CN114806099A - Manufacturing method of graphene master batch and graphene seismic film - Google Patents
Manufacturing method of graphene master batch and graphene seismic film Download PDFInfo
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Abstract
The invention discloses a manufacturing method of a graphene master batch and a graphene seismic film, wherein the manufacturing method of the graphene master batch comprises the following steps: melting and mixing a high polymer material and graphene powder with a weight percentage of 2 wt.% to 8 wt.% to form a mixture; uniformly adding an additive and a rubber chain agent to the mixture; preparing a plurality of graphene master batches from a molten raw material which is molten and mixed with a high polymer material, graphene powder, an additive and a glue chain agent. The invention further comprises a manufacturing method of the graphene seismic film by taking the graphene master batch as a raw material. The invention solves the technical problems of high manufacturing difficulty, difficult reduction of manufacturing cost and incapability of optimizing the physical characteristics of the manufactured products in the prior art, and achieves the purposes of reducing the manufacturing cost and easily adjusting the physical characteristics to be optimized.
Description
Technical Field
The invention relates to a manufacturing method of a master batch and a seismic film, in particular to a manufacturing method of a graphene master batch containing graphene powder and a graphene seismic film.
Background
The plastic film generally available on the market has a limited application range because of insufficient rigidity, and the application needs to additionally enhance the rigidity or other physical properties of the plastic film according to different requirements. In the application field of the vibrating membrane of the earphone or the loudspeaker, in the prior art, because the rigidity of a common plastic membrane is generally insufficient, the shape of the plastic membrane is usually supported by a paper or plastic bracket, and a special coating is coated on the surface of the formed plastic membrane after shaping to increase the rigidity of the plastic membrane. However, because the material properties or the elasticity of the coated special coating and the adhesive film are different, the deformation of the special coating and the adhesive film at each part is inconsistent after coating and stretching, so that the film forming quality of the seismic film is uneven, and the quality of the final product of the seismic film is affected, therefore, the special coating can be coated only after the adhesive film is formed in general conditions, the manufacturing process difficulty of the combination of the bracket and the coating of the special coating is higher, and the flow steps are complicated, so that the whole manufacturing cost of the seismic film is difficult to reduce.
Further, in the manufacturing process of the seismic diaphragm in the prior art, the ester raw material must be heated to prepare the mixture, and the mixture is heated again to prepare the ester particles. Then the ester particles and any high molecular material are melted and mixed again for product demand, and then the product is made by extension or injection molding. However, since the above-mentioned manufacturing process requires a plurality of heating processes, chain scission and defects occur between constituent material molecules during each heating process, and thus physical properties of the manufactured product cannot be optimized.
Therefore, how to design a method for manufacturing a graphene master batch and a method for manufacturing a graphene seismic film, especially to solve the technical problems of high process difficulty, difficulty in reducing the manufacturing cost and incapability of optimizing the physical properties of the processed product in the prior art, is an important subject studied by the inventors of the present application.
Disclosure of Invention
An object of the present invention is to provide a method for manufacturing graphene master batch, which solves the technical problems of the prior art that the manufacturing difficulty is high, the manufacturing cost is difficult to reduce, and the physical properties of the manufactured product cannot be optimized, and achieves the purposes of reducing the manufacturing cost and easily adjusting the physical properties to be optimized.
In order to achieve the above object, the method for manufacturing graphene masterbatch provided by the present invention includes the following steps: melting and mixing a high polymer material and graphene powder with a weight percentage of 2 wt.% to 8 wt.% to form a mixture; uniformly adding an additive comprising a coupling agent, a dispersing agent and a catalyst into the mixture; uniformly adding a rubber chain agent comprising a curing agent and a linking agent to the mixture; and preparing a plurality of short cylindrical granular graphene master batches from the molten raw materials which are molten and mixed with the high polymer material, the graphene powder, the additive and the adhesive chain agent. Wherein the molecular weight of at least one of the coupling agent and the dispersing agent is the same as that of the high molecular material. Wherein the catalyst accounts for 20 wt.% to 22 wt.% of the molten raw material, and the total of the binder, the coupling agent and the dispersant accounts for 70 wt.% of the molten raw material.
In the method for manufacturing the graphene masterbatch, the polymer material includes at least one of polyacrylonitrile, polycarbonate, polypropylene, polyethylene terephthalate, polyamide, nylon, polystyrene, polymethyl methacrylate, and polylactic acid.
In the method for manufacturing the graphene masterbatch, the catalyst includes at least one of a germanium catalyst, an antimony catalyst, and a titanium catalyst.
Further, in the method for manufacturing the graphene master batch, the ratio of the curing agent to the linking agent in the adhesive linking agent is between 9:1 and 5: 5.
Further, in the method for manufacturing the graphene master batch, the weight percentage of the graphene powder in the mixture is 5 wt.%.
Further, in the method for manufacturing the graphene master batch, the intrinsic viscosity of each graphene master batch is between 0.6 dl/g and 0.7 dl/g.
Another objective of the present invention is to provide a method for manufacturing a graphene seismic film, which solves the technical problems of the prior art that the manufacturing difficulty is high, the manufacturing cost is difficult to reduce, and the physical properties of the manufactured product cannot be optimized, so as to achieve the purpose of reducing the manufacturing cost and easily adjusting the physical properties to be optimized.
In order to achieve the above another object, the present invention provides a method for manufacturing a graphene seismic film, including the following steps: melting the plurality of graphene master batches; carrying out biaxial stretching on the melted graphene master batches by using a biaxial stretcher to form a graphene seismic film; wherein the polymer material comprises polyethylene terephthalate.
Further, in the method for manufacturing the graphene seismic film, the thickness of the graphene seismic film is between 10 micrometers and 25 micrometers.
Still another objective of the present invention is to provide a method for manufacturing a graphene seismic film, which solves the technical problems of high process difficulty, complicated process steps, non-uniform molding quality, and difficulty in reducing manufacturing cost in the prior art, and achieves the purpose of easy and low-cost manufacturing.
In order to achieve the above and other objects, the present invention provides a method for manufacturing a graphene seismic film, comprising the following steps: melting the plurality of graphene master batches; then carrying out biaxial stretching on the melted graphene master batches through a biaxial stretcher, or carrying out radial stretching on the melted graphene master batches through an injection molding machine to form a graphene seismic film; wherein the high molecular material is polyethylene terephthalate or polypropylene.
When the manufacturing method of the graphene master batch and the graphene seismic film is used, the graphene powder used in the first step of the invention only accounts for 2 wt.% to 8 wt.%, and therefore, the original material characteristics of the high polymer material cannot be completely shielded. In material science, graphene has excellent mechanical properties, and is specific to high rigidity, high thermal conductivity and high electron mobility, and is also an ideal filler for a polymeric material, and the physical properties of a high polymer material can be enhanced by only a small amount of graphene. However, for powdered materials, Van der Waals force (Van der Waals force) must still be overcome. Particularly, for graphene, a crystal structure of graphite (graphite) is formed by stacking one layer of graphene sheets and another layer of graphene sheets, and the graphene sheets are connected to each other according to van der waals force, but in a process of modifying a polymer material by using graphene, a molecular chain of the polymer material is easily affected by van der waals force between the graphene sheets and cannot form uniform and stable bonding, and finally, the condition that the melt mixing of the graphene and the polymer material is not uniform may occur to affect the uniformity and quality of subsequent seismic film forming.
Further, in the second step of the present invention, an additive including a coupling agent, a dispersing agent, and a catalyst is uniformly added to the mixture. The coupling agent (coupling agent) can be used to enhance the chain state of the side chain of the polymer material. The dispersing agent (dispersant) can prevent the agglomeration phenomenon or the sedimentation phenomenon of material molecules, can enable the physical properties of the material at all positions to be more uniform, and can obtain graphene master batches and graphene seismic films with uniform physical properties in the subsequent degradation process. The catalyst (catalyst) can be used to change the physical properties of the mixture, such as mechanical strength (e.g., the ability to resist external force impact without generating strain), chemical strength (e.g., the chain state of the side chain is strengthened so that the molecular chain is not easy to break, i.e., toughness), and physical strength (e.g., the ability to resist internal stress to improve rigidity or ductility, etc.).
In the third step of the present invention, a rubber chain agent including a curing agent (curing agent) and a chain agent (chain extender) is uniformly added to the mixture, so as to change the Intrinsic Viscosity (IV) of the material itself, which can be adjusted according to the subsequent processing (such as injection molding, casting, calendering, etc.) of the material, thereby improving the elongation property and impact resistance of the seismic film. Finally, the melted raw materials which are melted and mixed with the high polymer material, the graphene powder, the additive and the adhesive chain agent are prepared into a plurality of short cylindrical granular graphene master batches. The preparation process of the plurality of graphene master batches only needs one-time melting and heating, so that chain breakage and defects among material molecules caused by multiple times of heating can be avoided, and further, the physical properties of the product in the preparation process can be controlled to be optimized.
Therefore, the manufacturing method of the graphene master batch and the graphene seismic film solves the technical problems that the manufacturing difficulty is high, the manufacturing cost is difficult to reduce and the physical properties of the manufactured product cannot be optimized in the prior art, and achieves the purposes of reducing the manufacturing cost and easily adjusting the physical properties to be optimized.
For a further understanding of the nature, means, and efficacy of the invention to be achieved, reference should be made to the following detailed description of the invention and accompanying drawings which are believed to be in full and illustrative embodiments of the invention, and the same will be understood by reference to the following drawings, which are provided for purposes of illustration and description only and are not intended to be limiting.
Drawings
Fig. 1 is a flowchart of a method for manufacturing graphene master batch according to the present invention;
FIG. 2 is a flow chart of a method for fabricating a graphene seismic film according to an embodiment of the present invention;
FIGS. 3 and 4 are schematic views illustrating the processing of the graphene vibration molded BOPET film according to the present invention;
FIG. 5 is a flow chart of another embodiment of a method for fabricating a graphene seismic film according to the present invention; and
fig. 6 is a schematic view of the process of vibration molding the graphene into the PP film according to the present invention.
Symbolic illustration in the drawings:
10, graphene master batch;
20, BOPET film;
30, PP film;
S1-S6;
MD is the moving direction;
TD is vertical direction;
S1-S7.
Detailed Description
The technical contents and the detailed description of the present invention are described below with reference to the drawings.
Please refer to fig. 1 to 3. Fig. 1 is a flowchart of a manufacturing method of the graphene master batch of the present invention, fig. 2 is a flowchart of an embodiment of a manufacturing method of the graphene seismic film of the present invention, and fig. 3 and 4 are schematic processing diagrams of the graphene seismic film of the present invention formed into a BOPET film. In an embodiment of the present invention, the manufacturing method of the graphene masterbatch 10 includes the following four steps: a first step of melt-mixing a polymer material and graphene (graphene) powder with a weight percentage of 2 wt.% to 8 wt.% to form a mixture, as shown in step S1 of fig. 1. Further, the graphene powder may include a plurality of graphene micro-sheets (not shown), and a ratio of 95% or more of the plurality of graphene micro-sheets may have a maximum sheet diameter of less than 45 micrometers (μm). In the embodiment of the present invention, the polymer material may include at least one of Polyacrylonitrile (PAN), Polycarbonate (PC), polypropylene (PP), polyethylene terephthalate (PET), Polyamide (PA), Nylon (Nylon), Polystyrene (PS), polymethyl methacrylate (PMMA), and polylactic acid (PLA). Further, the graphene powder may be 5 wt.% of the mixture.
In the embodiment of the present invention, the second step is to uniformly add additives including a coupling agent (coupling agent), a dispersant (dispersant) and a catalyst (catalyst) to the aforementioned mixture, as shown in step S2 of fig. 1. Wherein the coupling agent can be used for enhancing the chain bonding state of the side chain of the high polymer material. The dispersing agent can prevent the agglomeration phenomenon or the sedimentation phenomenon of material molecules, so that the physical properties of the material at all positions are more uniform, and the graphene master batch 10 and the graphene seismic film with uniform physical properties can be obtained in the subsequent degradation process. The catalyst can be used to change the physical properties of the mixture, such as mechanical strength (e.g., ability to resist external force impact without generating strain), chemical strength (e.g., strength of the side chains to make the molecular chains less prone to breaking, i.e., toughness), and physical strength (e.g., resistance to internal stress to improve rigidity or ductility, etc.). Further, the molecular weight of at least one of the coupling agent and the dispersing agent is the same as the molecular weight of the polymer material, and the coupling agent and the dispersing agent are used for enhancing the chain bonding state of the side chain of the polymer material while maintaining a specific Intrinsic Viscosity (IV). Further, the catalyst may include at least one of a germanium (Ge) catalyst, an antimony (Sb) catalyst, and a titanium (Ti) catalyst, and the germanium catalyst, the antimony catalyst, and the titanium catalyst are all heterogeneous catalysts (hetereogenous catalysts), which may also be referred to as heterogeneous catalysts.
In the embodiment of the present invention, the germanium catalyst is used to enhance the mechanical strength, the antimony catalyst is used to enhance the chemical strength, and the titanium catalyst is used to enhance the physical strength. The heterogeneous catalyst represents that a catalyst participating in a reaction and a reactant are different phases, in the heterogeneous catalytic reaction, the reactant is firstly adsorbed on the surface of the catalyst, then an original chemical bond in the structure of the reactant is broken and a new chemical bond is generated, and finally a product is desorbed from the surface of the catalyst (desorption) and leaves.
In the embodiment of the present invention, the third step is to uniformly add a rubber-based binder including a curing agent and a binder to the mixture, as shown in step S3 of fig. 1. The curing agent may be an Ultraviolet (UV) curing or solvent with other curing means. And further, the ratio of the curing agent to the bonding agent in the rubber chain agent is between 9:1 and 5: 5.
In the embodiment of the present invention, the fourth step is to prepare a plurality of graphene mother particles 10 each having a short cylindrical particle shape from the molten raw material in which the polymer material, the graphene powder, the additive and the binder are melt-mixed, as shown in step S4 of fig. 1. The plurality of graphene masterbatches 10 may be melted to form the graphene seismic film. Wherein the Intrinsic Viscosity (IV) of each graphene master batch can be between 0.6 dl/g and 0.7 dl/g (wherein the unit dl/g means deciliter per gram), the weight percentage of the catalyst in the molten raw material can be between 20 wt.% and 22 wt.%, and the total weight percentage of the adhesive chain agent, the coupling agent and the dispersing agent in the molten raw material can be 70 wt.%. Further, the concentration of the graphene powder in the molten raw material may be between 100ppm and 5000 ppm.
In the embodiment of the present invention, the manufactured graphene seismic film may be a biaxially-oriented polyester (BOPET) film 20 or an arc-shaped PP film 30. Wherein, the BOPET film 20 has the characteristics of high mechanical strength, high rigidity, high transparency, high surface gloss and the like. For practitioners producing seismic films, the graphene master batch 10 as described above may be selected for further processing. As shown in fig. 2 and 3, the plurality of graphene mother particles 10 are melted (step S5), and the melted plurality of graphene mother particles 10 are biaxially stretched by a biaxial stretcher (not shown) to form a graphene seismic film (step S6). Further, when the selected polymer material is polyethylene terephthalate (PET), the graphene seismic film may be made into the BOPET film 20, so as to achieve the purpose of changing the physical properties of the seismic film by uniformly adding graphene into the seismic film, for example, the tensile strength and the properties of impact resistance, cold resistance, heat resistance, puncture resistance, wear resistance and the like can be increased, and the seismic film can be applied to the fields of speakers, earphones and the like. As shown in fig. 4, the BOPET film 20 may be stretched in both directions along the Machine Direction (MD) and the Transverse Direction (TD), and subjected to appropriate cooling, heat treatment or surface processing (such as coating slurry or plasma) to complete the whole process. The BOPET film 20 may have a thickness of between 10 and 25 microns.
