CN116535735A - Efficient acid-base-free green wet-process micro-degradation regeneration method for polyimide - Google Patents
Efficient acid-base-free green wet-process micro-degradation regeneration method for polyimide Download PDFInfo
- Publication number
- CN116535735A CN116535735A CN202310380060.XA CN202310380060A CN116535735A CN 116535735 A CN116535735 A CN 116535735A CN 202310380060 A CN202310380060 A CN 202310380060A CN 116535735 A CN116535735 A CN 116535735A
- Authority
- CN
- China
- Prior art keywords
- polyimide
- base
- acid
- regenerating
- free green
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 90
- 239000004642 Polyimide Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 26
- 238000011069 regeneration method Methods 0.000 title claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 230000015556 catabolic process Effects 0.000 claims abstract description 18
- 230000001172 regenerating effect Effects 0.000 claims abstract description 18
- 239000004952 Polyamide Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 15
- 229920002647 polyamide Polymers 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000008929 regeneration Effects 0.000 claims abstract description 4
- 229920005575 poly(amic acid) Polymers 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012456 homogeneous solution Substances 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000005576 amination reaction Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a method for regenerating polyimide by high-efficiency acid-base-free green wet micro-degradation, belonging to the technical field of green recycling economy and light material synthesis. The preparation method of the invention comprises the following steps: mixing polyimide material, ring-opening agent and organic solvent, and then reacting in a closed container to obtain polyamide acid homogeneous mixed solution; the obtained polyamide acid homogeneous mixed solution can be used as a raw material to be mixed with polyamide acid for preparing a polyimide composite film by hot-press amination. The invention utilizes the green wet degradation technology to recycle and obtain the polyimide film. Compared with the prior art, the method has the advantages of simple and mild operation process, low cost, no acid-base wastewater, high economic benefit, low energy consumption, less environmental pollution and high added value, and realizes the green regeneration of polyimide waste.
Description
Technical Field
The invention belongs to the technical fields of green recycling economy and light material synthesis, and particularly relates to a method for regenerating polyimide by efficient acid-base-free green wet micro-degradation.
Background
Polyimide is a high molecular polymer with imide ring (-CO-NR-CO) on its main chain, and is one of the organic high molecular materials with optimal comprehensive performance. It can be used for a long time within the range of-200-300 ℃, and has excellent performances of temperature resistance, chemical corrosion resistance, electrical insulation and the like. Polyimide has been widely used in various fields such as solar floors, photoresists, separation membranes, liquid crystal displays, etc. due to its excellent properties. Meanwhile, the use of polyimide in large quantities causes the continuous increase of waste resources, so that the reasonable recycling of polyimide is of great interest.
Polyimide is mainly prepared from aromatic diamine and aromatic dianhydride. The preparation process of the aromatic diamine and the aromatic dianhydride is complex and expensive, so that the polyamide acid with high added value is recovered from polyimide waste, and the polyimide film is obtained through secondary reaction, thereby not only reducing the resource waste and avoiding environmental pollution, but also providing a new method for preparing the synthesized polyimide film and realizing green regeneration.
Chinese patent CN 115057769A discloses a recovery method of polyimide waste film, which mainly converts the polyimide waste film into a monomer for preparing the polyimide film under the environment of high temperature and strong alkali: 4,4' -diaminodiphenyl ether (ODA) and pyromellitic anhydride (PMDA) realize the recycling of the polyimide waste film, and have higher economic benefit and environmental protection benefit. However, the high temperature and strong alkali conditions have high requirements on instruments and equipment, and the method has high energy consumption for converting the polyimide waste film completely polymerized into a monomer.
Chinese patent CN 103553906B discloses a method for recycling polyimide raw materials by hydrolyzing polyimide waste films with ammonia water, which mainly converts the polyimide waste films into PMDA and ODA in ammonia water solution, and the purity of the polyimide waste films can reach 99.5 percent. However, the reaction requires higher pressure, and the ammonia water has strong volatility, which is not beneficial to industrialization.
Disclosure of Invention
Aiming at the problems existing in the prior art, the technical problem to be solved by the invention is to provide a method for efficiently regenerating polyimide by acid-base-free green wet micro-degradation.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation comprises the following steps: mixing polyimide material, ring-opening agent and organic solvent, and then reacting in a closed container to obtain polyamide acid homogeneous mixed solution; and mixing the obtained polyamic acid homogeneous solution with a polyamic acid raw material, and performing thermal imidization reaction to obtain the polyimide composite film.
The invention recovers polyamide acid with high added value by selectively breaking imide bond, and the reaction process is as follows:
the polyamide acid is obtained by controlling the mass ratio of the ring-opening agent to the organic solvent to controllably degrade, the recovery method is simple and easy to implement, industrial acid-base wastewater is not generated, the recovery and utilization of chemical raw materials are promoted, the production cost is reduced, and the green regeneration of polyimide waste is realized.
