EVA/polypyrrole/MXene composite material and preparation method and application thereof
阅读说明：本技术 一种EVA/聚吡咯/MXene复合材料及其制备方法与应用 (EVA/polypyrrole/MXene composite material and preparation method and application thereof ) 是由 金花 于 2021-09-27 设计创作，主要内容包括：本发明公开了一种EVA/聚吡咯/MXene复合材料及其制备方法与应用,将吡咯溶液逐滴加入到MXene分散液中,得到聚吡咯/MXene混合溶液；将EVA与聚吡咯/MXene配合助剂进行混炼加工,制得母料,将所得的母料热压成型,制得EVA/聚吡咯/MXene复合材料。本发明一种EVA/聚吡咯/MXene复合材料及其制备方法与应用解决了现有技术中存在的制备电磁屏蔽材料制备工艺复杂、重量大、环境耐受性差、难以承受一定程度加工变形的问题。(The invention discloses an EVA/polypyrrole/MXene composite material and a preparation method and application thereof, wherein a pyrrole solution is dropwise added into MXene dispersion liquid to obtain a polypyrrole/MXene mixed solution; mixing EVA and polypyrrole/MXene with an auxiliary agent to prepare a master batch, and carrying out hot press molding on the obtained master batch to prepare the EVA/polypyrrole/MXene composite material. The EVA/polypyrrole/MXene composite material and the preparation method and application thereof solve the problems of complex preparation process, heavy weight, poor environmental tolerance and difficulty in bearing certain degree of processing deformation in the prior art for preparing the electromagnetic shielding material.)
1. A preparation method of EVA/polypyrrole/MXene composite material is characterized in that pyrrole solution is dropwise added into MXene dispersion liquid to obtain polypyrrole/MXene mixed solution; mixing EVA and polypyrrole/MXene with an auxiliary agent to prepare a master batch, and carrying out hot press molding on the obtained master batch to prepare the EVA/polypyrrole/MXene composite material.
2. The preparation method of the EVA/polypyrrole/MXene composite material according to claim 1, characterized by comprising the following steps:
1) dispersing MXene in deionized water, and performing ultrasonic treatment for 1h to obtain MXene dispersion liquid;
2) dissolving pyrrole monomer in 2mL of isopropanol solution, then dropwise adding the solution into 6mL of methyl naphthalene dispersion liquid, stirring and reacting at room temperature for 12-24 h to obtain a polypyrrole/MXene mixed solution, and freeze-drying to obtain polypyrrole/MXene powder;
3) drying the EVA microspheres in an oven at 45 ℃ for 3h, and then uniformly mixing the EVA microspheres, polypyrrole/MXene powder and a crosslinking agent to obtain a powder mixture; mixing the obtained powder to prepare a master batch;
4) and carrying out hot-press molding on the obtained master batch, cooling and demolding to obtain the EVA/polypyrrole/MXene composite material.
3. The method for preparing EVA/polypyrrole/MXene composite material according to claim 2, wherein in step 1), MXene nanosheet is Ti3C2Tx。
4. The method for preparing the EVA/polypyrrole/MXene composite material according to claim 2, wherein in the step 2), the mass ratio of the mole fraction of pyrrole to MXene is 1 (0.5-2.5).
5. The method for preparing the EVA/polypyrrole/MXene composite material of claim 2, wherein in the step 3), the weight ratio of the EVA microspheres to the polypyrrole/MXene powder to the crosslinking agent is 100 (1-10) to (0.1-2).
6. The method for preparing EVA/polypyrrole/MXene composite according to claim 2, wherein in step 3), the crosslinking agent is triallyl isocyanurate or dicumyl peroxide.
7. The method for preparing the EVA/polypyrrole/MXene composite material according to claim 2, wherein in step 3), the mixing process is performed in a torque rheometer, and the process parameters of the mixing process are as follows: the temperature is 50-100 ℃, the rotating speed is 10-50 rpm, and the time is 2-8 min;
in the step 3), the hot-press molding is carried out in a hot press, and the technological parameters of the hot-press molding are as follows: the temperature is 160-200 ℃, the pressure is 10-30 MPa, and the time is 8-20 min.
8. The EVA/polypyrrole/MXene composite material prepared by the preparation method of any one of claims 1 to 7.
9. The EVA/polypyrrole/MXene composite according to claim 8, wherein the electromagnetic shielding performance is 40dB when the composite is 2mm thick.