Please refer to fig. 5 and 6. Fig. 5 is a flowchart of another embodiment of the method for manufacturing a graphene seismic film according to the present invention, and fig. 6 is a schematic processing diagram of a PP thin film formed by seismic molding of graphene according to the present invention. In this embodiment, the same as the previous embodiment, but after the plurality of graphene base particles 10 are melted (step S5), the plurality of melted graphene base particles 10 are radially stretched by an injection molding machine (not shown) to form a graphene seismic film (step S7). Further, when the selected polymer material is polypropylene (PP), the graphene seismic film may be made into the PP thin film 30. In the present embodiment, the thickness of the PP film 30 may be between 10 micrometers and 25 micrometers, and the PP film 30 may be used as a horn film for a vehicle, however, the application of the present invention is not limited thereto.
When the manufacturing method of the graphene master batch and the graphene seismic film is used, the graphene powder used in the first step of the invention only accounts for 2 wt.% to 8 wt.%, and therefore, the original material characteristics of the high polymer material cannot be completely shielded. In material science, graphene has excellent mechanical properties, and is specific to high rigidity, high thermal conductivity and high electron mobility, and is also an ideal filler for a polymeric material, and the physical properties of a high polymer material can be enhanced by only a small amount of graphene. However, for powdered materials, Van der Waals force (Van der Waals force) must still be overcome. Particularly, for graphene, since the crystal structure of graphite (graphite) is formed by stacking graphene sheets in a single atomic layer one after another, and the graphene sheets are connected to each other by van der waals force, in the process of modifying a polymer material by using graphene, molecular chains of the polymer material are easily affected by van der waals force between the graphene sheets and cannot form uniform and stable bonding, which may eventually cause uneven melt mixing of graphene and polymer material and affect uniformity and quality of subsequent film forming. Further, in the second step of the present invention, additives including a coupling agent, a dispersing agent, and a catalyst are uniformly added to the mixture. The coupling agent can be used for enhancing the chain bonding state of the side chain of the high polymer material. The dispersant can prevent an agglomeration phenomenon or a sedimentation phenomenon of material molecules. The catalyst may be used to alter the physical properties of the mixture. In the third step of the present invention, a rubber-chain agent including a curing agent and a linking agent is uniformly added to the mixture, so that the Intrinsic Viscosity (IV) of the material itself can be changed. Finally, the melted raw materials which are melted and mixed with the high polymer material, the graphene powder, the additive and the adhesive chain agent are prepared into a plurality of short cylindrical granular graphene master batches. The preparation process of the plurality of graphene master batches only needs one-time melting and heating, so that chain breakage and defects among material molecules caused by multiple times of heating can be avoided, and further, the physical properties of the product in the preparation process can be controlled to be optimized.
Therefore, the manufacturing method of the graphene master batch and the graphene seismic film solves the technical problems that the manufacturing difficulty is high, the manufacturing cost is difficult to reduce and the physical properties of the manufactured product cannot be optimized in the prior art, and achieves the purposes of reducing the manufacturing cost and easily adjusting the physical properties to be optimized.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
It should be understood that the structures, ratios, sizes, and numbers of elements shown in the drawings and described in the specification are only used for understanding and reading the present disclosure, and are not to be construed as limiting the scope of the present disclosure, which is not essential to the technology, and any modifications of the structures, changes of the ratios, or adjustments of the sizes may be made without affecting the efficacy and attainment of the same.
Claims (10)
1. A method for manufacturing graphene master batch is characterized by comprising the following steps:
melting and mixing a high polymer material and 2 wt.% to 8 wt.% of graphene powder to form a mixture;
uniformly adding an additive comprising a coupling agent, a dispersing agent and a catalyst to the mixture;
uniformly adding a rubber chain agent comprising a curing agent and a linking agent to the mixture; and
preparing a melting raw material which is melted and mixed with the high polymer material, the graphene powder, the additive and the adhesive agent into a plurality of graphene master batches which are respectively in a short cylindrical granular shape;
wherein the molecular weight of at least one of the coupling agent and the dispersing agent is the same as that of the high molecular material;
wherein the catalyst accounts for 20 wt.% to 22 wt.% of the molten raw material, and the total of the binder, the coupling agent and the dispersant accounts for 70 wt.% of the molten raw material.