Preferably, the polyimide material has the following structural formula:
wherein Ar is 1 The structure comprises the following steps:
Ar 2 the structure comprises the following steps:
preferably, the organic solvent is selected from any one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, m-cresol, nitrobenzene, dimethylsulfoxide, toluene, formamide and acetamide. The organic solvent is used for improving the wettability of the degradation system and the polyimide material and dissolving degradation products, and the organic solvent selected by the scheme has good swelling effect and good reaction performance on the degradation of the polyimide material.
Preferably, the ring-opening agent is selected from any one or more of tertiary butanol, n-hexanol, propanol, cyclopentanol, 2-propanol, methanol, ethanol, water, benzyl alcohol, ethylene glycol and glycerol. The ring-opening agent selected by the scheme has better selective cleavage effect on imide bonds, and can change the mass ratio of polyimide repeating units to the ring-opening agent to control and generate different reaction products.
Preferably, the mass ratio of the polyimide material to the organic solvent is 1:5-15, and the mass ratio of the polyimide material to the ring-opening agent is 1:0.1-10. When the mass ratio of the polyimide material to the organic solvent is too large, the organic solvent cannot fully swell the polyimide, so that the ring-opening agent is not beneficial to acting on the polyimide, and the ring-opening effect is reduced; when the mass ratio of the polyimide material to the organic solvent is too small, the organic solvent is used in a large amount, the relative content of degradation products is low, and the economy is poor. When the mass ratio of the polyimide material to the ring-opening agent is too large, the ring-opening agent cannot play the ring-opening function, and degradation reaction basically does not occur; when the mass ratio of the polyimide material to the ring-opening agent is too small, the polyimide material is completely degraded into monomers by the excessive amount of the ring-opening agent, and the polyamic acid solution cannot be obtained.
Preferably, the reaction temperature is 40-250 ℃ and the reaction time is 1-12 h. When the reaction temperature is lower than 40 ℃, the reaction does not occur, whereas above 250 ℃, side reactions occur. When the reaction time is less than 1h, the reaction is insufficient; when the reaction time is more than 12 hours, the reaction effect is not obviously improved, the energy waste is caused, and the reaction period is prolonged.
Preferably, the mass ratio of the polyamic acid to the polyamic acid homogeneous solution is 1:0.05-0.5; the mixing time is 1-12 h; the mixing temperature is 25-80 ℃. According to the method, the polyamide acid solution is prepared by a two-solution compounding method, the viscosity change caused by the metering error of the same degree is greatly reduced, the problem of difficult mass transfer is solved, and the uniformity of the polyamide acid solution is greatly improved. When the reaction temperature is lower than 25 ℃, the reaction does not occur, whereas above 80 ℃, side reactions occur. When the reaction time is less than 1h, the polycondensation reaction is insufficient; when the reaction time is more than 12 hours, the reaction effect is not obviously improved.
Preferably, the high temperature imidization temperature is 200-300 ℃ and the imidization time is 2-12 h. When the imidization temperature is lower than 200 ℃ or the reaction time is less than 2 hours, the imidization degree is insufficient; when the imidization temperature is higher than 300 ℃ or the reaction time is longer than 12 hours, side reactions occur, and the imidization degree is not affected.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
1. the method for regenerating polyimide by high-efficiency acid-base-free green wet micro-degradation has the advantages of relatively mild reaction process conditions, simple and feasible recovery method, no generation of acid-base industrial wastewater, high economic added value and capability of avoiding huge energy consumption caused by degrading and recovering polyimide materials.
2. The invention realizes the controllable degradation of polyimide materials by selectively breaking imide bonds, and recovers polyamide acid with high added value.
3. The preparation process is simple, the cost is low, and the prepared polyimide composite film has excellent performance and can be widely applied to the fields of electronic communication, aerospace, microelectronics and the like.
Drawings
FIG. 1 is a schematic diagram of a process for recovering a polyamic acid solution;
FIG. 2 is an infrared spectrum of recovered polyimide film trim;
FIG. 3 is a tensile stress strain diagram of a polyimide composite film;
fig. 4 is a thermal stability diagram of a polyimide composite film.
Detailed Description
The invention is further described below in connection with specific embodiments. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In the following examples, unless otherwise specified, the experimental procedures used were conventional. The raw materials used are commercially available from public sources unless otherwise specified.
In the following examples, the test methods used were:
tensile strength: the tensile strength of the polyimide composite film material was tested according to GB 13022-91.
