CN113372212A - Method for recovering polyimide by selectively breaking imide bonds - Google Patents
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- C07C51/06—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid amides
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- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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Abstract
The invention belongs to the field of recycling of waste high polymer materials, and particularly relates to a method for recovering polyimide by selectively breaking imide bonds. The invention prepares polyimide waste, solvent and catalyst into a reaction system, and places the reaction system in a homogeneous reactor for degradation reaction. Filtering after degradation is finished, and adding deionized water to wash a filter cake to obtain aromatic diamine; the solvent in the filtrate is evaporated, and hydrochloric acid is added to obtain the aromatic pyromellitic acid. The invention utilizes the alkaline catalyst to selectively break imide bonds to obtain aromatic diamine and aromatic o-phthalic tetracarboxylic acid. The invention has the advantages of simple operation process, low recovery cost and easy separation to obtain products with high added value.
Description
Technical Field
The invention belongs to the field of recycling of waste high polymer materials, and particularly relates to a method for recovering polyimide by selectively breaking imide bonds.
Background
Polyimide is one of the organic polymer materials with the best combination property. The nano-composite material can be used for a long time within the temperature range of-200-300 ℃, has excellent wear resistance, chemical corrosion resistance, electrical insulation and the like, and is widely applied to the fields of aviation, aerospace, microelectronics, nano-scale, liquid crystal, separation membranes, laser and the like. Meanwhile, the use of polyimide in large quantities leads to the continuous increase of waste resources, and the recycling of polyimide is also concerned widely.
Polyimides are mainly prepared from aromatic diamines and aromatic dianhydrides. The preparation process of the aromatic diamine and the aromatic dianhydride is complex and expensive, so that the monomer with high added value is recovered from the polyimide waste, the resource waste can be reduced, the environmental pollution is avoided, and a new method is provided for preparing the raw material for synthesizing the polyimide.
There are two types of patent technologies for degrading polyimide waste disclosed at present: one is the use of ammonia or hydrazine hydrate, as disclosed in chinese patents CN103553906B and CN 109503614B. Another is an aqueous solution of sodium hydroxide or potassium hydroxide, as disclosed in chinese patents CN101519359B and CN 111073035A.
Patent CN103553906B discloses a method for recovering polyimide raw material by hydrolyzing polyimide waste film with ammonia water, which comprises the following steps: adding the polyimide waste film crushed into 5-10 mm length into ammonia water by adopting ammonia water with the concentration of 25-30 weight percent, controlling the solid content to be 20 weight percent, and carrying out hydrolysis reaction for 3 hours in a hydrolysis autoclave at the temperature of 200 ℃ and the pressure of 1.4 MPa.
Patent CN109503614B discloses a method for recycling polyimide waste, which provides the following steps: adding the polyimide waste to be recovered into a reactor, introducing nitrogen into the reactor, and completely replacing air in the reactor with the nitrogen; adding hydrazine hydrate with the hydrazine content of 10-95% into the reactor, and carrying out a hydrazinolysis reaction with the polyimide waste under the conditions of normal pressure and 20-130 ℃.
Patent CN101519359B discloses a polyimide hydrolysis recovery method, which comprises the following steps: hydrolyzing the polyimide waste in a sodium hydroxide or potassium hydroxide aqueous solution under the nitrogen atmosphere at 90-99 ℃ until the materials are dissolved, and filtering to remove insoluble substances; and heating the filtrate to boiling, continuously hydrolyzing, evaporating part of water, and continuously refluxing for 3-4 hours under the conditions of introducing nitrogen and boiling.
Patent CN111073035A discloses a method for rapidly degrading and recovering polyimide material, which provides the following steps: firstly, soaking a polyimide material in a dimethyl sulfoxide solvent, and heating to 60-120 ℃ to fully swell the material; taking out the swelled polyimide material, draining, soaking in 1-15 wt% concentration sodium hydroxide aqua and maintaining at 60-100 deg.c.
