CN115073405B - Preparation method of super-trace high-purity diphenyl ether dianhydride - Google Patents
Preparation method of super-trace high-purity diphenyl ether dianhydride Download PDFInfo
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- CN115073405B CN115073405B CN202210893502.6A CN202210893502A CN115073405B CN 115073405 B CN115073405 B CN 115073405B CN 202210893502 A CN202210893502 A CN 202210893502A CN 115073405 B CN115073405 B CN 115073405B
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- 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
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Abstract
The application relates to the technical field of refining and purification, and particularly discloses a preparation method of super-trace high-purity diphenyl ether dianhydride. The preparation method comprises the following steps: respectively adding the diphenyl ether tetracarboxylic acid and the hydrochloric acid into a solvent, dissolving for 1-3 hours at the temperature of 125-140 ℃, then adding sodium silicate under the stirring condition, stirring for 0.5-1 hour, cooling to 20-30 ℃, and filtering to obtain a filter cake; and drying and sublimating the filter cake in vacuum to obtain the diphenyl ether dianhydride. By adopting the preparation method provided by the application, the target product can be obtained after once treatment of the diphenyl ether tetracarboxylic acid, the product yield is up to about 95%, the product purity is up to more than 99.95%, the content of metal ions in the product is lower than 80ppb, no waste water is generated basically in the production process, and the process is simple, thereby being beneficial to industrial popularization and application.
Description
Technical Field
The application relates to the technical field of refining and purification, in particular to a preparation method of ultra-trace high-purity diphenyl ether dianhydride.
Background
The diphenyl ether dianhydride (ODPA) can be widely applied to the fields of aerospace, microelectronics, nano-scale, liquid crystal, separation filter membranes and the like. The requirements for purity and cleanliness of the diphenyl ether dianhydride product are different according to the application fields. For example, the electronic cascade phenyl ether dianhydride is a main raw material for preparing polyimide, and the electronic polar polyimide for aerospace has strict requirements on the purity, cleanliness, particle crystal form, organic residues, metal ions and other pollutants, even the requirement on the metal ions reaches the part per bililion level, and the purity of the product is required to be more than 99.95%, so that the electronic polar polyimide for aerospace has extremely high requirements on the purity and cleanliness of the raw material for preparing the electronic polar polyimide.
The ODPA prepared by the prior art has the purity of 99.5-99.9%, and metal ions can only reach ppm level, so that the ODPA is difficult to meet the requirement of the electronic polar polyimide applied to aerospace on raw materials. Even if the metal ions are removed by adding a large amount of mixed solvent, only ODPA with the metal ions of 1000ppb to 5000ppb is obtained, and a large amount of waste liquid is generated, so that the environmental protection problem is caused. Therefore, in order to meet the requirement of continuous development of polyimide as a special engineering material in the application field, a preparation method of high-purity ODPA with ultra-trace metal ions is needed to be searched, and the method has important significance for opening ODPA high-end markets of enterprises and reducing environmental protection pressure of the enterprises.
Disclosure of Invention
In view of the above, the application provides a preparation method of ultra-trace high-purity ODPA, which utilizes the reaction of hydrochloric acid and sodium silicate to generate silicic acid colloid, then makes the silicic acid colloid and the diphenyl ether tetracarboxylic acid molecules carry out full gluing through cooling to form a three-dimensional net structure, can fully remove contained metal ions, and then obtains the ultra-trace high-purity ODPA of the metal ions through high-temperature dehydration and sublimation of one-step diphenyl ether tetracarboxylic acid.
In order to achieve the above purpose, the embodiment of the application adopts the following technical scheme:
a method for preparing super-trace high-purity diphenyl ether dianhydride, which comprises the following steps:
respectively adding diphenyl ether tetracarboxylic acid and hydrochloric acid into a solvent, dissolving for 1-3 h at 125-140 ℃, then adding sodium silicate under stirring, stirring for 0.5-1 h, cooling to 20-30 ℃, and filtering to obtain a filter cake, wherein the mass ratio of the hydrochloric acid to the sodium silicate is 1-3:0.5-1;
and step two, drying the filter cake and sublimating in vacuum to obtain the diphenyl ether dianhydride.
