CN1324789A - Polyimide hydrolyzing recovery process - Google Patents
Polyimide hydrolyzing recovery process Download PDFInfo
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- CN1324789A CN1324789A CN01129547A CN01129547A CN1324789A CN 1324789 A CN1324789 A CN 1324789A CN 01129547 A CN01129547 A CN 01129547A CN 01129547 A CN01129547 A CN 01129547A CN 1324789 A CN1324789 A CN 1324789A
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- polyimide
- diamines
- hydrolyzing
- distillation
- water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A method for hydrolyzing and recovering polyimide waste material includes the following steps: heating polyimide waste material in aqueous solution of alkali for decomposition, recovering water-insoluble diamine, water-washing crude diamine, recrystallizing or subliming for purification so to obtain the recovered diamine with monomer-level purity; acidifying the filtrate, then recovering tetraacid, water-washing the obtained tetraacid to remove salt, and then heating or jointly heating it and acetic anhydride so as to obtain dianhydride with monomer-level purity. Their recovery rate can be up to above 80%.
Description
The invention belongs to the hydrolyzing recovery process of polyimide.
Polyimide combines good mechanical property, electrical insulation capability, radiation resistance and dimensional stability etc. again simultaneously owing to have very high thermostability, and as insulating material, application in every respect such as engineering plastics just constantly enlarges.Polyimide can make it have organic solvent-resistant according to different requirements and maybe can be dissolved in some organic solvents owing to various in style, so that processing.
The hydrolyzing recovery process that the purpose of this invention is to provide a kind of polyimide.With the aqueous solution under heating the hydrolysis of treatment of polyimide waste with alkali, reclaim water-fast diamines, thick diamines is through washing, and recrystallization or distillation are purified, and obtain the recovery diamines of monomer level purity; Filtrate is reclaimed tetracid through acidifying, and tetracid is total to the dianhydride that heat just can obtain monomer level purity with heating or with aceticanhydride after washing is desalted.
The anti-diluted acid of polyimide, but can react with the vitriol oil or concentrated nitric acid, polyimide is because the difference of structure is also different for the stability of hydrolysis, and for example, the polyimide kind that has can be stood thousands of sterilizations.But common less stable to alkaline hydrolysis.The present invention utilizes this performance of polyimide that treatment of polyimide waste is carried out alkaline hydrolysis just, reclaims dianhydride and diacid monomer.
The present invention is to Kapton, fiber or granular plastics, and with the alkali aqueous solution of concentration 10-30%, the alkali of employing has sodium hydroxide, potassium hydroxide, ammonium hydroxide.Its consumption is the 6-10 equivalent of polyimide, at 100-150 ℃ of following heating hydrolysis 8-15 hour, reclaims water-fast diamines, washes with water, and 70 ℃ of oven dry in vacuum drying oven, distillation or use ethyl alcohol recrystallization obtain the recovery diamines of monomer level purity; The filtrate of diamines leaches thick tetracid after being 2 with sulfuric acid acidation to pH value, heats half an hour in 50% sulfuric acid, is cooled to room temperature, purifies with cold deionized water wash, oven dry, distillation, gets tetracid; Again through distillation or again with etc. weight aceticanhydride hot half an hour altogether, be cooled to room temperature, filter, oven dry, monomer level dianhydride.
The present invention to the rate of recovery of monomer level dianhydride and diamines more than 80%.
Embodiment provided by the invention is as follows:
Embodiment 1.
Will be by equal benzene dianhydride and 4, Kapton that 4 '-phenyl ether diamines obtains, 382 grams and 320 gram sodium hydroxide and 2 premium on currency reflux 8 hours in stirring, leach insoluble 4,4 '-phenyl ether diamines, wash with water 3 times, 70 ℃ of oven dry in vacuum drying oven, distillation obtains the monomer level 4 of white crystals, 4 '-phenyl ether diamines, 155 grams, yield is 85%.Filtrate is 2 with sulfuric acid acidation to pH value, is cooled to room temperature, filters, and filter cake heats half an hour in 50% sulfuric acid, be cooled to room temperature, with cold deionized water wash 2 times, 100 ℃ of oven dry, distillation is purified, and gets equal benzene dianhydride 159 grams of white crystals monomer level, yield 80%.
Embodiment 2.