The first method of hydrolyzing polyimide with ammonia water requires high pressure, and ammonia water has high volatility, which is not favorable for industrialization. The subsequent treatment process of the degradation product is complicated by using hydrazine hydrate to recover the polyimide. The second method of recovering polyimide with sodium hydroxide or potassium hydroxide solution has complicated degradation process and the obtained product is unknown small molecular compound.
Disclosure of Invention
The invention provides a method for recovering polyimide by selectively breaking imide bonds based on the defects in the prior art.
In order to realize the purpose, the invention is realized by the following technical scheme:
a method for recovering polyimide by selectively cleaving imide bonds, comprising the steps of: mixing a solvent and a catalyst to prepare a reaction system I, mixing a polyimide material with the reaction system I, adding the mixture into a reaction kettle, sealing the reaction kettle, and placing the reaction kettle into a homogeneous reactor for heating reaction; after the reaction is finished, cooling to room temperature, filtering, and adding deionized water to wash a filter cake to obtain an aromatic diamine monomer; evaporating the organic solvent in the filtrate, adding hydrochloric acid to precipitate the aromatic pyromellitic acid, filtering and drying to obtain the aromatic pyromellitic acid.
Further, the catalyst is LiOH, RbOH, CsOH, (CH)3)4NOH、(CH3CH2)4NOH、CH3CH2·N(CH3)3OH、Na2CO3、K2CO3Any one of them. The invention utilizes the alkaline catalyst to selectively break the imide bond in the polyimide to prepare the aromatic diamine and the aromatic o-phthalic acid, and the catalyst has better catalytic action on the selective breaking of the imide bond.
Further, the solvent is water or a mixed solution of water and an organic reagent, wherein the mass ratio of the water to the organic reagent is 1: 1-10. The alkaline catalyst has good dissolving effect in water, active groups required by the degradation of the polyimide are dissociated, and the degradation products can be dissolved in the water, so that the reaction process and the subsequent product separation can be accelerated; the organic solvent is used for improving the wettability of the reaction system and the polyimide material.
Further, the organic reagent is any one of acetone, chloroform, pyridine, propanol, butanol, isopropanol, N-methylpyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, tetrahydrofuran, and m-cresol. The solvent selected by the scheme has better swelling effect and reaction performance on polyimide.
Further, the mass ratio of the polyimide material to the reaction system I is 1: 1-100; the mass fraction of the catalyst is 20-40%. When the mass ratio of the polyimide material to the reaction system I is too large, the solvent cannot fully swell the polyimide material, so that the catalytic action of the catalyst is not facilitated; when the mass ratio of the polyimide material to the reaction system I is too small, the use amount of the solvent is large, and the economy is not good. When the mass fraction of the catalyst is less than 20%, the concentration of the catalyst is low, which is not beneficial to the reaction; when the mass fraction of the catalyst is more than 40%, the catalyst is excessive, which is not beneficial to the separation of subsequent products and also causes unnecessary waste.
Further, the heating temperature is 110-250 ℃, and the reaction time is 1-7 h. When the heating temperature is lower than 110 ℃, the reaction does not occur, and when the heating temperature is higher than 250 ℃, side reactions occur. When the reaction time is less than 1h, the reaction is insufficient; when the reaction time is more than 7h, the reaction effect is not obviously improved.
Further, the polyimide to be recycled has the following structure:
wherein Ar is1The structure comprises the following structures:
Ar2the structure comprises the following structures:
compared with the prior art, the invention has the following beneficial effects:
(1) the controllable degradation of polyimide is realized by selectively breaking imide bonds, and monomers with high added values are recycled, and the reaction mechanism is as follows:
(2) under the reaction condition, the recovery rate of the two monomers can reach 90-100%.
Drawings
FIG. 1 is a nuclear magnetic resonance carbon spectrum of pyromellitic acid monomer;
FIG. 2 is a carbon NMR spectrum of 4, 4' -diaminodiphenyl ether;
FIG. 3 is a nuclear magnetic resonance carbon spectrum of 4, 4' -diaminodiphenylmethane;
FIG. 4 is a NMR carbon spectrum of p-phenylenediamine.