Compared with the prior art, the preparation method of the ultra-trace high-purity biphenyl ether dianhydride has the following advantages:
the application is dissolved by hydrochloric acid and provides an acidic environment, then the silicic acid colloid obtained by the reaction of hydrochloric acid and sodium silicate is utilized, and then the silicic acid colloid and the diphenyl ether tetracarboxylic acid molecules are fully glued by cooling to form a three-dimensional reticular structure, so that the contained metal ions can be fully bound in the reticular structure, and further the metal ions are fully removed; and then carrying out high-temperature dehydration and sublimation on the biphenyl ether tetracarboxylic acid to obtain the high-purity ODPA with ultra-trace metal ions.
By adopting the preparation method provided by the application, the target product can be obtained after once treatment of the diphenyl ether tetracarboxylic acid, the product yield is up to about 95%, the product purity is up to more than 99.95%, the content of metal ions in the product is lower than 80ppb, no waste water is generated basically in the production process, and the process is simple, thereby being beneficial to industrial popularization.
Optionally, the mass ratio of the hydrochloric acid to the biphenyl ether tetracarboxylic acid is 0.01-0.03:1.
Through the optimized mass ratio, the method is favorable for promoting the even dispersion of the diphenyl ether tetracarboxylic acid in the solvent, promoting the full reaction of the hydrochloric acid and the sodium silicate to obtain the silicic acid colloid, avoiding the risk of introducing new impurities due to excessive sodium silicate, ensuring that the process can not generate solid waste, and being favorable for recycling the residual materials.
Optionally, the solvent is an aqueous ethanol solution with the volume concentration of 60% -70%.
Optionally, the mass ratio of the biphenyl ether tetracarboxylic acid to the solvent is 1:4.5-5.5.
The preferable solvent and the mass ratio thereof are beneficial to the generation of a three-dimensional network structure by hydrochloric acid, sodium silicate and biphenyl ether tetracarboxylic acid and promote the removal of metal ions.
Optionally, the sodium silicate has a modulus of 2.5 or 3.3.
Optionally, the sodium silicate is added dropwise, and the dropwise adding time is 25-35 min.
By controlling sodium silicate (Na 2 SiO 3 ·9H 2 O) ensures that the mixture fully reacts with hydrochloric acid to obtain silicic acid colloid.
Optionally, the stirring speed is 800 rpm-1000 rpm.
Optionally, the concentration of the hydrochloric acid is 25-32 wt%.
Optionally, the conditions of vacuum sublimation are: the temperature is 210-240 ℃ and the vacuum degree is 1-3 mmHg.
Through the optimized vacuum sublimation condition, the high-temperature dehydration and sublimation of the one-step diphenyl ether tetracarboxylic acid are ensured to produce the ultra-trace diphenyl ether dianhydride.
Optionally, the temperature of the drying is 100-105 ℃.
Optionally, the pressure in the dissolution process is 0.8 Mpa-1 Mpa.
Optionally, the rotating speed in the cooling process is 100 rpm-200 rpm.
The preparation method provided by the application is suitable for preparing the diphenyl ether dianhydride from the diphenyl ether tetracarboxylic acid with the content of more than 95%. If the content of the diphenyl ether tetracarboxylic acid is low, the preparation method can be repeated for a plurality of times to obtain the high-purity ODPA with ultra-trace metal ions.
Detailed Description
The present application will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
Example 1
The embodiment provides a preparation method of super-trace high-purity diphenyl ether dianhydride, which comprises the following steps:
step one, adding 100g of biphenyl ether tetracarboxylic acid into 450g of ethanol water solution with the volume concentration of 70% under the stirring condition of 850rpm, adding 1.0g of hydrochloric acid with the concentration of 30wt%, dissolving for 1h at 140 ℃, then pumping in 3.3 modulus, adding 0.5g of sodium silicate, stirring for 0.5h after the pumping in for 30min, cooling to 20 ℃, and filtering to obtain 107.5g of filter cake wet product;
step two, drying the filter cake at 105 ℃ to obtain 102.8g of mixture; and (3) putting the mixture into a sublimator, performing vacuum sublimation at 220 ℃ and a vacuum degree of 1mmHg, and collecting 1.24g of fractions before sublimation, 85.4g of main fractions and 1.95g of sublimated tailings to obtain the diphenyl ether dianhydride.
The prepared front fraction and biochemical tailing are used for recycling; the content of diphenyl ether dianhydride in the main fraction was 99.95% and the molar yield was 95.31%.
