CN114456577B - Antistatic E-TPU material and preparation method thereof - Google Patents
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Abstract
The application discloses an antistatic E-TPU material and a preparation method thereof, wherein graphene oxide is dispersed in deionized water to obtain graphene oxide dispersion liquid; dispersing the graphene oxide dispersion liquid in an organic solvent to obtain a graphene oxide organic solution; carrying out dipping treatment on the E-TPU granules by using the graphene oxide organic solution, and then carrying out drying treatment to obtain E-TPU granules coated by graphene oxide; completely soaking the graphene oxide coated E-TPU granules in a reducing agent solution for reduction treatment to obtain graphene coated E-TPU granules; and carrying out heating forming treatment on the E-TPU granules coated by the graphene to obtain the antistatic E-TPU material. According to the application, graphene oxide and E-TPU granules are used as raw materials, and the preparation process of dipping, drying, reduction and heating forming is adopted to realize filling of graphene among E-TPU granules, so that the antistatic E-TPIU material with greatly improved antistatic performance is obtained, the stability is good, the preparation process is simple and easy, and the production cost is low.
Description
Technical Field
The application relates to the technical field of functional materials, in particular to an antistatic E-TPU material and a preparation method thereof.
Background
The E-TPU material is a novel polymer material with sufficient elasticity and light weight, and after foaming, the volume of the particle material expands several times, and the size and the shape of the particle material are the same as those of popcorn, so the E-TPU material is also vividly called "popcorn"; meanwhile, the E-TPU material integrates the characteristics of TPU and the advantages of foam, overcomes the defects of high weight, high hardness, poor shock absorption performance and the like of TPU raw materials, and has the characteristics of excellent ultralow density, high rebound resilience, wear resistance, folding resistance and the like; the E-TPU material at the present stage is widely applied to a plurality of industries such as shoe materials, packaging materials, buffer gaskets, vibration damping materials, automotive interiors, tires and the like, and particularly in the field of sports shoes, compared with the traditional EVA midsole, the E-TPU midsole is made of physically foamed polyurethane materials, is in a popcorn shape after being molded, has excellent rebound resilience and deformation recovery, and has performances far exceeding those of the traditional EVA materials.
However, with the increasing use of E-TPU materials, higher requirements are being placed on E-TPU materials in some special fields and places, such as antistatic properties and yellowing resistance; in the prior art, the traditional additive method is mostly adopted for the functional research of the E-TPU material, the process is complicated, the processing difficulty is high, and the research of the antistatic property of the E-TPU material is not carried out in the prior art.
Therefore, an improved antistatic E-TPU material and a preparation method thereof are needed, the antistatic performance of the E-TPU material is improved, the process flow is simplified, and the cost is reduced.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides an antistatic E-TPU material and a preparation method thereof, which can realize good antistatic performance, simplify the process and reduce the cost.
The technical scheme is as follows:
the application provides a preparation method of an antistatic E-TPU material, which comprises the following steps:
s1, dispersing graphene oxide in deionized water to obtain graphene oxide dispersion liquid;
s2, dispersing the graphene oxide dispersion liquid in an organic solvent to obtain a graphene oxide organic solution; wherein the weight ratio of the organic solvent to the deionized water is (1-9) 1;
s3, carrying out dipping treatment on the E-TPU granules by using the graphene oxide organic solution, and then carrying out drying treatment to obtain E-TPU granules coated by graphene oxide;
s4, completely soaking the E-TPU granules coated with the graphene oxide in a reducing agent solution for reduction treatment to obtain E-TPU granules coated with the graphene oxide;
and S5, performing heat forming treatment on the E-TPU granules coated by the graphene to obtain the antistatic E-TPU material.
Further, the organic solvent is at least one of tetrahydrofuran and N, N-dimethylformamide.
Further, the concentration of graphene oxide in the graphene oxide organic solution is 0.1-2 g/L.
Further, the step S2 includes:
dispersing the graphene oxide dispersion liquid in an organic solvent for 5min, and performing high-frequency ultrasound for 10-20 min to obtain the graphene oxide organic solution.
Further, the drying process in the step S3 is as follows:
and drying the E-TPU granules subjected to the impregnation treatment in a vacuum environment at 60-80 ℃ to obtain the E-TPU granules coated with the graphene oxide.
Further, the reducing agent in the reducing agent solution is at least one of sodium citrate or sodium ascorbate.