Detailed Description
The following will describe embodiments of the present invention in detail with reference to the examples, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented. It should be noted that, unless conflicting, the embodiments and the features in the embodiments of the present invention may be combined with each other, and the formed technical solutions are within the scope of the present invention.
Example 1
In this embodiment, a method for recovering polyimide by selectively breaking imide bonds includes the following steps:
preparing water and m-cresol into a mixed solution according to the mass ratio of 1:1, preparing the mixed solution and LiOH into a reaction system I according to the mass fraction of 20% of a catalyst, mixing a polyimide material and the reaction system I according to the mass ratio of 1:1, adding the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor, heating the mixture to 220 ℃, and reacting for 7 hours. After the reaction is finished, cooling to room temperature, filtering, and adding deionized water to wash a filter cake to obtain 4, 4' -diaminodiphenyl ether; evaporating the organic solvent in the filtrate, adding hydrochloric acid to separate out aromatic pyromellitic acid, filtering and drying to obtain pyromellitic acid.
FIG. 1 is a nuclear magnetic resonance carbon spectrum of a recovered pyromellitic acid monomer; FIG. 2 is a carbon nuclear magnetic resonance spectrum of 4, 4' -diaminodiphenyl ether monomer. It can be seen from fig. 1 and 2 that the recovered pyromellitic acid and 4, 4' -diaminodiphenyl ether are high in purity and hardly have any impurity peak.
Example 2
In this embodiment, a method for recovering polyimide by selectively breaking imide bonds includes the following steps:
preparing water and N, N' -dimethylacetamide into a mixed solution according to the mass ratio of 1:5, and mixing the mixed solution with (CH)3)4Preparing a reaction system I from NOH according to the mass fraction of 30 percent of a catalyst, mixing a polyimide material and the reaction system I according to the mass ratio of 1:10, adding the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle into a homogeneous reactor, heating the reaction kettle to 110 ℃,and reacting for 6 h. After the reaction is finished, cooling to room temperature, filtering, adding deionized water to wash a filter cake to obtain 4,4 '-diaminodiphenylmethane, wherein the nuclear magnetic resonance carbon spectrum of the 4, 4' -diaminodiphenylmethane is shown in figure 3; evaporating the organic solvent in the filtrate, adding hydrochloric acid to precipitate aromatic pyromellitic acid, filtering and drying to obtain pyromellitic acid.
Example 3
In this embodiment, a method for recovering polyimide by selectively breaking imide bonds includes the following steps:
preparing water and N-methyl pyrrolidone into a mixed solution according to the mass ratio of 1:8, preparing a reaction system I from the mixed solution and CsOH according to the mass fraction of 20% of a catalyst, mixing a polyimide material and the reaction system I according to the mass ratio of 1:30, adding the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor, heating the mixture to 160 ℃, and reacting for 7 hours. After the reaction is finished, cooling to room temperature, filtering, adding deionized water to wash a filter cake to obtain p-phenylenediamine, wherein the nuclear magnetic resonance carbon spectrum of the p-phenylenediamine is shown in figure 4; evaporating the organic solvent in the filtrate, adding hydrochloric acid to precipitate aromatic pyromellitic acid, filtering and drying to obtain biphenyl tetracarboxylic acid.
Example 4
In this embodiment, a method for recovering polyimide by selectively breaking imide bonds includes the following steps:
preparing water and butanol into a mixed solution according to the mass ratio of 1:10, preparing the mixed solution and RbOH according to the mass fraction of 40% of a catalyst into a reaction system I, mixing a polyimide material and the reaction system I according to the mass ratio of 1:70, adding the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor, heating the reaction kettle to 250 ℃, and reacting for 1 hour. After the reaction is finished, cooling to room temperature, filtering, and adding deionized water to wash a filter cake to obtain p-phenylenediamine; evaporating the organic solvent in the filtrate, adding hydrochloric acid to precipitate aromatic o-phthalic tetracarboxylic acid, filtering and drying to obtain diphenyl ether tetracarboxylic acid.
Example 5
In this embodiment, a method for recovering polyimide by selectively breaking imide bonds includes the following steps:
preparing water and pyridine into a mixed solution according to the mass ratio of 1:7, and mixing the mixed solution with Na2CO3Preparing a reaction system I according to 25% of the mass fraction of a catalyst, mixing a polyimide material and the reaction system I according to the mass ratio of 1:100, adding the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor, heating the mixture to 240 ℃, and reacting for 7 hours. After the reaction is finished, cooling to room temperature, filtering, and adding deionized water to wash a filter cake to obtain 4, 4' -diaminodiphenyl ether; evaporating the organic solvent in the filtrate, adding hydrochloric acid to precipitate aromatic pyromellitic acid, filtering and drying to obtain benzophenone tetracarboxylic acid.
Example 6
In this embodiment, a method for recovering polyimide by selectively breaking imide bonds includes the following steps:
preparing water and isopropanol into a mixed solution according to the mass ratio of 1:6, and mixing the mixed solution with (CH)3CH2)4Preparing a reaction system I from NOH according to the mass fraction of 30% of a catalyst, mixing a polyimide material and the reaction system I according to the mass ratio of 1:80, adding the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor, heating the reaction kettle to 200 ℃, and reacting for 4 hours. After the reaction is finished, cooling to room temperature, filtering, and adding deionized water to wash a filter cake to obtain 4, 4' -diaminodiphenylmethane; evaporating the organic solvent in the filtrate, adding hydrochloric acid to precipitate aromatic pyromellitic acid, filtering and drying to obtain biphenyl tetracarboxylic acid.
Example 7
In this embodiment, a method for recovering polyimide by selectively breaking imide bonds includes the following steps:
preparing water and tetrahydrofuran into a mixed solution according to the mass ratio of 1:3, and mixing the mixed solution with K2CO3Preparing a reaction system I according to the mass fraction of 35% of a catalyst, mixing a polyimide material and the reaction system I according to the mass ratio of 1:40, adding the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor, heating the mixture to 140 ℃, and reacting for 4 hours. After the reaction is finished, cooling to room temperature, filtering, and adding deionized water to wash a filter cake to obtain 4, 4' -diaminodiphenyl ether; evaporating the organic solvent in the filtrate, adding hydrochloric acid to precipitate aromatic o-phthalic tetracarboxylic acid, filtering and drying to obtain diphenyl ether tetracarboxylic acid.
Example 8
In this embodiment, a method for recovering polyimide by selectively breaking imide bonds includes the following steps:
preparing water and acetone into a mixed solution according to the mass ratio of 1:4, and mixing the mixed solution with CH3CH2·N(CH3)3Preparing a reaction system I from OH according to 20% of the mass fraction of a catalyst, mixing a polyimide material and the reaction system I according to the mass ratio of 1:50, adding the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor, heating the reaction kettle to 150 ℃, and reacting for 6 hours. After the reaction is finished, cooling to room temperature, filtering, and adding deionized water to wash a filter cake to obtain 4, 4' -diaminodiphenylmethane; evaporating the organic solvent in the filtrate, adding hydrochloric acid to precipitate aromatic o-phthalic tetracarboxylic acid, filtering and drying to obtain diphenyl ether tetracarboxylic acid.
Example 9
In this embodiment, a method for recovering polyimide by selectively breaking imide bonds includes the following steps:
preparing water and propanol into a mixed solution according to the mass ratio of 1:2, preparing the mixed solution and CsOH into a reaction system I according to the mass fraction of 35% of a catalyst, mixing a polyimide material and the reaction system I according to the mass ratio of 1:60, adding the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor, heating the mixture to 230 ℃, and reacting for 5 hours. After the reaction is finished, cooling to room temperature, filtering, and adding deionized water to wash a filter cake to obtain 4, 4' -diaminodiphenylmethane; evaporating the organic solvent in the filtrate, adding hydrochloric acid to precipitate aromatic pyromellitic acid, filtering and drying to obtain benzophenone tetracarboxylic acid.
