CN108822317A - A kind of preparation method of graphene polyimide heating film - Google Patents
A kind of preparation method of graphene polyimide heating film Download PDFInfo
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- CN108822317A CN108822317A CN201810526763.8A CN201810526763A CN108822317A CN 108822317 A CN108822317 A CN 108822317A CN 201810526763 A CN201810526763 A CN 201810526763A CN 108822317 A CN108822317 A CN 108822317A
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- Materials Engineering (AREA)
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention prepares graphene polyimide heating film using multi-layer compound structure, by dianhydride and diamine monomer carry out pre-polymerization, and graphene modifying agent is added in polyamide solution, heating limitation imidization obtains surface layer and bottom, graphene heating layer is added in centre, and surface layer coating is carried out when bottom is half-dried, it is coated with surface layer, carry out the imidizate that heating carries out composite material, make each interlayer of graphene polyimide heating film that there is good associativity, the advantages of having both graphene and polyimides simultaneously has good conductive and heating property.The corrugated unique texture of flower-shaped graphene oxide simultaneously is beneficial to the dispersion of graphene oxide in the feed, and improve the mechanical property of graphene polyimide heating film so that its activity increases.
Description
Technical field
The invention belongs to field of compound material, and in particular to a kind of preparation method of graphene polyimide heating film.
Background technique
The two-dimension single layer stratified material that graphene is made of carbon atom.Graphene has excellent optics, electricity, mechanics
Characteristic, materialogy, micro-nano technology, the energy, biomedicine and in terms of it is with important application prospects, be considered
It is a kind of future revolutionary material.The spies such as the owned high-intensitive, high thermal conductivity of graphene and good barrier properties for gases
Property, it is a kind of ideal laminar nano filler.Polyimides has good mechanical performance, thermal stability, solvent resistance, resistance toization
Learn other excellent properties such as corrosivity, the application study of decades show the high-mechanical property of polyimides with it is resistant to chemical etching
Property is adapted to requirement of the various harsh environments to material property.Thus it is widely used in the numerous areas of national economy,
Such as the high-tech industries such as manned space flight, large aircraft, nuclear power station, telecommunications, automobile.It is right but with the expansion of application
The requirement of polyimides Related product is continuously improved.The exothermic material and product structure form of heating film are to determine heating film product
The principal element of performance, wherein exothermic material plays a decisive role.According to exothermic material it is different heating film be divided into macromolecule,
Ink, carbon fiber, four seed type of wire (piece) are printed, the heating film of these four types is because belong to electrical heating elements, institute
It is common or similar to have the characteristics that, but the properties such as the inborn physics of different heat material, chemistry, electrochemistry, electric heating are different, again
Determine that different type fever film properties are variant, the present invention studies the heating film of polyimides, and graphene is added, and increases
The additive amount of big additive improves the performance of composite membrane.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of preparation of graphene polyimide heating film
Method.The heating film has excellent fever and mechanical property.
The purpose of the present invention is what is be achieved through the following technical solutions：A kind of preparation side of graphene polyimide heating film
Method includes the following steps：
(1) first diamines is dissolved in organic solvent, is stirred under nitrogen protection, add dianhydride and organic solvent,
It carries out polycondensation reaction under de-oxidizing environment, end-capping reagent is added and is blocked, obtain solid content in the polyamide solution of 18-24wt%,
Then graphene oxide raw material is added, stirs to get composite solution, scrapes to obtain just film by applying after filtering, heat drying is to half-dried
Obtain film A, wherein the quality of graphene oxide is the 0.5wt%-5wt% of polyamic acid and graphene oxide total amount；
(2) graphene powder is mixed with binder and is applied to the just surface film A formation enhancement layer C；
(3) composite solution is prepared using the preparation method of step (1), blade coating obtains just film B on enhancement layer, obtains
Compound just film；
(4) compound just film obtained by step (3) is heat-treated completely and carries out imidizate, obtain graphene-polyimides hair
Hotting mask.
Further, binder employed in step (2) is polyimide binder.
Further, dianhydride monomer includes triphen diether tetracarboxylic acid dianhydride, 4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids, and two
Amine monomers include 2,2 '-bis- (trifluoromethyl) -4,4 '-diamino-phenyl ethers, 4,4 '-bis trifluoromethyl biphenyl.
Further, it is molten to can be flower-shaped graphene oxide powder, flower-shaped graphene oxide for the graphene oxide raw material
Liquid etc..
Further, the solvent in the step 1 can be water, DMF, DMAc, NMP, DMSO, methanol, ethyl alcohol equal solvent.
Further, the material of dianhydride and diamines compares for 45-60:50-55.
The beneficial effects of the present invention are：The present invention prepares graphene polyimide heating film using multi-layer compound structure,
By dianhydride and diamine monomer carry out pre-polymerization, and in polyamide solution be added graphene modifying agent, heating limitation imidization
Surface layer and bottom are obtained, graphene heating layer is added in centre, and carry out surface layer coating when bottom is half-dried, is coated with surface layer,
The imidizate that heating carries out composite material is carried out, makes each interlayer of graphene polyimide heating film that there is good associativity,
The advantages of having both graphene and polyimides simultaneously has good conductive and heating property.Flower-shaped graphene oxide pleat simultaneously
The unique texture of wrinkleization is beneficial to the dispersion of graphene oxide in the feed so that its activity increases, and it is poly- to improve graphene
The mechanical property of acid imide heating film.
Detailed description of the invention
Fig. 1 is fever membrane structure diagram.