Further, the reduction processing in the step S4 is as follows:
and (3) placing the graphene oxide coated E-TPU granules into a reducing agent solution with the concentration of 5-50 g/L, and reducing for 2-8 hours at the reducing temperature of 60-70 ℃ to obtain the graphene coated E-TPU granules.
Further, the heat forming treatment is a steam heat forming treatment or a microwave heat forming treatment.
Further, the steam heat molding process includes:
and heating the graphene-coated E-TPU granules for 5 to 60 seconds at a heating temperature of 120 to 150 ℃ to obtain the antistatic E-TPU material.
The application also provides an antistatic E-TPU material, which is obtained by the preparation method of the antistatic E-TPU material, and comprises E-TPU particles and graphene filled among the E-TPU particles in a skeleton form.
The implementation of the application has the following beneficial effects:
1. according to the antistatic E-TPU material and the preparation method thereof, an impregnation method is adopted, and through micro-swelling of an organic solvent on the surface of E-TPU granules, solvent molecules can penetrate into the surface layer of the E-TPU granules with graphene oxide, and then, through drying treatment and reduction treatment, the E-TPU granules are coated with graphene; in addition, the application combines special heating forming treatment to ensure that the 'popcorn' structure of the E-TPU material is unchanged, so that graphene is filled among E-TPU particles in a skeleton form to form a conductive network passage, and good antistatic performance can be realized; meanwhile, the preparation method is simple and easy to implement, greatly reduces the process difficulty, simplifies the process flow, reduces the production cost, and can be widely applied to the fields of antistatic soles, antistatic tires and the like.
2. According to the application, the reduced graphene is used as the conductive agent, and only the surface layer of the E-TPU is required to be coated, so that compared with the conventional process of adding the conductive agent and remelting and extruding, the conductive agent is less in use amount, and the material cost is reduced.
3. According to the application, vc aqueous solution is used as a reducing agent to chemically reduce the E-TPU granules coated with graphene oxide, so that the self structure of the E-TPU is not damaged, the reduction process is more sufficient, the reduction effect is good, and in addition, sodium citrate or sodium ascorbate is used as a reducing agent and water is used as a solvent, so that the environment-friendly chemical process concept is fully embodied.
Drawings
In order to more clearly illustrate the technical solution of the present application, the following description will briefly explain the drawings used in the embodiments, in which like elements are denoted by like reference numerals. It is evident that the drawings in the following description are only some embodiments of the present application and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a flow chart of a process for preparing an antistatic E-TPU material in one possible embodiment of the present application;
FIG. 2 is a surface SEM image of an antistatic E-TPU material of example 2.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments, and thus should not be construed as limiting the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It should be noted that the terms "first," "second," and the like in the description and the claims and drawings of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that embodiments of the application may be practiced otherwise than as specifically described or illustrated. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or server that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed or inherent to such process, method, article, or apparatus, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1
In order to realize the improvement of antistatic performance by combining the special structure of the E-TPU material, the application provides a preparation method of the antistatic E-TPU material, which is shown in the attached figure 1 of the specification, and comprises the following steps:
s1, dispersing graphene oxide in deionized water to obtain graphene oxide dispersion liquid;
s2, dispersing the graphene oxide dispersion liquid in an organic solvent to obtain a graphene oxide organic solution; wherein the weight ratio of the organic solvent to the deionized water is (1-9) 1;
s3, carrying out dipping treatment on the E-TPU granules by using the graphene oxide organic solution, and then carrying out drying treatment to obtain E-TPU granules coated by graphene oxide;
s4, completely soaking the E-TPU granules coated with the graphene oxide in a reducing agent solution for reduction treatment to obtain E-TPU granules coated with the graphene oxide;
and S5, performing heat forming treatment on the E-TPU granules coated by the graphene to obtain the antistatic E-TPU material.
Specifically, in one possible embodiment of the present specification, the organic solvent used in step S2 is at least one of tetrahydrofuran and N, N-dimethylformamide.
