202011532951A CN112574148B CN 112574148 B CN112574148 B CN 112574148B CN 202011532951 A CN202011532951 A CN 202011532951A CN 112574148 B CN112574148 B CN 112574148B
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Abstract
The invention provides a preparation method of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride), which comprises the following steps: dissolving 4,4' -isopropylidene diphenol sodium and 4-chlorophthalic acid in a solvent, adding a copper catalyst, heating to a reaction temperature, maintaining the temperature until the raw materials are completely reacted, cooling to 70 ℃, carrying out reduced pressure distillation to recover 80% of the solvent, then adding toluene, evaporating 60%, cooling, filtering, washing, paving on an enamel disc, and carrying out vacuum drying to obtain a product 4,4' - (4,4' -isopropylidene diphenoxy) bis (phthalic anhydride). The method has the advantages of high yield, few operation steps, normal-pressure reaction, no need of nitrogen protection, recyclable solvent and low production cost.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride).
Background
4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) is a key raw material for preparing polyimide dianhydride monomer.
4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) is an important material for preparing aromatic polyimide, and the polyimide material prepared by the product has excellent comprehensive properties such as higher thermal stability, low dielectric constant, low dielectric loss and the like, and is widely applied to industries such as liquid crystal, aerospace, wires and cables, separation membranes, lasers and the like.
Currently relevant reports for the preparation of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) are:
1) patent CN108148029 discloses a preparation method of bisphenol a diether dianhydride, which comprises the following steps: adding a sodium hydroxide aqueous solution and bisphenol A into a reactor, heating, stirring and dissolving, heating to 85-90 ℃, adding trimethylbenzene and benzyltriethylammonium chloride accounting for 46 wt% of the total amount, heating, refluxing, dehydrating, stirring and reacting at 172 ℃ for 15-18 hours, cooling to 130 ℃, adding 4-chlorophthalic anhydride and benzyltriethylammonium chloride accounting for 54 wt% of the total amount, heating to 140-145 ℃, refluxing and reacting for 5-6 hours, filtering while hot, cooling the filtrate to room temperature, filtering, washing precipitates with deionized water and ethanol respectively, filtering to obtain a wet material, and drying to obtain a bisphenol A diether dianhydride product, wherein the yield is 80-85%.
2) Patent CN104529966 discloses a preparation method of bisphenol A diether dianhydride, which takes bisphenol A and chlorophthalic anhydride as raw materials, and the dosage of the bisphenol A and the chlorophthalic anhydride is bisPhenol A and chlorophthalic anhydride (mol/mol) ═ 1: 1-1: 10, adding solvent and bisphenol A and chlorophthalic anhydride into reactor with drying and distilling device, adding N 2 Heating and refluxing for 20-80min under the protection condition, adding an alkali compound and a catalyst, performing reflux reaction for 3-24 h, cooling and filtering to obtain a crude product, wherein the yield is 50-95%; washing the crude product, recrystallizing with a recrystallization solvent, filtering, drying, and dehydrating to form a ring to obtain bisphenol A diether dianhydride; the bisphenol A diether dianhydride comprises the following components: 4,4'- (4,4' -isopropyldiphenoxy) bis (phthalic anhydride), 3, 3 '- (4,4' -isopropyldiphenoxy) bis (phthalic anhydride).
At present, the preparation method of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) in the prior art has the defects of multiple steps, long time, low yield and the like.
Disclosure of Invention
In view of the above, the present invention is directed to a method for preparing 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride), which can improve the product yield and reduce the cost.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a process for the preparation of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) comprising the steps of: dissolving 4,4' -isopropylidene diphenol sodium and 4-chlorophthalic acid in a solvent, adding a copper catalyst, heating to a reaction temperature, maintaining the temperature until the raw materials are completely reacted, cooling to 70 ℃, carrying out reduced pressure distillation to recover 80% of the solvent, then adding toluene, evaporating 60%, cooling, filtering, washing with water, paving on an enamel disc, and carrying out vacuum drying to obtain a product 4,4' - (4,4' -isopropylidene diphenoxy) bis (phthalic anhydride). White solid, melting point 185-.
The reaction equation is as follows:
preferably, the copper catalyst is a copper salt catalyst or an aromatic copper catalyst, the copper salt catalyst is one of cuprous chloride, copper iodide and copper acetate, and the aromatic copper catalyst is one of tris (triphenyl phosphorus) copper bromide, tetraethyl cyanide copper hexafluorophosphate, (1, 10-phenanthroline) trifluoro-methylthiocopper and (1, 10-phenanthroline) trifluoromethyl copper.
More preferably, the copper catalyst is copper tris (triphenylphosphine) bromide.
Preferably, the polar solvent is one of N-methylpyrrolidone, dimethylbutyramide, sulfolane, trimethylbenzene, and dimethylacetamide.