Example 2
The embodiment provides a preparation method of super-trace high-purity diphenyl ether dianhydride, which comprises the following steps:
step one, adding 100g of biphenyl ether tetracarboxylic acid into 500g of ethanol water solution with the volume concentration of 65% under the stirring condition of 900rpm, adding 3g of hydrochloric acid with the concentration of 25wt%, dissolving for 3 hours at the temperature of 125 ℃, pumping 3.3 g of modulus, adding 0.85g of sodium silicate, stirring for 1 hour after pumping for 25 minutes, cooling to the temperature of 25 ℃, and filtering to obtain 108.7g of filter cake wet product;
step two, drying the filter cake at 100 ℃ to obtain 103.1g of mixture; and (3) putting the mixture into a sublimator, performing vacuum sublimation at the temperature of 210 ℃ and the vacuum degree of 3mmHg, and collecting 1.14g of a fraction before sublimation, 84.6g of a main fraction and 1.95g of a sublimating tailing to obtain the diphenyl ether dianhydride.
The prepared front fraction and biochemical tailing are used for recycling; the content of diphenyl ether dianhydride in the main fraction was 99.96% and the molar yield was 94.4%.
Example 3
The embodiment provides a preparation method of super-trace high-purity diphenyl ether dianhydride, which comprises the following steps:
step one, adding 100g of biphenyl ether tetracarboxylic acid into 550g of ethanol water solution with the volume concentration of 60% under the stirring condition of 1000rpm, adding 2.2g of hydrochloric acid with the concentration of 32wt%, dissolving for 2 hours at 130 ℃, then pumping in 2.5 modulus, adding 0.95g of sodium silicate, stirring for 0.8 hours after pumping in for 35 minutes, cooling to 30 ℃, and filtering to obtain 111.4g of filter cake wet product;
step two, drying the filter cake at 105 ℃ to obtain 103.2g of mixture; and (3) putting the mixture into a sublimator, performing vacuum sublimation at the temperature of 240 ℃ and the vacuum degree of 2.2mmHg, and collecting 0.93g of a fraction before sublimation, 85.2g of a main fraction and 1.59g of a sublimating tail material to obtain the diphenyl ether dianhydride.
The prepared front fraction and biochemical tailing are used for recycling; the content of diphenyl ether dianhydride in the main fraction was 99.98% and the molar yield was 95.09%.
In order to better illustrate the technical solutions of the present application, the following is further compared with examples of the present application.
Comparative example 1
The comparative example provides a preparation method of super-trace high-purity diphenyl ether dianhydride, which is different from example 1 in that sodium silicate is not added, 3.93g of distillation before sublimation, 80.5g of main product and 3.49g of sublimation tail are collected, and diphenyl ether dianhydride is obtained.
The content of diphenyl ether dianhydride in the main fraction was 99.78% and the molar yield was 89.84%.
Comparative example 2
The comparative example provides a preparation method of super trace high-purity diphenyl ether dianhydride, which is different from example 1 in that the adding amount of sodium silicate is 2.5g, 1.44g of fraction before sublimation, 71.4g of main product and 1.95g of sublimated tailing are collected, and diphenyl ether dianhydride is obtained.
The content of diphenyl ether dianhydride in the main fraction was 99.88% and the molar yield was 79.68%.
Comparative example 3
The comparative example provides a process for preparing super trace high purity diphenyl ether dianhydride, which is different from example 1 in that after cooling to 60 ℃, filtering is carried out, 1.22g of distillation before sublimation, 85.6g of main product and 1.91g of sublimation tail are collected, and diphenyl ether dianhydride is obtained.
The content of diphenyl ether dianhydride in the main fraction was 99.86%, and the molar yield was 95.31%.
The results of detection of metal ions in the raw material (diphenyl ether tetracarboxylic acid) and the product (main fraction) are shown below, in accordance with the diphenyl ether tetracarboxylic acid used in examples 1 to 3 and comparative examples 1 to 3.
TABLE 1
As can be seen from Table 1, according to the preparation method provided by the application, the silicic acid colloid is obtained by reacting hydrochloric acid with sodium silicate in a specific proportion, and then the metal ion binding body is formed by cooling, so that the ultra-trace high-purity ODPA of the metal ion can be obtained.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the application.