The surface of the graphene oxide contains a large amount of oxygen-containing functional groups, taking N, N-Dimethylformamide (DMF) as an organic solvent as an example, if the graphene oxide is directly dispersed in a DMF solution, the graphene oxide is extremely easy to stand and settle, so that the dispersion effect of the graphene oxide is poor, and the subsequent preparation process is influenced, so that the final antistatic performance of the antistatic E-TPU material is adversely affected; based on the consideration, in the step S1-S2, the graphene oxide is dispersed in deionized water firstly by utilizing the characteristic that the graphene oxide has a large amount of oxygen-containing functional groups and is extremely easy to disperse in aqueous solution, so that the uniformity of dispersion is ensured, and then the graphene oxide dispersion liquid is mixed with an organic solvent to disperse by utilizing the mutual solubility characteristic of the deionized water and N, N-dimethylformamide (or tetrahydrofuran), so that the graphene oxide can be well and stably dispersed in the mixed solvent.
Specifically, in one possible embodiment of the present specification, the step of dispersing the graphene oxide dispersion liquid in the organic solvent in the S2 step may specifically be:
dispersing the graphene oxide dispersion liquid in an organic solvent, mechanically dispersing for 5min, and performing high-frequency ultrasonic treatment for 10-20 min to obtain the graphene oxide organic solution.
The mechanical dispersion can be selected to be stirring, so that the graphene oxide is primarily dispersed, and then high-frequency ultrasound further ensures that the graphene oxide can be uniformly and stably dispersed into the organic solvent, so that the organic solvent can conveniently carry the graphene oxide to move in the subsequent steps.
Specifically, in one possible embodiment of the present specification, the concentration of graphene oxide in the graphene oxide organic solution obtained in the step S2 is 0.1-2 g/L, so that the mass percentage of the graphene oxide is between 0.01-0.2%, and this concentration can ensure that the antistatic E-TPU material has good antistatic performance, and meanwhile, avoid the production cost that may occur due to higher concentration; compared with the traditional preparation process of the antistatic material, the preparation method of the antistatic E-TPU material provided by the embodiment requires fewer graphene oxide raw materials, can greatly reduce the material cost, and can realize the improvement of the antistatic performance to a greater extent with fewer graphene oxide addition, and has good conductive performance improving effect.
Specifically, in other possible embodiments of the present specification, the weight ratio between the organic solvent and deionized water in the step S2 is (1-5): 1.
specifically, in the step S3, the E-TPU granules are subjected to impregnation treatment for 30-60S by using the graphene oxide organic solution, and the proper extension of the impregnation time is beneficial to the dispersion of the graphene oxide, the impregnation uniformity is improved, and the uniformity of the conductive performance of the antistatic E-TPU material of the finished product is further ensured; compared with the common TPU granules, the E-TPU granules have the advantages that the volume expansion is 5-8 times after foaming, the cell diameter is about 30-300 mu m, and in the step S3, the micro-swelling of the E-TPU granules can be further realized through the dipping treatment, namely, the E-TPU granules in the step finally show a surface layer micron-scale swelling state through the dipping treatment, so that organic solvent molecules can conveniently permeate into the surface layer of the micro-swelled E-TPU granules with graphene oxide.
Specifically, the drying process in step S3 is:
and drying the E-TPU granules subjected to the impregnation treatment in a vacuum environment at 60-80 ℃ to obtain the E-TPU granules coated with the graphene oxide.
Before the drying process starts, graphene oxide permeates into the E-TPU pellet surface layer along with an organic solvent, so that the drying treatment can recover the E-TPU pellet surface layer from a micro-swelling state, the graphene oxide is ensured to be embedded into the E-TPU pellet surface layer, the embedding is firm, and the coating of the E-TPU pellet by the graphene oxide is realized; on the other hand, the drying treatment can also extrude the organic solvent molecules in the E-TPU granules after the dipping treatment or volatilize the organic solvent molecules, thereby being beneficial to improving the overall antistatic performance of the antistatic E-TPU material.
Specifically, in the step S4, the reducing agent in the reducing agent solution is at least one of sodium citrate or sodium ascorbate, namely in the step, the reducing treatment is chemical reducing treatment of the E-TPU granules coated by graphene oxide by utilizing the strong reducibility of Vc aqueous solution; meanwhile, the chemical reduction treatment method not only can realize reduction of carboxyl functional groups on the surface of the graphene oxide, but also can realize reduction of carboxyl, epoxy groups and other functional groups, and has good reduction effect; moreover, the original structural advantage of the E-TPU granules is not destroyed by the reduction treatment with the Vc aqueous solution, and the situation that the E-TPU granules soften or even deform irreversibly due to the fact that the E-TPU granules are subjected to excessive temperature (for example, 200 ℃) in the traditional thermal reduction method can be avoided.