Example 10
In this embodiment, a method for recovering polyimide by selectively breaking imide bonds includes the following steps:
preparing water and chloroform into a mixed solution according to the mass ratio of 1:9, preparing the mixed solution and RbOH into a reaction system I according to the mass fraction of 30% of a catalyst, mixing a polyimide material and the reaction system I according to the mass ratio of 1:25, adding the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor, heating the mixture to 180 ℃, and reacting for 6 hours. After the reaction is finished, cooling to room temperature, filtering, and adding deionized water to wash a filter cake to obtain p-phenylenediamine; evaporating the organic solvent in the filtrate, adding hydrochloric acid to precipitate aromatic pyromellitic acid, filtering and drying to obtain pyromellitic acid.
Example 11
In this embodiment, a method for recovering polyimide by selectively breaking imide bonds includes the following steps:
preparing water and N, N' -dimethylformamide into a mixed solution according to the mass ratio of 1:9, and mixing the mixed solution with Na2CO3Preparing a reaction system I according to the mass fraction of a catalyst of 28 percent, mixing the polyimide material and the reaction system I according to the mass ratio of 1:20, adding the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor, heating the mixture to 230 ℃, and reacting for 5 hours. After the reaction is finished, cooling to room temperature, filtering, and adding deionized water to wash a filter cake to obtain 4, 4' -diaminodiphenyl ether; evaporating the organic solvent in the filtrate, adding hydrochloric acid to precipitate aromatic pyromellitic acid, filtering and drying to obtain biphenyl tetracarboxylic acid.
Example 12
In this embodiment, a method for recovering polyimide by selectively breaking imide bonds includes the following steps:
preparing water and LiOH into a reaction system I according to the mass fraction of 20% of a catalyst, mixing a polyimide material and the reaction system I according to the mass ratio of 1:10, adding the mixture into a reaction kettle, sealing the reaction kettle, placing the reaction kettle into a homogeneous reactor, heating the mixture to 150 ℃, and reacting for 6 hours. After the reaction is finished, cooling to room temperature, filtering, and adding deionized water to wash a filter cake to obtain 4, 4' -diaminodiphenyl ether; evaporating the solvent in the filtrate, adding hydrochloric acid to precipitate aromatic pyromellitic acid, filtering and drying to obtain pyromellitic acid.
Claims (8)
1. A method for recovering polyimide by selectively breaking imide bonds is characterized by comprising the following steps: mixing a solvent and a catalyst to prepare a reaction system I, mixing a polyimide material with the reaction system I, adding the mixture into a reaction kettle, sealing the reaction kettle, and placing the reaction kettle into a homogeneous reactor for heating reaction; after the reaction is finished, cooling to room temperature, filtering, and adding deionized water to wash a filter cake to obtain aromatic diamine; evaporating the solvent in the filtrate, adding hydrochloric acid to precipitate aromatic pyromellitic acid, filtering and drying to obtain the aromatic pyromellitic acid.
2. The method of claim 1 for recovering polyimide by selectively cleaving imide bonds, wherein: the solvent is water or a mixed solution of water and an organic reagent, wherein the mass ratio of the water to the organic reagent is 1: 1-10.
3. The method for recovering polyimide by selectively breaking imide bonds as claimed in claim 2, wherein: the organic reagent is any one of acetone, chloroform, pyridine, propanol, butanol, isopropanol, N-methylpyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, tetrahydrofuran and m-cresol.
4. The method of claim 1 for recovering polyimide by selectively cleaving imide bonds, wherein: the catalyst is LiOH, RbOH, CsOH, (CH)3)4NOH、(CH3CH2)4NOH、CH3CH2·N(CH3)3OH、Na2CO3、K2CO3Any one of them.
5. The method of claim 1 for recovering polyimide by selectively cleaving imide bonds, wherein: the mass ratio of the polyimide material to the reaction system I is 1: 1-100.
6. The method of claim 1 for recovering polyimide by selectively cleaving imide bonds, wherein: the mass fraction of the catalyst is 20-40%.