Restrain by triphen two ether dianhydrides and 4 574, it is particle about 2mm that the polyimide plastic that 4 '-diphenylmethane diamine obtains is ground into diameter, with 400 gram potassium hydroxide and 3600 premium on currency at 150 ℃, 0.5Mpa following heated and stirred 8 hours, cooled and filtered, with filter cake 70 ℃ of oven dry in vacuum drying oven, with the dissolve with ethanol of 10 times of weight, elimination insolubles, filtrate is concentrated into half volume, cooling, obtain 4, cold water washing 3 times are used in the crystallization of 4 '-diphenylmethane diamine, recrystallization is purified in ethanol again, get monomer level 4,4 '-diphenylmethane diamine, 149 grams, yield 80%.The filtrate of thick diamines is 2 with sulfuric acid acidation to pH value, is cooled to room temperature, filters, filter cake heated and stirred half an hour in 50% sulfuric acid, be cooled to room temperature, use deionized water wash 6 times, 100 ℃ of oven dry, with the triphen diether tetracid that obtains again with etc. aceticanhydride hot half an hour altogether of weight, be cooled to room temperature, filter the following 200 ℃ of oven dry of vacuum, get monomer level triphen two ether dianhydrides 349 grams, yield 90%.
Embodiment 3.
Will be by phenyl ether dianhydride and 4, Kapton 474 grams that 4 '-phenyl ether diamines obtains, in 25% ammoniacal liquor of 1400 grams, 120 ℃ of heating are 15 hours in autoclave, leach after the cooling thick 4,4 '-phenyl ether diamines, handle as embodiment 1, get monomer level 4,4 '-phenyl ether diamines, 146 grams, yield 80%.The filtrate treatment process such as the embodiment 2 of thick diamines reclaim monomer level phenyl ether dianhydride 245 grams, yield 85%.
Embodiment 4.
Will be by hexafluorodianhydride and 3, the 150 ℃ of heating 10 hours in 480 gram sodium hydroxide and 4500 premium on currency of Kapton that 3 '-p-diaminodiphenyl obtains, 620 grams leach thick 3 after the cooling, 3 '-p-diaminodiphenyl, 170 grams are handled as embodiment 2, get monomer level 3,3 '-p-diaminodiphenyl, yield 85%.The filtrate treatment process such as the embodiment 2 of thick diamines reclaim monomer level hexafluorodianhydride 344 grams, yield 82%.
Embodiment 5
To be broken into 5 * 5mm particle, 453 grams by benzophenone dianhydride and mphenylenediamine and the prepared composite polyimide material of 15% glass fibre, reflux is 15 hours in 2 premium on currency that are dissolved with 240 gram sodium hydroxide, after the cooling solid is leached, 60 ℃ of dryings of vacuum, use diluted hydrochloric acid dissolution again, leach glass fibre, with filtrate with sodium hydroxide alkalize to pH be 12, leach the mphenylenediamine of separating out, with cold water washing 2 times, the following 60 ℃ of dry back distillations of vacuum are purified, and must reclaim mphenylenediamine 92 grams, yield 80%.Handle to such an extent that recovery benzophenone dianhydride 250 restrain yield 85% by embodiment 2 filtrate after the hydrolysis.
Claims (2)
1. the hydrolyzing recovery process of a polyimide, it is characterized in that Kapton, fiber or granular plastics, alkali aqueous solution with concentration 10-30%, its consumption is the 6-10 equivalent of polyimide, at 100-150 ℃ of following heating hydrolysis 8-15 hour, reclaim water-fast diamines, wash with water, 70 ℃ of oven dry in vacuum drying oven, distillation or use ethyl alcohol recrystallization obtain the recovery diamines of monomer level purity; The filtrate of diamines leaches thick tetracid after being 2 with sulfuric acid acidation to pH value, heats half an hour in 50% sulfuric acid, is cooled to room temperature, purifies with cold deionized water wash, oven dry, distillation, gets tetracid; Again through distillation or again with etc. weight aceticanhydride hot half an hour altogether, be cooled to room temperature, filter, oven dry, monomer level dianhydride.