Young's modulus: young's modulus of composite film material was measured according to ISO 527-2-2012
Thermal decomposition temperature: measurement of thermal decomposition temperature of composite film Material according to GB/T13464-2008 example 1
A method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation comprises the following steps:
(1) 10g will beHN polyimide film rim charge (structural formula is shown below) and 50g of N, N-dimethylformamide and 1g of tertiary butanol are taken as ring opening agents, and the mixture is reacted for 12 hours at 40 ℃ in a closed container with the pressure of 0MPa to obtain polyamide acid homogeneous phase mixed solution.
(2) 100g of polyamic acid solution and 5g of polyamic acid homogeneous mixed solution are mixed for 12 hours at 25 ℃, biaxially stretched, and imidized for 12 hours at 200 ℃ in a high-temperature oven to obtain the polyimide composite film.
The basic performance of the polyimide composite film obtained by testing is as follows:
tensile strength: 23.2MPa
Young's modulus: 8GPa (8 GPa)
Thermal decomposition temperature: 548 DEG C
FIG. 1 is an infrared spectrogram of a recovered polyimide film rim charge; as can be seen from FIG. 1, 1778cm of the infrared spectrum of PI -1 、1717cm -1 Symmetrical and asymmetrical stretching vibration peaks of carbonyl respectively appear, and at the same time, 1373cm -1 The infrared of the imine ring appears, which indicates that the polyimide film rim charge is partially degraded.
Example 2
A method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation comprises the following steps:
(1) 50g of colorless transparent polyimide molding powder (the structural formula is shown below) and 750g of dimethyl sulfoxide, and 500g of tertiary butanol are used as ring-opening agents, and are reacted for 1h at 250 ℃ in a closed container with the pressure of 5MPa, so as to obtain polyamide acid homogeneous mixed solution.
(2) 100g of polyamic acid solution and 50g of polyamic acid homogeneous mixed solution are mixed for 1h at 80 ℃, and subjected to biaxial stretching and imidization for 2h at 300 ℃ in a high-temperature oven to obtain the polyimide composite film.
The basic properties of the polyimide composite film prepared by the test are as follows:
tensile strength: 17MPa of
Young's modulus: 7.3GPa
Thermal decomposition temperature: 530 DEG C
FIG. 2 is a drawing showing the tensile strain of the polyimide film materials of examples 1, 2 and pure; as can be seen from fig. 2, the tensile properties of the composite film material after the composite modification were slightly lowered compared with the pure polyimide film material, but the tensile strength was still maintained at 15MPa or more.
Example 3
A method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation comprises the following steps:
(1) 1000g of polyimide material (with the structural formula shown below) and 10000g of N-methylpyrrolidone are reacted for 6 hours at 125 ℃ in a closed container with the pressure of 2.5MPa by using 5000g of water as a ring-opening agent, so as to obtain a polyamide acid homogeneous mixed solution.
(2) 100g of polyamic acid solution and 25g of polyamic acid homogeneous mixed solution are mixed for 4 hours at 40 ℃, and subjected to biaxial stretching and imidization for 8 hours at 250 ℃ in a high-temperature oven to obtain the polyimide composite film.
The basic properties of the polyimide composite film prepared by the test are as follows:
tensile strength: 27.2MPa
Young's modulus: 15.2GPa
Thermal decomposition temperature: 550 DEG C
Example 4
A method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation comprises the following steps:
(1) 30g of polyimide film (structure formula is shown below) and 240g of toluene, and 240g of glycerol are used as ring-opening agents, and the mixture is reacted for 4 hours at 200 ℃ in a closed container with the pressure of 3MPa to obtain polyamide acid homogeneous mixed solution.
(2) 100g of polyamic acid solution and 40g of polyamic acid homogeneous mixed solution are mixed for 6 hours at 60 ℃, and subjected to biaxial stretching and imidization for 8 hours at 250 ℃ in a high-temperature oven to obtain the polyimide composite film.
The basic properties of the polyimide composite film prepared by the test are as follows:
tensile strength: 28MPa of
Young's modulus: 10.3GPa
Thermal decomposition temperature: 520 DEG C
FIG. 4 is a thermal stability diagram of a pure polyimide film material, example 1, example 2, example 3, and example 4; as can be seen from fig. 4, the thermal stability of the composite polyimide film is slightly reduced compared with the pure polyimide film material, but the decomposition temperature of 5% is greater than 520 ℃, and the carbon residue at 1000 ℃ is increased.
Claims (10)
1. The method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation is characterized by comprising the following steps of: mixing polyimide material, ring-opening agent and organic solvent, and then reacting in a closed container to obtain polyamide acid homogeneous mixed solution; and mixing the obtained polyamic acid homogeneous solution with a polyamic acid raw material, and performing thermal imidization reaction to obtain the polyimide composite film.