7. The method of claim 1 for recovering polyimide by selectively cleaving imide bonds, wherein: the heating temperature is 110-250 ℃, and the reaction time is 1-7 h.
8. The method of claim 1 for recovering polyimide by selectively cleaving imide bonds, wherein: the polyimide to be recycled has the following structure:
wherein Ar is1The structure comprises the following structures:
Ar2the structure comprises the following structures:
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115057769A (en) * | 2022-07-27 | 2022-09-16 | 河北海力香料股份有限公司 | Method for recycling waste polyimide film |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324789A (en) * | 2001-06-26 | 2001-12-05 | 中国科学院长春应用化学研究所 | Polyimide hydrolyzing recovery process |
| CN103553906A (en) * | 2013-11-05 | 2014-02-05 | 上海固创化工新材料有限公司 | Method of recovering polyimide raw material by hydrolyzing polyimide waste thin film by ammonia water |
| CN104844819A (en) * | 2015-05-06 | 2015-08-19 | 无锡顺铉新材料有限公司 | Modified polyimide film and modified polyimide precursor composite film waste material recovery processing method |
| CN105017560A (en) * | 2015-05-06 | 2015-11-04 | 无锡顺铉新材料有限公司 | Waste recovery processing method for modified polyimide precursor composition film |
| CN109503614A (en) * | 2018-12-04 | 2019-03-22 | 宏威高新材料有限公司 | A method of recycling polyimides waste |
| CN110563570A (en) * | 2019-09-24 | 2019-12-13 | 中国科学院山西煤炭化学研究所 | Method for preparing terephthalic acid and p-phenylenediamine by degrading p-aramid |
| CN111073035A (en) * | 2019-12-12 | 2020-04-28 | 江苏奥神新材料股份有限公司 | Method for rapidly degrading and recycling polyimide material |
| WO2021091420A1 (en) * | 2019-11-07 | 2021-05-14 | Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской Академии наук (ФГБУН ИПХФ РАН) | Method for processing polyimide materials |
-
2021
- 2021-06-17 CN CN202110673745.4A patent/CN113372212A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324789A (en) * | 2001-06-26 | 2001-12-05 | 中国科学院长春应用化学研究所 | Polyimide hydrolyzing recovery process |
| CN103553906A (en) * | 2013-11-05 | 2014-02-05 | 上海固创化工新材料有限公司 | Method of recovering polyimide raw material by hydrolyzing polyimide waste thin film by ammonia water |
| CN104844819A (en) * | 2015-05-06 | 2015-08-19 | 无锡顺铉新材料有限公司 | Modified polyimide film and modified polyimide precursor composite film waste material recovery processing method |
| CN105017560A (en) * | 2015-05-06 | 2015-11-04 | 无锡顺铉新材料有限公司 | Waste recovery processing method for modified polyimide precursor composition film |
| CN109503614A (en) * | 2018-12-04 | 2019-03-22 | 宏威高新材料有限公司 | A method of recycling polyimides waste |
| CN110563570A (en) * | 2019-09-24 | 2019-12-13 | 中国科学院山西煤炭化学研究所 | Method for preparing terephthalic acid and p-phenylenediamine by degrading p-aramid |
| WO2021091420A1 (en) * | 2019-11-07 | 2021-05-14 | Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской Академии наук (ФГБУН ИПХФ РАН) | Method for processing polyimide materials |
| CN111073035A (en) * | 2019-12-12 | 2020-04-28 | 江苏奥神新材料股份有限公司 | Method for rapidly degrading and recycling polyimide material |
Non-Patent Citations (1)
| Title |
|---|
| TETSUO HONMA: "Hydrolysis kinetics of PMDA/ODA polyimide for monomer recovery using sodium hydroxide in high-temperature water", THE JOURNAL OF SUPERCRITICAL FLUIDS, vol. 166, pages 1 - 6 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115057769A (en) * | 2022-07-27 | 2022-09-16 | 河北海力香料股份有限公司 | Method for recycling waste polyimide film |
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