2. the hydrolyzing recovery process of polyimide as claimed in claim 1 is characterized in that described alkali aqueous solution, and the alkali of employing has sodium hydroxide, potassium hydroxide, ammonium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01129547A CN1324789A (en) | 2001-06-26 | 2001-06-26 | Polyimide hydrolyzing recovery process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01129547A CN1324789A (en) | 2001-06-26 | 2001-06-26 | Polyimide hydrolyzing recovery process |
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|---|---|
| CN1324789A true CN1324789A (en) | 2001-12-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN01129547A Pending CN1324789A (en) | 2001-06-26 | 2001-06-26 | Polyimide hydrolyzing recovery process |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423623B (en) * | 2007-11-02 | 2011-05-11 | 宁波大学 | Depolymerization and recovery method of high temperature resistant nylon poly-para-phenylene diformyl hexane diamine |
| CN101519359B (en) * | 2009-04-16 | 2012-07-25 | 李汉毅 | Method for recovering polyimide through hydrolysis |
| CN103012837A (en) * | 2011-09-28 | 2013-04-03 | 广州源骏电子科技有限公司 | Recovery processing method of polyimide film |
| 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 |
| CN104761915A (en) * | 2015-03-20 | 2015-07-08 | 巨化集团技术中心 | Preparation method of wear-resistant polyimide and fluorine-containing polymer composition |
| 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 |
| CN104945268A (en) * | 2015-05-06 | 2015-09-30 | 无锡顺铉新材料有限公司 | Method for recovery processing of modified polyimide film wastes |
| 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 |
| WO2016093385A1 (en) * | 2014-12-10 | 2016-06-16 | 주식회사 엔케이이씨 | Method for recovering polyimide |
| CN109503614A (en) * | 2018-12-04 | 2019-03-22 | 宏威高新材料有限公司 | A method of recycling polyimides waste |
| 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 |
| CN112028366A (en) * | 2020-09-01 | 2020-12-04 | 上海固创化工新材料有限公司 | Method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride |
| CN113354527A (en) * | 2021-06-17 | 2021-09-07 | 中国科学院山西煤炭化学研究所 | Method for degrading polyimide material by microwave |
| CN113372212A (en) * | 2021-06-17 | 2021-09-10 | 中国科学院山西煤炭化学研究所 | Method for recovering polyimide by selectively breaking imide bonds |
-
2001
- 2001-06-26 CN CN01129547A patent/CN1324789A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423623B (en) * | 2007-11-02 | 2011-05-11 | 宁波大学 | Depolymerization and recovery method of high temperature resistant nylon poly-para-phenylene diformyl hexane diamine |
| CN101519359B (en) * | 2009-04-16 | 2012-07-25 | 李汉毅 | Method for recovering polyimide through hydrolysis |
| CN103012837A (en) * | 2011-09-28 | 2013-04-03 | 广州源骏电子科技有限公司 | Recovery processing method of polyimide film |
| 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 |
| CN103553906B (en) * | 2013-11-05 | 2015-09-23 | 上海固创化工新材料有限公司 | A kind of ammoniacal liquor hydrolysis polyimide waste film reclaims the method for polyimide raw material |
| WO2016093385A1 (en) * | 2014-12-10 | 2016-06-16 | 주식회사 엔케이이씨 | Method for recovering polyimide |
| CN104761915A (en) * | 2015-03-20 | 2015-07-08 | 巨化集团技术中心 | Preparation method of wear-resistant polyimide and fluorine-containing polymer composition |
| 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 |
| CN104945268A (en) * | 2015-05-06 | 2015-09-30 | 无锡顺铉新材料有限公司 | Method for recovery processing of modified polyimide film wastes |
| 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 |
| CN109503614A (en) * | 2018-12-04 | 2019-03-22 | 宏威高新材料有限公司 | A method of recycling polyimides waste |
| CN109503614B (en) * | 2018-12-04 | 2020-10-02 | 宏威高新材料有限公司 | Method for recycling polyimide waste |
| 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 |
| CN111073035B (en) * | 2019-12-12 | 2022-04-26 | 江苏奥神新材料股份有限公司 | Method for rapidly degrading and recycling polyimide material |
| CN112028366A (en) * | 2020-09-01 | 2020-12-04 | 上海固创化工新材料有限公司 | Method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride |
| CN113354527A (en) * | 2021-06-17 | 2021-09-07 | 中国科学院山西煤炭化学研究所 | Method for degrading polyimide material by microwave |
| CN113372212A (en) * | 2021-06-17 | 2021-09-10 | 中国科学院山西煤炭化学研究所 | Method for recovering polyimide by selectively breaking imide bonds |
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