CN112917955A - Manufacturing method of graphene-doped polyimide composite film - Google Patents
Manufacturing method of graphene-doped polyimide composite film Download PDFInfo
- Publication number
- CN112917955A CN112917955A CN202110013896.7A CN202110013896A CN112917955A CN 112917955 A CN112917955 A CN 112917955A CN 202110013896 A CN202110013896 A CN 202110013896A CN 112917955 A CN112917955 A CN 112917955A
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- Prior art keywords
- graphene
- polyimide
- dianhydride
- diamine
- epoxy resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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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
- 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
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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing a graphene-doped polyimide composite film, which comprises the specific steps of adopting an in-situ polymerization method to mix and react required graphene with a solvent, diamine and dianhydride to prepare polyamic acid with the graphene, then uniformly coating the polyamic acid on a planar plate by using a film coating machine, then putting the planar plate into a high-temperature oven to perform imidization to generate the required polyimide, finally taking out a product to peel off the polyimide film on the plate to prepare a required polyimide layer, then putting the polyimide layer in the middle, respectively paving an epoxy resin layer on the polyimide layer, and calendering and combining the epoxy resin layers by using a calender to prepare the required material.
Description
Technical Field
The invention relates to a film manufacturing method, in particular to a graphene-doped polyimide composite film manufacturing method.
Background
Polyimide (PI) is a polymer material containing imide rings on a main chain, is a special polymer material which is industrialized at present, has excellent comprehensive physical and mechanical properties and excellent electrical and chemical stability, is widely applied to the high and new technical field, a polyimide film is one of the earliest products and is also one of the largest using amount, the novel high-temperature resistant organic polymer film is one of the film insulating materials with the best performance and the most expensive film materials in the world at present, and is called as a gold film, the excellent performance of the polyimide film enables the polyimide film to play more and more important roles in the field, and the polyimide film, carbon fibers and aramid fibers are considered as three bottleneck key polymer materials which restrict the development of high-tech industries in China at present.
At present, the domestic polyimide film has the defects of poor product quality, unstable comprehensive performance, insufficient product refinement degree, few varieties and the like, and influences the application of the polyimide film, graphene has excellent mechanical properties, electrical properties, optical properties and thermal properties as the thinnest two-dimensional material so far, and becomes a hotspot of the research of new materials at present, and the polymer material has the characteristics of easiness in forming, low cost and the like and has wide application.
Disclosure of Invention
The invention aims to provide a method for manufacturing a graphene-doped polyimide film, and the produced polyimide film has good mechanical property and electric conductivity and can be applied to a plurality of special fields
The technical scheme is as follows:
a method for manufacturing a graphene-doped polyimide composite film,
the method comprises the following steps: mixing and reacting the required graphene with a solvent, diamine and dianhydride by adopting an in-situ polymerization method to prepare polyamic acid with graphene;
step two: uniformly coating polyamic acid on a plane plate by using a film coating machine, and putting the plane plate into a high-temperature oven for imidization to generate the required polyimide;
step three: taking out the product and stripping the polyimide film on the plane plate to obtain the required polyimide layer;
step four: then putting the polyimide layer in the middle, respectively laying an epoxy resin layer on the upper and lower sides of the polyimide layer, and rolling and combining the epoxy resin layers by using a rolling machine to obtain the required material.
Further, the preparation method of the polyamic acid comprises the steps of firstly dissolving graphene into diamine and a solvent, then slowly adding dianhydride, and stopping adding the dianhydride when the molar numbers of the diamine and the dianhydride are equal, wherein the viscosity of a system is rapidly increased.
Further, the diamine in the invention is 44-diaminodiphenyl ether or p-phenylenediamine, the dianhydride is pyromellitic dianhydride or biphenyl tetracarboxylic dianhydride, and the solvent is dimethylacetamide or dimethylformamide.
Furthermore, the flat plate is a toughened glass plate, and the thickness of the thin film coated on the flat plate is 5-200 microns.
Further, the plane plate in the invention is a stainless steel plate.