Specifically, the reduction process in step S4 is:
and (3) placing the graphene oxide coated E-TPU granules into a reducing agent solution with the concentration of 5-50 g/L, and reducing for 2-8 hours at the reducing temperature of 60-70 ℃ to obtain the graphene coated E-TPU granules.
Specifically, in one possible embodiment of the present specification, the concentration of the reducing agent solution in the S4 step is 25 to 50g/L.
Specifically, in one possible embodiment of the present specification, the heat forming process in the step S5 is a steam heat forming process, and then the steam heat forming process is to heat the graphene-coated E-TPU pellets for 5 to 60S at a heating temperature of 120 to 150 ℃ to obtain the antistatic E-TPU material.
And the water vapor is simultaneously introduced into the upper and lower parts of the mold of the E-TPU granules coated by the graphene, so that the water vapor conducts heat on the surfaces of the E-TPU granules coated by the graphene, heating is realized through physical heat conduction, the density of the antistatic E-TPI material is reduced, and the overall performance is improved.
Specifically, in another possible embodiment of the present specification, the heating forming treatment in the step S5 is a microwave heating forming treatment, and the E-TPU pellets coated with graphene are placed at a frequency of 300MHz-300GHz and heated for 5-30S, so as to obtain an antistatic E-TPU material; in the process, microwave heating utilizes radiation penetrating heating, so that the E-TPU granules coated by the graphene are heated uniformly, and the molding efficiency is higher.
Preferably, in other possible embodiments of the present specification, the microwave frequency is set to 2450MHz, and the resulting antistatic E-TPU material is heated at that frequency for 30s, resulting in an antistatic E-TPU material.
Furthermore, either the steam heat-forming process or the microwave heat-forming process may be performed in the mold so that the popcorn structure of the E-TPU pellets remains unchanged under the protection of the mold.
The embodiment also provides an antistatic E-TPU material, which is obtained by the preparation method of the antistatic E-TPU material, and comprises E-TPU particles and graphene filled among the E-TPU particles in a skeleton form, so that the graphene forms a conductive network path among the E-TPU particles, and the antistatic E-TPU material has excellent antistatic performance.
In this example, an antistatic E-TPU composite A is also provided, which is prepared by the following preparation method:
dispersing graphene oxide in deionized water to obtain graphene oxide dispersion liquid;
dispersing graphene oxide dispersion liquid in an organic solvent according to the weight ratio of the organic solvent to deionized water of 9:1 for 5min, and performing high-frequency ultrasonic treatment for 10min to obtain a graphene oxide organic solution with the concentration of 0.1 g/L;
carrying out dipping treatment on the E-TPU granules by using a graphene oxide organic solution for 60s, and then carrying out drying treatment to obtain E-TPU granules coated by graphene oxide;
completely soaking the E-TPU granules coated with graphene oxide in a 5g/L reducer solution, and carrying out reduction treatment for 8 hours at 60 ℃ to obtain the E-TPU granules coated with graphene;
and carrying out steam heating forming treatment on the E-TPU granules coated by the graphene to obtain an antistatic E-TPU material, namely an E-TPU composite material A.
Example 2
The preparation method of the antistatic E-TPU material comprises the following steps:
dispersing graphene oxide in deionized water to obtain graphene oxide dispersion liquid;
dispersing graphene oxide dispersion liquid in an organic solvent according to the weight ratio of the organic solvent to deionized water of 1:1 for 5min, and performing high-frequency ultrasonic treatment for 20min to obtain a graphene oxide organic solution with the concentration of 2 g/L;
carrying out dipping treatment on the E-TPU granules by using a graphene oxide organic solution for 30s, and then carrying out drying treatment to obtain E-TPU granules coated by graphene oxide;
completely soaking the E-TPU granules coated with graphene oxide in a 50g/L reducer solution, and carrying out reduction treatment for 2 hours at 60 ℃ to obtain the E-TPU granules coated with graphene;
and carrying out microwave heating forming treatment on the E-TPU granules coated by the graphene to obtain an antistatic E-TPU material, namely an E-TPU composite material B.
Example 3
The preparation method of the antistatic E-TPU material comprises the following steps:
dispersing graphene oxide in deionized water to obtain graphene oxide dispersion liquid;
dispersing graphene oxide dispersion liquid in an organic solvent according to the weight ratio of the organic solvent to deionized water of 5:1 for 5min, and performing high-frequency ultrasonic treatment for 20min to obtain a graphene oxide organic solution with the concentration of 1 g/L;
carrying out dipping treatment on the E-TPU granules by using a graphene oxide organic solution for 40s, and then carrying out drying treatment to obtain E-TPU granules coated by graphene oxide;
completely soaking the E-TPU granules coated with graphene oxide in 25g/L reducer solution, and carrying out reduction treatment for 4 hours at 60 ℃ to obtain the E-TPU granules coated with graphene;
and carrying out steam heating forming treatment on the E-TPU granules coated by the graphene to obtain an antistatic E-TPU material, namely an E-TPU composite material C.
Comparative example 1
After 99.9 percent by weight of TPU and 0.1 percent by weight of graphene oxide are physically mixed, twin-screw extrusion is carried out at 170 ℃, and then a supercritical reaction kettle is adopted to prepare a popcorn structure, so that E-TPU composite graphene granules are obtained; and then, further carrying out steam heating forming treatment on the E-TPU composite graphene particles to obtain an E-TPU composite material D.
Comparative example 2
After 99.5 percent by weight of TPU and 0.5 percent by weight of graphene oxide are physically mixed, twin-screw extrusion is carried out at 200 ℃, and then a supercritical reaction kettle is adopted to prepare a popcorn structure, so that E-TPU composite graphene granules are obtained; and then, further carrying out steam heating forming treatment on the E-TPU composite graphene particles to obtain an E-TPU composite material E.
Comparative example 3
After 99%wt of TPU and 1%wt of graphene oxide are physically mixed, twin-screw extrusion is carried out at 200 ℃, and then a supercritical reaction kettle is adopted to prepare a popcorn structure, so that E-TPU composite graphene granules are obtained; and then, further carrying out steam heating forming treatment on the E-TPU composite graphene particles to obtain an E-TPU composite material F.
The volume resistivity of the E-TPU composites A to F described above was measured using a multimeter, respectively, and conductive paste was coated on both sides of the electrode contact to reduce contact resistance, and the volume resistivity measurement results of the E-TPU composites A to F prepared in examples 1 to 3 and comparative examples 1 to 3 above are shown in Table 1.
In comparative examples 1 to 3, graphene oxide was directly dispersed in TPU pellets, resulting in extremely easy aggregation, poor dispersibility, and poor conductivity; in addition, in the preparation process, the addition amount of the graphene oxide is large, but the volume conductivity is still high, the conductivity is poor, so that a great amount of graphene oxide is wasted, meanwhile, in order to obtain relatively good conductivity, the temperature is required to be controlled to be more than 170 ℃, the requirement on production equipment is higher, the production load is also increased, and the industrialized cost reduction and efficiency enhancement are not facilitated.
The preparation method of the antistatic E-TPU material provided by the application has the advantages of simple process, easy operation, low requirements on equipment and production conditions in the production process, and capability of greatly reducing the production cost, and particularly, as shown in the attached drawing 2 of the specification, in the E-TPU composite material B, the wrinkled graphene is embedded into the surface of the E-TPU, so that the volume resistivity can reach 1.09 multiplied by 10 at the lowest 6 Compared with the traditional E-TPU, the antistatic performance of the antistatic E-TPU material provided by the application is greatly improved.
TABLE 1 volume resistivity of antistatic E-TPU materials prepared in different examples
| Sample numbering | Volume resistivity/Ω cm | |
| Example 1 | E-TPU composite A | 6.88×10 8 |
| Example 2 | E-TPU composite B | 1.09×10 6 |
| Example 3 | E-TPU composite C | 7.91×10 6 |
| Comparative example 1 | E-TPU composite material D | 1.42×10 13 |
| Comparative example 2 | E-TPU composite E | 3.99×10 8 |
| Comparative example 3 | E-TPU composite F | 8.50×10 6 |
While the application has been described with respect to certain embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the application, and it is intended to cover the application as defined by the appended claims.