More preferably, the polar solvent is sulfolane.
Preferably, the molar ratio of the raw materials is: sodium 4,4' -isopropylidenediphenol: 4-chlorophthalic acid: tris (triphenylphosphine) copper bromide: solvent 1: (2-2.1): (0.001-0.03): (1-3).
More preferably, the molar ratio of the raw materials is: 4,4' -isopropylidenediphenol sodium: 4-chlorophthalic acid: tris (triphenylphosphine) copper bromide: solvent 1: (2-2.1): (0.02-0.03): (1-3).
Preferably, the reaction temperature is 100-200 ℃, and more preferably, the reaction temperature is 130-160 ℃.
More preferably, when the solvent is sulfolane, the reaction temperature is 150-180 ℃.
Preferably, the temperature of vacuum drying is 100-160 ℃, and the drying time is 8-15 hours.
The invention has the following beneficial effects:
the method has the advantages of high reaction yield, few operation steps, normal-pressure reaction, no need of nitrogen protection, recyclable solvent and low production cost because the catalyst is copper tris (triphenylphosphine) bromide.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples are all conventional reagents unless otherwise specified; the experimental methods are all conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
Example 1
A process for the preparation of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) comprising the steps of:
13.6g of 4,4' -isopropylidenediphenol sodium, 20.5g of 4-chlorophthalic acid, 1g of copper tris (triphenylphosphine) bromide and 80g of sulfolane are added into a reaction bottle, the temperature is slowly raised to about 160 ℃ for reaction, the temperature is maintained until the raw materials are completely reacted, the temperature is reduced to 70 ℃, 80% of sulfolane is recovered by reduced pressure distillation (the sulfolane can be used after being steamed again), then toluene is added, 60% of the sulfolane is distilled out, the temperature is reduced, the filtrate is filtered, the filtrate is washed, the washed product is spread on an enamel plate, and the vacuum drying is carried out at 150 ℃ for 8 hours to obtain 25.6g of the product 4,4' - (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) as a white solid, wherein the yield is 98.46%.
Example 2
A process for the preparation of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) comprising the steps of:
13.6g of 4,4' -isopropylidenediphenol sodium, 20g of 4-chlorophthalic acid, 0.5g of copper tris (triphenylphosphine) bromide and 61g of sulfolane are added into a reaction bottle, the temperature is slowly raised to about 120 ℃ for reaction, the temperature is maintained until the raw materials are completely reacted, the temperature is reduced to 70 ℃, 80% of sulfolane is recovered by reduced pressure distillation (the sulfolane can be used after being steamed again), then toluene is added, 60% of the sulfolane is distilled out, the temperature is reduced, the filtered and washed, the washed product is spread on an enamel plate, and the vacuum drying is carried out at 150 ℃ for 8 hours to obtain 23.1g of 4,4' - (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) as a product, wherein the white solid is obtained, and the yield is 88.46%.
Example 3
A process for the preparation of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) comprising the steps of:
13.6g of 4,4' -isopropylidenediphenoxy sodium, 21g of 4-chlorophthalic acid, 1.5g of tris (triphenylphosphine) copper bromide and 180g of sulfolane are added into a reaction bottle, the temperature is slowly raised to about 180 ℃ for reaction, the temperature is maintained until the raw materials are completely reacted, the temperature is reduced to 70 ℃, 80% of sulfolane is recovered by reduced pressure distillation (the sulfolane can be reused after being steamed again), then toluene is added, 60% of the sulfolane is distilled out, the temperature is reduced, the filtrate is filtered, the product is washed by water, and the product is dried in vacuum at 150 ℃ for 8 hours to obtain 25.7g of the product 4,4' - (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride), white solid, and the yield is 98.84%.
Example 4
A process for the preparation of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) comprising the steps of:
13.6g of 4,4' -isopropylidenediphenol sodium, 20.2g of 4-chlorophthalic acid, 1g of copper tris (triphenylphosphine) bromide and 90g of sulfolane are added into a reaction bottle, the temperature is slowly raised to about 150 ℃ for reaction, the temperature is maintained until the raw materials are completely reacted, the temperature is reduced to 70 ℃, 80% of sulfolane is recovered by reduced pressure distillation (the sulfolane can be used after being steamed again), then toluene is added, 60% of the sulfolane is distilled out, the temperature is reduced, the filtered and washed, the washed product is spread on an enamel plate, and the vacuum drying is carried out at 150 ℃ for 8 hours to obtain 24.1g of the product 4,4' - (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) as a white solid with the yield of 92.69%.