2. The method of claim 1, wherein the polymer material comprises at least one of polyacrylonitrile, polycarbonate, polypropylene, polyethylene terephthalate, polyamide, nylon, polystyrene, polymethyl methacrylate, and polylactic acid.
3. The method of claim 1, wherein the catalyst comprises at least one of a germanium catalyst, an antimony catalyst, and a titanium catalyst.
4. The method of claim 1, wherein the ratio of the curing agent to the linking agent in the adhesive is between 9:1 and 5: 5.
5. The method of claim 1, wherein the graphene powder is 5 wt.% of the mixture.
6. The method for producing the graphene masterbatch according to claim 1, wherein the intrinsic viscosity of each graphene masterbatch is between 0.6 dl/g and 0.7 dl/g.
7. A method for manufacturing a graphene seismic film, comprising:
melting the plurality of graphene master batches prepared by the manufacturing method according to claim 1; and
carrying out biaxial stretching on the plurality of melted graphene master batches by a biaxial stretcher to form a graphene seismic film;
wherein the polymer material of claim 1 is polyethylene terephthalate.
8. The method of claim 7, wherein the graphene seismic film has a thickness of 10-25 μm.
9. A method for manufacturing a graphene seismic film, comprising:
melting the plurality of graphene master batches prepared by the manufacturing method according to claim 1; and
radially stretching the plurality of melted graphene master batches by using an injection molding machine to form a graphene seismic film;
wherein the polymer material of claim 1 is polypropylene.
10. The method of claim 9, wherein the graphene seismic film has a thickness of 10 to 25 microns.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103929710A (en) * | 2014-04-25 | 2014-07-16 | 瑞声光电科技(常州)有限公司 | Preparation method of composite vibrating diaphragm |
| CN103929709A (en) * | 2014-04-25 | 2014-07-16 | 瑞声光电科技(常州)有限公司 | Preparation method of composite vibrating diaphragm |
| CN105025428A (en) * | 2014-04-30 | 2015-11-04 | 福建省辉锐材料科技有限公司 | Loudspeaker diaphragm preparation method |
| CN106117744A (en) * | 2016-07-19 | 2016-11-16 | 暨南大学 | A kind of Graphene/polyolefin plastics composite food package thin film and preparation method thereof |
| CN106863965A (en) * | 2017-02-27 | 2017-06-20 | 合肥中科富华新材料有限公司 | A kind of self-priming water, shock film and preparation method |
| CN107379684A (en) * | 2017-07-25 | 2017-11-24 | 合肥威斯伏新材料有限公司 | A kind of self-priming water, shock film and preparation method |
-
2021
- 2021-01-28 CN CN202110117495.6A patent/CN114806099A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103929710A (en) * | 2014-04-25 | 2014-07-16 | 瑞声光电科技(常州)有限公司 | Preparation method of composite vibrating diaphragm |
| CN103929709A (en) * | 2014-04-25 | 2014-07-16 | 瑞声光电科技(常州)有限公司 | Preparation method of composite vibrating diaphragm |
| CN105025428A (en) * | 2014-04-30 | 2015-11-04 | 福建省辉锐材料科技有限公司 | Loudspeaker diaphragm preparation method |
| CN106117744A (en) * | 2016-07-19 | 2016-11-16 | 暨南大学 | A kind of Graphene/polyolefin plastics composite food package thin film and preparation method thereof |
| CN106863965A (en) * | 2017-02-27 | 2017-06-20 | 合肥中科富华新材料有限公司 | A kind of self-priming water, shock film and preparation method |
| CN107379684A (en) * | 2017-07-25 | 2017-11-24 | 合肥威斯伏新材料有限公司 | A kind of self-priming water, shock film and preparation method |
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