2. The method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation according to claim 1, wherein the polyimide material has the following structural formula:
wherein Ar is 1 The structure comprises the following steps:
Ar 2 the structure comprises the following steps:
3. the method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation according to claim 1, wherein the organic solvent is selected from any one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, m-cresol, nitrobenzene, dimethylsulfoxide, toluene, formamide and acetamide.
4. The method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation according to claim 1, wherein the ring-opening agent is selected from any one or more of tertiary butanol, n-hexanol, propanol, cyclopentanol, 1-propanol, methanol, ethanol, water, benzyl alcohol, ethylene glycol and glycerol.
5. The method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation according to claim 1, wherein the mass ratio of the polyimide material to the organic solvent is 1:5-15, and the mass ratio of the polyimide material to the ring-opening agent is 1:0.1-10.
6. The method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation according to claim 1, wherein the reaction temperature is 40-250 ℃ and the reaction time is 1-12 h.
7. The method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation according to claim 1, wherein the pressure of the closed container is 0-5 MPa.
8. The method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation according to claim 1, wherein the mass ratio of the homogeneous solution of polyamic acid to the mixture of polyamic acid is 1:0.05-0.5, the mixing time is 1-12 h, and the mixing temperature is 25-80 ℃.
9. The method for regenerating polyimide by high-efficiency acid-base-free green wet micro degradation according to claim 1, wherein the thermal imidization temperature is 200-300 ℃ and the imidization time is 2-12 h.
10. The method for high-efficiency acid-base-free green wet micro-degradation regeneration of polyimide according to any one of claims 1 to 9, so as to obtain a polyimide composite film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310380060.XA CN116535735A (en) | 2023-04-11 | 2023-04-11 | Efficient acid-base-free green wet-process micro-degradation regeneration method for polyimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310380060.XA CN116535735A (en) | 2023-04-11 | 2023-04-11 | Efficient acid-base-free green wet-process micro-degradation regeneration method for polyimide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116535735A true CN116535735A (en) | 2023-08-04 |
Family
ID=87449685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310380060.XA Pending CN116535735A (en) | 2023-04-11 | 2023-04-11 | Efficient acid-base-free green wet-process micro-degradation regeneration method for polyimide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116535735A (en) |
-
2023
- 2023-04-11 CN CN202310380060.XA patent/CN116535735A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101392059B (en) | Colorless transparent aromatic polyimide film and preparation method thereof | |
| CN102492141B (en) | Soluble polyimide molded plastic and preparation method thereof | |
| CN110396194B (en) | Fluorine-containing wear-resistant polyamide-imide material and preparation method thereof | |
| CN101921483A (en) | Polybenzimidazole imide membrane and preparation method thereof | |
| EP2832768A1 (en) | Preparation method of polyimide | |
| CN114213696A (en) | Light flexible high-temperature-resistant heat-insulating polyimide foam and preparation method and application thereof | |
| CN114605638B (en) | Preparation method of polyimide or polyetherimide | |
| Xu et al. | Facile preparation of rapidly recyclable tough thermosetting composites via cross-linking structure regulation | |
| CN113788979B (en) | Hard closed-cell polyimide foam and preparation method thereof | |
| CN101709515A (en) | Polyimide fiber containing amido link structure and preparation method thereof | |
| CN112574411B (en) | Polyimide precursor, polyimide film, preparation method of polyimide film and display device | |
| CN116535735A (en) | Efficient acid-base-free green wet-process micro-degradation regeneration method for polyimide | |
| CN115109302B (en) | Micro-foaming material for injection molding of automobile plastic part and preparation method thereof | |
| CN114149586B (en) | Chain-extended polysulfate and preparation method thereof | |
| CN113372212A (en) | Method for recovering polyimide by selectively breaking imide bonds | |
| CN116178673A (en) | Process for preparing composite material by vacuum infusion method | |
| CN112062958B (en) | Polyimide material and preparation method thereof | |
| CN113354527A (en) | Method for degrading polyimide material by microwave | |
| CN114044903A (en) | Hard polyimide foam and preparation method and application thereof | |
| CN101973147A (en) | Preparation method of high-temperature resistant polyimide glass fabric laminated board | |
| CN102504211B (en) | preparation method of thermoset imide resin modified silazane and its composite material | |
| CN111793009A (en) | Phthalonitrile monomer containing spiro structure and resin thereof | |
| CN110776737A (en) | Graphene-polyimide resin heat-conducting composite material and preparation method thereof | |
| CN110862539A (en) | Green preparation method of polyimide | |
| CN114797487B (en) | Preparation method of polyimide organic solvent nanofiltration membrane containing spiro bisindane structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |