CN108822317B - Preparation method of graphene polyimide heating film - Google Patents
Preparation method of graphene polyimide heating film Download PDFInfo
- Publication number
- CN108822317B CN108822317B CN201810526763.8A CN201810526763A CN108822317B CN 108822317 B CN108822317 B CN 108822317B CN 201810526763 A CN201810526763 A CN 201810526763A CN 108822317 B CN108822317 B CN 108822317B
- Authority
- CN
- China
- Prior art keywords
- graphene
- heating
- graphene oxide
- polyimide
- heating film
- 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.)
- Active
Links
Images
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
- 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
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Abstract
According to the invention, a multilayer composite structure is adopted to prepare the graphene polyimide heating film, the dianhydride and the diamine monomer are used for pre-polymerization, the graphene modifier is added into the polyamide solution, the surface layer and the bottom layer are obtained by heating and limiting imidization, the graphene heating layer is added in the middle, the surface layer is coated when the bottom layer is semi-dry, the surface layer is coated, and heating is carried out to carry out imidization on the composite material, so that the graphene polyimide heating film has good bonding property among the layers, has the advantages of graphene and polyimide, and has good electric conduction and heating performances. Meanwhile, due to the unique structure of the flower-shaped graphene oxide wrinkling, the activity of the graphene oxide wrinkling-based heating film is increased, the dispersion of the graphene oxide in raw materials is facilitated, and the mechanical property of the graphene polyimide heating film is improved.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a preparation method of a graphene polyimide heating film.
Background
Graphene is a two-dimensional monolayer layered material composed of carbon atoms. The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future. Graphene has the characteristics of high strength, high thermal conductivity, good gas barrier property and the like, and is an ideal layered nano filler. The polyimide has other excellent properties such as good mechanical property, thermal stability, solvent resistance, chemical corrosion resistance and the like, and application researches for decades show that the high mechanical property and the chemical corrosion resistance of the polyimide can meet the requirements of various harsh environments on the material performance. Therefore, the method is widely applied to various fields of national economy, such as high-tech industries of manned spaceflight, large airplanes, nuclear power plants, electronic communication, automobiles and the like. However, with the expansion of applications, the requirements for polyimide-related products are continuously increasing. The heating material and the product structure form of the heating film are main factors determining the product performance of the heating film, wherein the heating material plays a decisive role. The heating film is divided into four types of high molecules, printing ink, carbon fiber and metal wires (sheets) according to the difference of heating materials, the four types of heating films have common or similar characteristics because the four types of heating films belong to electric heating elements, but the inherent physical, chemical, electrochemical, electric heating and other properties of different heating materials are different, and the difference of the performances of different types of heating films is determined.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a graphene polyimide heating film. The heating film has excellent heating and mechanical properties.
The purpose of the invention is realized by the following technical scheme: a preparation method of a graphene polyimide heating film comprises the following steps:
(1) dissolving diamine in an organic solvent, stirring under the protection of nitrogen, adding dianhydride and the organic solvent, carrying out polycondensation reaction in a deoxygenation environment, adding a capping agent for capping to obtain a polyamide solution with the solid content of 18-24 wt%, adding a graphene oxide raw material, stirring to obtain a composite solution, filtering, coating and scraping to obtain a primary membrane, and heating and drying to be semi-dry to obtain a membrane A, wherein the mass of the graphene oxide is 0.5-5 wt% of the total mass of polyamide acid and graphene oxide;
(2) mixing graphene powder and a binder, and coating the mixture on the surface of the primary film A to form an enhancement layer C;
(3) preparing a composite solution by adopting the preparation method in the step (1), and blade-coating the reinforced layer to obtain a primary film B and obtain a composite primary film;
(4) and (4) performing complete heat treatment on the composite primary film obtained in the step (3) to perform imidization, so as to obtain the graphene-polyimide heating film.
Further, the adhesive used in step (2) is a polyimide adhesive.
Further, the dianhydride monomer includes triphenediether tetracarboxylic dianhydride, 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, and the diamine monomer includes 2, 2' -bis (trifluoromethyl) -4,4 '-diaminophenyl ether, 4, 4' -bistrifluoromethylbiphenyl.
Further, the graphene oxide raw material may be flower-like graphene oxide powder, a flower-like graphene oxide solution, or the like.
Further, the solvent in step 1 may be water, DMF, DMAc, NMP, DMSO, methanol, ethanol, or the like.
Further, the material ratio of dianhydride to diamine is 45-60: 50-55.
The invention has the beneficial effects that: according to the invention, a multilayer composite structure is adopted to prepare the graphene polyimide heating film, the dianhydride and the diamine monomer are used for pre-polymerization, the graphene modifier is added into the polyamide solution, the surface layer and the bottom layer are obtained by heating and limiting imidization, the graphene heating layer is added in the middle, the surface layer is coated when the bottom layer is semi-dry, the surface layer is coated, and heating is carried out to carry out imidization on the composite material, so that the graphene polyimide heating film has good bonding property among the layers, has the advantages of graphene and polyimide, and has good electric conduction and heating performances. Meanwhile, due to the unique structure of the flower-shaped graphene oxide wrinkling, the activity of the graphene oxide wrinkling-based heating film is increased, the dispersion of the graphene oxide in raw materials is facilitated, and the mechanical property of the graphene polyimide heating film is improved.
Drawings
Fig. 1 is a schematic view of a heating film structure.
Detailed Description
Example 1:
(1) dissolving diamine in DMF, stirring under the protection of nitrogen, adding dianhydride and an organic solvent, carrying out polycondensation reaction in a deoxygenation environment, adding a capping agent for capping to obtain a polyamide solution with the solid content of 18 wt%, then adding flower-shaped graphene oxide powder, stirring to obtain a composite solution, filtering, coating and scraping to obtain a primary membrane, heating and drying to be semi-dry to obtain a membrane A, wherein the mass of the graphene oxide is 1.5-5 wt% of the total mass of the polyamide acid and the graphene oxide, and the feeding ratio of the diamine to the dianhydride is 45: 45;
(2) mixing graphene powder and a polyimide binder, and coating the mixture on the surface of the primary membrane A to form an enhancement layer C;
(3) preparing a composite solution by adopting the preparation method in the step (1), and blade-coating the reinforced layer to obtain a primary film B and obtain a composite primary film;
(4) and (4) performing complete heat treatment on the composite primary film obtained in the step (3) to perform imidization, so as to obtain the graphene-polyimide heating film.
Wherein the dianhydride monomer is triphenyl diether tetracarboxylic dianhydride, and the diamine monomer is 2,2 '-bis (trifluoromethyl) -4, 4' -diaminophenyl ether.
The mechanical properties of the film were measured by a tensile machine, and the tensile strength was 73.5MPa and the Young's modulus was 5.12 GPa.
Example 2
(1) Dissolving diamine in DMAc, stirring under the protection of nitrogen, adding dianhydride and an organic solvent, carrying out polycondensation reaction in a deoxygenation environment, adding a capping agent for capping to obtain a polyamide solution with the solid content of 20 wt%, then adding flower-shaped graphene oxide powder, stirring to obtain a composite solution, filtering, coating and scraping to obtain a primary membrane, heating and drying to be semi-dry to obtain a membrane A, wherein the mass of the graphene oxide is 3 wt% of the total mass of the polyamide acid and the graphene oxide, and the feeding ratio of the diamine to the dianhydride is 45: 50;
(2) mixing graphene powder and a polyimide binder, and coating the mixture on the surface of the primary membrane A to form an enhancement layer C;
(3) preparing a composite solution by adopting the preparation method in the step (1), and blade-coating the reinforced layer to obtain a primary film B and obtain a composite primary film;
(4) and (4) performing complete heat treatment on the composite primary film obtained in the step (3) to perform imidization, so as to obtain the graphene-polyimide heating film.
Wherein the dianhydride monomer is 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, and the diamine monomer is 4, 4' -bistrifluoromethylbiphenyl.
The mechanical properties of the film were measured by a tensile machine, and the tensile strength was 70.1MPa and the Young's modulus was 5.10 GPa.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (6)
1. A preparation method of a graphene polyimide heating film comprises the following steps:
(1) dissolving diamine in an organic solvent, stirring under the protection of nitrogen, adding dianhydride and the organic solvent, carrying out polycondensation reaction in a deoxygenation environment, adding a capping agent for capping to obtain a polyamide solution with the solid content of 18-24 wt%, adding a graphene oxide raw material, stirring to obtain a composite solution, filtering, coating and scraping to obtain a primary membrane, and heating and drying to be semi-dry to obtain a membrane A, wherein the mass of the graphene oxide is 0.5-5 wt% of the total mass of polyamide acid and graphene oxide;
(2) mixing graphene powder and a binder, and coating the mixture on the surface of the primary film A to form an enhancement layer C;
(3) preparing a composite solution by adopting the preparation method in the step (1), and blade-coating the reinforced layer to obtain a primary film B and obtain a composite primary film;
(4) and (4) performing complete heat treatment on the composite primary film obtained in the step (3) to perform imidization, so as to obtain the graphene-polyimide heating film.
2. The production method according to claim 1, wherein the binder used in the step (2) is a polyimide binder.
3. The method of claim 1, wherein the dianhydride monomer comprises triphenethylene tetracarboxylic dianhydride, 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, and the diamine monomer comprises 2, 2' -bis (trifluoromethyl) -4,4 '-diaminophenyl ether, 4, 4' -bistrifluoromethylbiphenyl.
4. The preparation method according to claim 1, wherein the graphene oxide raw material is flower-like graphene oxide powder or flower-like graphene oxide solution.
5. The method according to claim 1, wherein the solvent used in step (1) is selected from water, DMF, DMAc, NMP, DMSO, methanol and ethanol.
6. The method of claim 1, wherein the ratio of dianhydride to diamine is 45-60: 50-55.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810336394 | 2018-04-11 | ||
| CN2018103363946 | 2018-04-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108822317A CN108822317A (en) | 2018-11-16 |
| CN108822317B true CN108822317B (en) | 2021-04-06 |
Family
ID=64145939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810526763.8A Active CN108822317B (en) | 2018-04-11 | 2018-05-29 | Preparation method of graphene polyimide heating film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108822317B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109673067B (en) * | 2018-12-21 | 2021-08-06 | 河南烯碳合成材料有限公司 | Metal-based graphene high-temperature-resistant far-infrared heating tube and preparation method thereof |
| CN110868769B (en) * | 2019-11-27 | 2021-03-30 | 北京航空航天大学 | Novel heating film and preparation method and application thereof |
| CN111432508A (en) * | 2020-04-15 | 2020-07-17 | 威海无缝新材料有限公司 | Graphene fast heating film and preparation method thereof |
| CN113088124A (en) * | 2021-04-02 | 2021-07-09 | 宁波龙圣新材料科技有限公司 | Preparation process and method of graphene heating film |
| CN113307972B (en) * | 2021-06-15 | 2022-06-07 | 中国科学院长春应用化学研究所 | Polyimide and preparation method thereof, and polyimide sealing ring and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011122901A2 (en) * | 2010-04-02 | 2011-10-06 | 부산대학교 산학협력단 | Polyimide nanocomposite and method for preparing same |
| CN103980489A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Low-melt-viscosity thermoplastic polyimide material and 3D printing moulding method thereof |
| CN107112302A (en) * | 2014-10-03 | 2017-08-29 | C3奈米有限公司 | Property reinforcer for clear coat and nesa coating |
-
2018
- 2018-05-29 CN CN201810526763.8A patent/CN108822317B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011122901A2 (en) * | 2010-04-02 | 2011-10-06 | 부산대학교 산학협력단 | Polyimide nanocomposite and method for preparing same |
| CN103980489A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Low-melt-viscosity thermoplastic polyimide material and 3D printing moulding method thereof |
| CN107112302A (en) * | 2014-10-03 | 2017-08-29 | C3奈米有限公司 | Property reinforcer for clear coat and nesa coating |
Non-Patent Citations (1)
| Title |
|---|
| 聚酰亚胺合成及应用进展;李华南等;《吉林建筑大学学报》;20170415 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108822317A (en) | 2018-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108822317B (en) | Preparation method of graphene polyimide heating film | |
| Wang et al. | Robust, lightweight, hydrophobic, and fire-retarded polyimide/MXene aerogels for effective oil/water separation | |
| Zhang et al. | Fabrication and investigation on the ultra-thin and flexible Ti3C2Tx/co-doped polyaniline electromagnetic interference shielding composite films | |
| Luo et al. | Solution processed boron nitride nanosheets: synthesis, assemblies and emerging applications | |
| CN110550956B (en) | Preparation method of graphene-polyimide-based composite sponge precursor heat-conducting film | |
| Sun et al. | Flexible conductive polyimide fiber/MXene composite film for electromagnetic interference shielding and joule heating with excellent harsh environment tolerance | |
| Gu et al. | Polyimide-based foams: fabrication and multifunctional applications | |
| Yao et al. | Superhydrophobic Ti3C2Tx MXene/aramid nanofiber films for high-performance electromagnetic interference shielding in thermal environment | |
| Lin et al. | Ultrathin nitrogen-doping graphene films for flexible and stretchable EMI shielding materials | |
| Jia et al. | Multifunctional ceramic composite system for simultaneous thermal protection and electromagnetic interference shielding for carbon fiber-reinforced polymer composites | |
| WO2020082738A1 (en) | Method employing aromatic fused ring molecule to modify assembly of carbon fiber surface, and method for preparing resin matrix composite material having carbon fiber reinforced interface | |
| CN106317407A (en) | Preparing method of polyimide aerogels and hybrid aerogels thereof | |
| Shi et al. | Fabrication and applications of polyimide nano-aerogels | |
| KR101321099B1 (en) | Multiple film based on epoxy resin having carbon nanoparticles and process for producing the same | |
| CN107099048B (en) | Preparation method of solvent-resistant porous polyimide film | |
| CN109206905B (en) | Graphene bismaleimide resin composite material and preparation method thereof | |
| Zhang et al. | Rational design and fabrication of lightweight porous polyimide composites containing polyaniline modified graphene oxide and multiwalled carbon nanotube hybrid fillers for heat-resistant electromagnetic interference shielding | |
| Ma et al. | Anisotropic all-aromatic polyimide aerogels with robust and high-temperature stable properties for flexible thermal protection | |
| CN103665866A (en) | Preparation method for graphene-polyimide composite film | |
| Ma et al. | Preparing multifunctional high-performance cross-linked polybenzoxazole aerogels from polybenzoxazine | |
| Yang et al. | Crown ether-containing polyimides with high dielectric constant | |
| Haleem et al. | Highly porous and thermally stable tribopositive hybrid bimetallic cryogel to boost up the performance of triboelectric nanogenerators | |
| Chaudhari et al. | Polyvinyl alcohol and graphene oxide blending surface coated alumina hollow fiber (AHF) membrane for pervaporation dehydration of epichlorohydrin (ECH)/isopropanol (IPA)/water ternary feed mixture | |
| CN102490423A (en) | Conductive polyimide film and preparation method thereof | |
| Fang et al. | Intrinsically atomic-oxygen-resistant POSS-containing polyimide aerogels: Synthesis and characterization |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chen Dabo Inventor after: Yang Yueren Inventor after: Yang Xin Inventor after: Wang Fengli Inventor before: Yang Xin Inventor before: Wang Fengli |