Claims (10)
1. The preparation method of the antistatic E-TPU material is characterized by comprising the following steps:
s1, dispersing graphene oxide in deionized water to obtain graphene oxide dispersion liquid;
s2, dispersing the graphene oxide dispersion liquid in an organic solvent to obtain a graphene oxide organic solution; wherein the weight ratio of the organic solvent to the deionized water is (1-9) 1;
s3, carrying out dipping treatment on the E-TPU granules by using the graphene oxide organic solution, and then carrying out drying treatment to obtain E-TPU granules coated by graphene oxide;
s4, completely soaking the E-TPU granules coated with the graphene oxide in a reducing agent solution for reduction treatment to obtain E-TPU granules coated with the graphene oxide;
and S5, carrying out heating forming treatment on the E-TPU granules coated by the graphene, so that the graphene is filled among the E-TPU granules on the surface layer in a skeleton form, and obtaining the antistatic E-TPU material.
2. The method for preparing an antistatic E-TPU material according to claim 1, wherein said organic solvent is at least one of tetrahydrofuran and N, N-dimethylformamide.
3. The method for preparing an antistatic E-TPU material according to claim 1, wherein the concentration of graphene oxide in the graphene oxide organic solution is 0.1-2 g/L.
4. The method for preparing an antistatic E-TPU material according to claim 1, wherein said step S2 comprises:
dispersing the graphene oxide dispersion liquid in an organic solvent for 5min, and performing high-frequency ultrasound for 10-20 min to obtain the graphene oxide organic solution.
5. The method for preparing an antistatic E-TPU material according to claim 1, wherein the drying process in step S3 is:
and drying the E-TPU granules subjected to the impregnation treatment in a vacuum environment at 60-80 ℃ to obtain the E-TPU granules coated with the graphene oxide.
6. The method for preparing an antistatic E-TPU according to claim 1, wherein the reducing agent in the reducing agent solution is at least one of sodium citrate or sodium ascorbate.
7. The method for preparing an antistatic E-TPU material according to claim 1, wherein the reducing treatment in step S4 is:
and (3) placing the graphene oxide coated E-TPU granules into a reducing agent solution with the concentration of 5-50 g/L, and reducing for 2-8 hours at the reducing temperature of 60-70 ℃ to obtain the graphene coated E-TPU granules.
8. The method for producing an antistatic E-TPU material according to claim 1, wherein said heat forming process is a steam heat forming process or a microwave heat forming process.
9. The method for preparing an antistatic E-TPU material according to claim 8, wherein said steam heat forming process comprises:
and heating the graphene-coated E-TPU granules for 5 to 60 seconds at a heating temperature of 120 to 150 ℃ to obtain the antistatic E-TPU material.
10. An antistatic E-TPU material, characterized in that it is obtained from a method of preparing an antistatic E-TPU material according to any one of claims 1-9, comprising E-TPU particles and graphene filled in a skeletal form between the E-TPU particles.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104039695A (en) * | 2011-09-19 | 2014-09-10 | 卧龙岗大学 | Reduced graphene oxide and method of producing same |
| CN104804204A (en) * | 2015-04-23 | 2015-07-29 | 福州大学 | Graphene/thermoplastic polyurethane composite and preparation method thereof |
| WO2019232124A1 (en) * | 2018-05-31 | 2019-12-05 | Nanotek Instruments, Inc. | Graphene foam-based sealing materials |
| CN110970234A (en) * | 2019-11-20 | 2020-04-07 | 南通纺织丝绸产业技术研究院 | Preparation method of vinylon fabric-based graphene/manganese dioxide electrode material |
| WO2020130499A2 (en) * | 2018-12-21 | 2020-06-25 | 한국과학기술원 | Porous structure-based graphene foam and manufacturing method therefor |
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| CN104039695A (en) * | 2011-09-19 | 2014-09-10 | 卧龙岗大学 | Reduced graphene oxide and method of producing same |
| CN104804204A (en) * | 2015-04-23 | 2015-07-29 | 福州大学 | Graphene/thermoplastic polyurethane composite and preparation method thereof |
| WO2019232124A1 (en) * | 2018-05-31 | 2019-12-05 | Nanotek Instruments, Inc. | Graphene foam-based sealing materials |
| WO2020130499A2 (en) * | 2018-12-21 | 2020-06-25 | 한국과학기술원 | Porous structure-based graphene foam and manufacturing method therefor |
| CN110970234A (en) * | 2019-11-20 | 2020-04-07 | 南通纺织丝绸产业技术研究院 | Preparation method of vinylon fabric-based graphene/manganese dioxide electrode material |
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