Specific embodiment
Embodiment 1：
(1) first diamines is dissolved in DMF, is stirred under nitrogen protection, add dianhydride and organic solvent, in deoxidation ring
Polycondensation reaction is carried out under border, end-capping reagent is added and is blocked, and obtains solid content in the polyamide solution of 18wt%, flower is then added
Shape graphene oxide powder stirs to get composite solution, scrapes to obtain first film by applying after filtering, and heat drying obtains film to half-dried
A, wherein the quality of graphene oxide is the 1.5wt%-5wt% of polyamic acid and graphene oxide total amount, diamines and dianhydride
Feed molar ratio is 45:45；
(2) graphene powder is mixed with polyimide binder and is applied to the just surface film A formation enhancement layer C；
(3) composite solution is prepared using the preparation method of step (1), blade coating obtains just film B on enhancement layer, obtains
Compound just film；
(4) compound just film obtained by step (3) is heat-treated completely and carries out imidizate, obtain graphene-polyimides hair
Hotting mask.
Wherein, dianhydride monomer be triphen diether tetracarboxylic acid dianhydride, diamine monomer 2,2 '-bis- (trifluoromethyl) -4,4 '-two
Aminophenyl ether.
Above-mentioned film mechanical performance, tensile strength 73.5MPa, Young's modulus 5.12GPa are measured using puller system.
Embodiment 2
(1) first diamines is dissolved in DMAc, is stirred under nitrogen protection, add dianhydride and organic solvent, in deoxidation
Polycondensation reaction is carried out under environment, and end-capping reagent is added and is blocked, obtains solid content in the polyamide solution of 20wt%, is then added
Flower-shaped graphene oxide powder stirs to get composite solution, scrapes to obtain first film by applying after filtering, and heat drying is obtained to half-dried
Film A, wherein the quality of graphene oxide is the 3wt% of polyamic acid and graphene oxide total amount, the feed molar ratio of diamines and dianhydride
It is 45:50；
(2) graphene powder is mixed with polyimide binder and is applied to the just surface film A formation enhancement layer C；
(3) composite solution is prepared using the preparation method of step (1), blade coating obtains just film B on enhancement layer, obtains
Compound just film；
(4) compound just film obtained by step (3) is heat-treated completely and carries out imidizate, obtain graphene-polyimides hair
Hotting mask.
Wherein, dianhydride monomer 4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids, 4,4 '-bis trifluoromethyl of diamine monomer connection
Benzene.
Above-mentioned film mechanical performance, tensile strength 70.1MPa, Young's modulus 5.10GPa are measured using puller system.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (6)
1. a kind of preparation method of graphene polyimide heating film, includes the following steps：
(1) first diamines is dissolved in organic solvent, is stirred under nitrogen protection, add dianhydride and organic solvent, in deoxidation
Polycondensation reaction is carried out under environment, and end-capping reagent is added and is blocked, obtains solid content in the polyamide solution of 18-24wt%, then
Graphene oxide raw material is added, stirs to get composite solution, scrapes to obtain first film by applying after filtering, heat drying is obtained to half-dried
Film A, wherein the quality of graphene oxide is the 0.5wt%-5wt% of polyamic acid and graphene oxide total amount；
(2) graphene powder is mixed with binder and is applied to the just surface film A formation enhancement layer C；
(3) composite solution is prepared using the preparation method of step (1), blade coating obtains just film B on enhancement layer, obtains compound
First film；
(4) compound just film obtained by step (3) is heat-treated completely and carries out imidizate, obtain graphene-polyimide heating film.
2. preparation method according to claim 1, binder employed in step (2) is polyimide binder.
3. preparation method according to claim 1, dianhydride monomer includes triphen diether tetracarboxylic acid dianhydride, and 4,4 '-(hexafluoro is different
Propylene) two anhydride phthalic acids, diamine monomer includes 2,2 '-bis- (trifluoromethyl) -4,4 '-diamino-phenyl ethers, 4,4 '-bis trifluoromethyls
Biphenyl.
4. preparation method according to claim 1, the graphene oxide raw material can be flower-shaped graphene oxide powder,
Flower-shaped graphene oxide solution.
5. preparation method according to claim 1, the solvent in the step 1 can be water, DMF, DMAc, NMP,
DMSO, methanol, ethyl alcohol.
6. the material of preparation method according to claim 1, dianhydride and diamines compares for 45-60:50-55.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN2018103363946 | 2018-04-11 | ||
| CN201810336394 | 2018-04-11 |
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| CN108822317A true CN108822317A (en) | 2018-11-16 |
| CN108822317B CN108822317B (en) | 2021-04-06 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109673067A (en) * | 2018-12-21 | 2019-04-23 | 河南烯碳合成材料有限公司 | A kind of Metal Substrate graphene high temperature resistant far-infrared heating tube and preparation method thereof, heat-resisting material |
| CN110868769A (en) * | 2019-11-27 | 2020-03-06 | 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 |
| CN113307972A (en) * | 2021-06-15 | 2021-08-27 | 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 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109673067A (en) * | 2018-12-21 | 2019-04-23 | 河南烯碳合成材料有限公司 | A kind of Metal Substrate graphene high temperature resistant far-infrared heating tube and preparation method thereof, heat-resisting material |
| 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 |
| CN110868769A (en) * | 2019-11-27 | 2020-03-06 | 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 |
| CN113307972A (en) * | 2021-06-15 | 2021-08-27 | 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 |
| 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 |
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