Claims (10)
1. A preparation method of super-trace high-purity diphenyl ether dianhydride is characterized by comprising the following steps: the preparation method comprises the following steps:
respectively adding diphenyl ether tetracarboxylic acid and hydrochloric acid into a solvent, dissolving for 1-3 h at 125-140 ℃, then adding sodium silicate under stirring, stirring for 0.5-1 h, cooling to 20-30 ℃, and filtering to obtain a filter cake, wherein the mass ratio of the hydrochloric acid to the sodium silicate is 1-3:0.5-1;
and step two, drying the filter cake and sublimating in vacuum to obtain the diphenyl ether dianhydride.
2. The process for preparing a high purity diphenyl ether dianhydride having a super trace as claimed in claim 1, wherein: the mass ratio of the hydrochloric acid to the biphenyl ether tetracarboxylic acid is 0.01-0.03:1.
3. The process for preparing a high purity diphenyl ether dianhydride having a super trace as claimed in claim 1, wherein: the solvent is ethanol water solution with volume concentration of 60% -70%.
4. The process for preparing a high purity diphenyl ether dianhydride having a super trace as claimed in claim 1, wherein: the mass ratio of the biphenyl ether tetracarboxylic acid to the solvent is 1:4.5-5.5.
5. The process for preparing a high purity diphenyl ether dianhydride having a super trace as claimed in claim 1, wherein: the modulus of the sodium silicate is 2.5 or 3.3.
6. The process for preparing a high purity diphenyl ether dianhydride having a super trace as claimed in claim 1, wherein: the sodium silicate is added dropwise, and the dropwise adding time is 25-35 min; and/or
The stirring speed is 800 rpm-1000 rpm.
7. The process for preparing a high purity diphenyl ether dianhydride having a super trace as claimed in claim 1, wherein: the concentration of the hydrochloric acid is 25-32 wt%.
8. The process for preparing a high purity diphenyl ether dianhydride having a super trace as claimed in claim 1, wherein: the conditions of the vacuum sublimation are as follows: the temperature is 210-240 ℃ and the vacuum degree is 1-3 mmHg.
9. The process for preparing a high purity diphenyl ether dianhydride having a super trace as claimed in claim 1, wherein: the temperature of the drying is 100-105 ℃.
10. The process for preparing a high purity diphenyl ether dianhydride having a super trace as claimed in claim 1, wherein:
the pressure in the dissolving process is 0.8 Mpa-1 Mpa; and/or
The rotating speed in the cooling process is 100 rpm-200 rpm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073436A (en) * | 1991-10-25 | 1993-06-23 | 西方化学公司 | The preparation method of the acid anhydrides of oxydiphthalic acid and its purifying |
| JP2002097185A (en) * | 2000-09-20 | 2002-04-02 | New Japan Chem Co Ltd | Method for producing aromatic tetracarboxylic dianhydride |
| CN1800170A (en) * | 2004-12-22 | 2006-07-12 | 通用电气公司 | Method of purifying dianhydrides |
| CN111187240A (en) * | 2020-02-26 | 2020-05-22 | 河北海力香料股份有限公司 | Preparation method of 4, 4-diphenyl ether dianhydride |
| CN112851611A (en) * | 2021-01-28 | 2021-05-28 | 南通汇顺化工有限公司 | Preparation method of 4, 4' -diphenyl ether tetracarboxylic dianhydride |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7446214B2 (en) * | 2005-09-23 | 2008-11-04 | Sabic Innovative Plastics Ip B.V. | Method for purifying oxybisphthalic anhydrides |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073436A (en) * | 1991-10-25 | 1993-06-23 | 西方化学公司 | The preparation method of the acid anhydrides of oxydiphthalic acid and its purifying |
| JP2002097185A (en) * | 2000-09-20 | 2002-04-02 | New Japan Chem Co Ltd | Method for producing aromatic tetracarboxylic dianhydride |
| CN1800170A (en) * | 2004-12-22 | 2006-07-12 | 通用电气公司 | Method of purifying dianhydrides |
| CN111187240A (en) * | 2020-02-26 | 2020-05-22 | 河北海力香料股份有限公司 | Preparation method of 4, 4-diphenyl ether dianhydride |
| CN112851611A (en) * | 2021-01-28 | 2021-05-28 | 南通汇顺化工有限公司 | Preparation method of 4, 4' -diphenyl ether tetracarboxylic dianhydride |
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