Further, the imidization temperature in the high-temperature oven in the present invention is first 1H at 80 ℃ followed by 30 minutes at 100 ℃,150 ℃,200 ℃,250 ℃, and 300 ℃.
Further, the total mass of the dianhydride and the diamine accounts for 10-30% of the mass of the solvent, and the graphene accounts for 1-200% of the total mass of the dianhydride and the diamine.
Furthermore, after the polyimide film is obtained, a layer of epoxy resin layer is laid on the upper part and the lower part of the polyimide film to be pressed and tightly combined, and the thickness ratio of the epoxy resin layer to the polyimide layer is 0.1-10.
The beneficial effects of the invention are as follows:
1. according to the invention, in-situ polymerization is adopted to dissolve graphene into polyamide acid, and then imidization is carried out to produce polyimide, so that the preparation method is simple, and the nanoparticles are well dispersed in the polyimide.
2. The polyimide composite film produced by the invention has the characteristics of high mechanical strength and high conductivity, and can be applied to some special fields.
Detailed Description
The technical solutions in the embodiments of the present invention will be described below by way of examples in conjunction with the method of the present invention, and it is obvious that the examples are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
Weighing 50g of diaminodiphenyl ether and 200g of graphene powder, dissolving the diaminodiphenyl ether and 200g of graphene powder in 400g of dimethylacetamide solution, slowly adding 63.2g of pyromellitic dianhydride while stirring, stirring until the viscosity of the solution increases and the rod climbing phenomenon occurs, taking out the liquid, uniformly coating the liquid on a toughened glass plate by using an automatic coating machine to ensure that the film thickness is 20 microns, then putting the toughened glass plate coated with the polyamic acid solution into a high-temperature oven, controlling the temperature rise and heat preservation speed to imidize the toughened glass plate, carrying out heat preservation at 80 ℃ for 1H, then carrying out heat preservation at 100 ℃,150 ℃,200 ℃,250 ℃, 300 ℃ for 30 minutes respectively, finally reducing the temperature of the oven, taking out the plate, stripping the polyimide film, then laying an epoxy resin layer with the thickness of 20 microns on the upper layer and the lower layer of the polyimide film, putting the plate into a calender until the polyimide layer is tightly combined with the epoxy resin layer, and finally, taking out the material to obtain the graphene-doped polyimide composite film.
In the invention, the adopted graphene filler is preferably graphene powder, oxidized graphene or redox graphene, and the graphene serving as a filler can effectively improve the performance of polyimide,
in the invention, the method for preparing polyamic acid is preferably that graphene and diaminodiphenyl ether are mixed and dissolved in dimethylacetamide, pyromellitic dianhydride is slowly added, when the molar numbers of the diaminodiphenyl ether and the pyromellitic dianhydride are equal, the viscosity of the system is rapidly increased, and at the moment, the adding of the pyromellitic dianhydride is stopped,
in the invention, the adopted plane plate is preferably a toughened glass plate, the adopted film thickness is 20 microns,
in the present invention, it is preferable that the imidization of the polyamic acid to be produced is carried out by holding the polyamic acid at 80 ℃ for 1H, holding the polyamic acid at 100 ℃,150 ℃,200 ℃,250 ℃, 300 ℃ for 30 minutes,
in the present invention, it is preferable that after the polyimide film is formed, an epoxy resin layer is further laminated on and under the polyimide film, and the polyimide film is tightly bonded to the epoxy resin layer by calendering with a calender, and the thickness of the epoxy resin layer used is 20 μm.
Claims (8)
1. A manufacturing method of a graphene-doped polyimide composite film is characterized by comprising the following steps:
the method comprises the following steps: mixing and reacting the required graphene with a solvent, diamine and dianhydride by adopting an in-situ polymerization method to prepare polyamic acid with graphene;
step two: uniformly coating polyamic acid on a plane plate by using a film coating machine, and putting the plane plate into a high-temperature oven for imidization to generate the required polyimide;
step three: taking out the product and stripping the polyimide film on the plane plate to obtain the required polyimide layer;
step four: then putting the polyimide layer in the middle, respectively laying an epoxy resin layer on the upper and lower sides of the polyimide layer, and rolling and combining the epoxy resin layers by using a rolling machine to obtain the required material.
2. The method for preparing a graphene-doped polyimide composite film according to claim 1, wherein the preparation method of the polyamic acid comprises the steps of firstly dissolving graphene in a diamine and a solvent, then slowly adding dianhydride, wherein when the molar numbers of the diamine and the dianhydride are equal, the viscosity of a system is rapidly increased, and at the moment, the dianhydride is stopped being added.
3. The method according to claim 2, wherein the diamine is 44-diaminodiphenyl ether or p-phenylenediamine, the dianhydride is pyromellitic dianhydride or biphenyltetracarboxylic dianhydride, and the solvent is dimethylacetamide or dimethylformamide.
4. The method for manufacturing the graphene-doped polyimide composite film according to claim 1, wherein the planar plate is a tempered glass plate, and the thickness of the film coated on the planar plate is 5-200 microns.
5. The method for manufacturing the graphene-doped polyimide composite film according to claim 4, wherein the planar plate is a stainless steel plate.
6. The method of claim 1, wherein the imidization temperature in the high temperature oven is 80 ℃ for 1H, followed by 100 ℃,150 ℃,200 ℃,250 ℃, and 300 ℃ for 30 minutes.
7. The method of claim 1, wherein the total mass of the dianhydride and the diamine accounts for 10 to 30% of the mass of the solvent, and the graphene accounts for 1 to 200% of the total mass of the dianhydride and the diamine.
8. The method for manufacturing a graphene-doped polyimide composite film according to claim 1, wherein after the polyimide film is obtained, an epoxy resin layer is laid on and under the polyimide film, and the epoxy resin layer and the polyimide layer are tightly bonded by rolling, wherein the thickness ratio of the epoxy resin layer to the polyimide layer is 0.1-10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110013896.7A CN112917955A (en) | 2021-01-06 | 2021-01-06 | Manufacturing method of graphene-doped polyimide composite film |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110013896.7A CN112917955A (en) | 2021-01-06 | 2021-01-06 | Manufacturing method of graphene-doped polyimide composite film |
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| CN112917955A true CN112917955A (en) | 2021-06-08 |
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| CN202110013896.7A Pending CN112917955A (en) | 2021-01-06 | 2021-01-06 | Manufacturing method of graphene-doped polyimide composite film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115819763A (en) * | 2022-10-20 | 2023-03-21 | 慧迈材料科技(广东)有限公司 | Preparation method of graphene-doped polyimide powder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128654A (en) * | 2019-06-11 | 2019-08-16 | 慧迈材料科技(广东)有限公司 | A kind of Kapton of novel containing graphene |
| CN110172149A (en) * | 2019-06-11 | 2019-08-27 | 慧迈材料科技(广东)有限公司 | A kind of graphene doped polyimide film |
| CN110172170A (en) * | 2019-06-11 | 2019-08-27 | 慧迈材料科技(广东)有限公司 | A kind of manufacturing method of polyimides and graphene composite film |
| CN110216955A (en) * | 2019-06-11 | 2019-09-10 | 慧迈材料科技(广东)有限公司 | It is a kind of can Inverter fed motor laminated film manufacturing method |
-
2021
- 2021-01-06 CN CN202110013896.7A patent/CN112917955A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128654A (en) * | 2019-06-11 | 2019-08-16 | 慧迈材料科技(广东)有限公司 | A kind of Kapton of novel containing graphene |
| CN110172149A (en) * | 2019-06-11 | 2019-08-27 | 慧迈材料科技(广东)有限公司 | A kind of graphene doped polyimide film |
| CN110172170A (en) * | 2019-06-11 | 2019-08-27 | 慧迈材料科技(广东)有限公司 | A kind of manufacturing method of polyimides and graphene composite film |
| CN110216955A (en) * | 2019-06-11 | 2019-09-10 | 慧迈材料科技(广东)有限公司 | It is a kind of can Inverter fed motor laminated film manufacturing method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115819763A (en) * | 2022-10-20 | 2023-03-21 | 慧迈材料科技(广东)有限公司 | Preparation method of graphene-doped polyimide powder |
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