Example 5
A process for the preparation of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) comprising the steps of:
13.6g of 4,4' -isopropylidenediphenol sodium, 20.6g of 4-chlorophthalic acid, 1.5g of copper tris (triphenylphosphine) bromide and 110g N-methyl pyrrolidone are added into a reaction bottle, the temperature is slowly raised to about 160 ℃ for reaction, the temperature is maintained until the raw materials are completely reacted, the temperature is reduced to 70 ℃, 80 percent of solvent is recovered by reduced pressure distillation, then water is added, the mixture is filtered and paved on an enamel plate, and the mixture is dried in vacuum at 150 ℃ for 9 hours to obtain 20.4g of 4,4' - (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) which is a product, white solid and the yield is 78.46 percent.
Example 6
A process for the preparation of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) comprising the steps of:
13.6g of 4,4' -isopropylidenediphenol sodium, 20.5g of 4-chlorophthalic acid, 1.5g of copper tris (triphenylphosphine) bromide and 100g of dimethylacetamide are added into a reaction bottle, the temperature is slowly raised to about 150 ℃ for reaction, the temperature is maintained until the raw materials are completely reacted, the temperature is reduced, reduced pressure distillation is carried out to recover 80% of solvent, then water is added, filtration is carried out, the mixture is spread on an enamel plate, vacuum drying is carried out for 9 hours at 150 ℃ to obtain 19.2g of product 4,4' - (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride), white solid is obtained, and the yield is 73.85%.
The above description is only exemplary of the present invention in different molar ratios, and should not be construed as limiting the present invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A process for the preparation of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) characterized by: the method comprises the following steps: dissolving 4,4' -isopropylidene diphenol sodium and 4-chlorophthalic acid in a solvent, adding a copper catalyst, heating to 130-160 ℃, maintaining the temperature until the raw materials react completely, cooling to 70 ℃, carrying out reduced pressure distillation to recover 80% of the solvent, then adding toluene, steaming out 60%, cooling, filtering, washing, paving on an enamel disc, and carrying out vacuum drying to obtain a product 4,4' - (4,4' -isopropylidene diphenoxy) bis (phthalic anhydride), wherein the solvent is one of N-methyl pyrrolidone, sulfolane and dimethylacetamide, and the copper catalyst is tris (triphenylphosphine) copper bromide.
2. The process of claim 1 wherein the reaction mixture is prepared from 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride): the solvent is sulfolane.
3. The process of claim 1 wherein the reaction mixture is prepared from 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride): the molar ratio of the raw materials is as follows: sodium 4,4' -isopropylidenediphenol: 4-chlorophthalic acid: tris (triphenylphosphine) copper bromide: solvent 1: (2-2.1): (0.001-0.03): (1-3).
4. A process for the preparation of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) according to claim 3, wherein: the molar ratio of the raw materials is as follows: sodium 4,4' -isopropylidenediphenol: 4-chlorophthalic acid: tris (triphenylphosphine) copper bromide: solvent 1: (2-2.1): (0.02-0.03): (1-3).
5. The process of claim 2 wherein the reaction mixture is prepared from 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride): when the solvent is sulfolane, the reaction temperature is 150-180 ℃.
6. A process for the preparation of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) according to any of claims 1 to 5, wherein: the temperature of vacuum drying is 100-160 ℃, and the drying time is 8-15 hours.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1827611A (en) * | 2006-04-14 | 2006-09-06 | 黑龙江省石油化学研究院 | Process for preparing 3,3',4,4'-tetracarboxydiphthalic ether dianhydride |
| CN104529966A (en) * | 2015-01-11 | 2015-04-22 | 景炜杰 | Preparation method of bisphenol A diether dianhydride |
| CN105330634A (en) * | 2015-12-07 | 2016-02-17 | 济南轩鸿生物医药有限公司 | One-pot method for preparing 3-hydroxyphtalic anhydride |
| JP2020007397A (en) * | 2018-07-03 | 2020-01-16 | 積水化学工業株式会社 | Curable resin composition, imide compound, adhesive, adhesive film, coverlay film, and flexible copper-clad laminate |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1827611A (en) * | 2006-04-14 | 2006-09-06 | 黑龙江省石油化学研究院 | Process for preparing 3,3',4,4'-tetracarboxydiphthalic ether dianhydride |
| CN104529966A (en) * | 2015-01-11 | 2015-04-22 | 景炜杰 | Preparation method of bisphenol A diether dianhydride |
| CN105330634A (en) * | 2015-12-07 | 2016-02-17 | 济南轩鸿生物医药有限公司 | One-pot method for preparing 3-hydroxyphtalic anhydride |
| JP2020007397A (en) * | 2018-07-03 | 2020-01-16 | 積水化学工業株式会社 | Curable resin composition, imide compound, adhesive, adhesive film, coverlay film, and flexible copper-clad laminate |
Non-Patent Citations (1)
| Title |
|---|
| 2-氯-4-(4-氯苯氧基)-苯乙酮合成方法的研究;翟智卫;《化工时刊》;20100831;第24卷(第8期);第63-65页 * |
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