10. Use of the EVA/polypyrrole/MXene composite material of claim 8 or 9 for preparing electromagnetic shielding composite material.
Technical Field
The invention belongs to the field of conductive composite materials, and relates to an EVA/polypyrrole/MXene composite material, and a preparation method and application thereof.
Background
As water pollution, solid waste pollution, and air pollution become more and more appreciated by humans, some potential other pollution is beginning to be of public concern, such as electromagnetic radiation pollution. Electromagnetic radiation not only can interfere with various electronic devices, but also can cause adverse effects on human health when a human body is in an environment with certain electromagnetic radiation intensity. Therefore, most countries have legal provisions that electronic and electrical hardware cannot emit electromagnetic waves to affect other devices or human bodies. The traditional electromagnetic interference shielding material is composed of metal and composite materials, and the materials have high conductivity and dielectric constant and good shielding effect. Although metals have excellent electromagnetic interference shielding properties, they also have the disadvantages of heavy weight, susceptibility to corrosion, poor processing, and the like.
To meet the requirements of lightweight emi shielding systems, polymer-based conductive composites are more attractive. Polypyrrole is a common conductive polymer, contains conjugated double bonds, and is widely concerned by people due to the characteristics of environmental friendliness, easiness in large-scale synthesis, low cost and the like. However, pure polypyrrole is difficult to be dissolved and melted and has poor ductility, so that it is difficult to be processed and molded, and thus it is difficult to be used alone as an electromagnetic shielding material. In order to improve the processability of polypyrrole, the preparation of composite polypyrrole materials is an effective and feasible method.
Disclosure of Invention
In order to achieve the purpose, the invention provides an EVA/polypyrrole/MXene composite material and a preparation method and application thereof, and solves the problems that the preparation process for preparing the electromagnetic shielding material is complex, heavy, poor in environmental tolerance and difficult to bear certain degree of processing deformation in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose: an EVA/polypyrrole/MXene composite material and a preparation method thereof are disclosed, wherein pyrrole solution is dropwise added into MXene dispersion liquid to obtain polypyrrole/MXene mixed solution; mixing EVA and polypyrrole/MXene with an auxiliary agent to prepare a master batch, and carrying out hot press molding on the obtained master batch to prepare the EVA/polypyrrole/MXene composite material.
Preferably, the preparation method specifically comprises the following steps:
1) dispersing MXene in deionized water, and performing ultrasonic treatment for 1h to obtain MXene dispersion liquid;
2) dissolving pyrrole monomer in 2mL of isopropanol solution, then dropwise adding the solution into 6mL of methyl naphthalene dispersion liquid, stirring and reacting at room temperature for 12-24 h to obtain a polypyrrole/MXene mixed solution, and freeze-drying to obtain polypyrrole/MXene powder;
3) drying the EVA microspheres in an oven at 45 ℃ for 3h, and then uniformly mixing the EVA microspheres, polypyrrole/MXene powder and a crosslinking agent to obtain a powder mixture; mixing the obtained powder to prepare a master batch;
4) and carrying out hot-press molding on the obtained master batch, cooling and demolding to obtain the EVA/polypyrrole/MXene composite material.
Preferably, in the step 1), MXene nanosheets are Ti3C2Tx。
Preferably, in the step 2), the mass ratio of the mole fraction of pyrrole to MXene is 1 (0.5-2.5).
Preferably, in the step 3), the weight ratio of the EVA microspheres to the polypyrrole/MXene powder to the crosslinking agent is 100 (1-10) to 0.1-2.
Preferably, in step 3), the crosslinking agent is triallyl isocyanurate or dicumyl peroxide.
Preferably, in step 3), the mixing process is performed in a torque rheometer, and the process parameters of the mixing process are as follows: the temperature is 50-100 ℃, the rotating speed is 10-50 rpm, and the time is 2-8 min;
preferably, in step 3), the hot press molding is performed in a hot press, and the process parameters of the hot press molding are as follows: the temperature is 160-200 ℃, the pressure is 10-30 MPa, and the time is 8-20 min.
The invention also discloses the EVA/polypyrrole/MXene composite material prepared by the preparation method.
Preferably, when the thickness of the EVA/polypyrrole/MXene composite material is 2mm, the electromagnetic shielding performance can reach 40 dB.
The invention also discloses application of the EVA/polypyrrole/MXene composite material in preparation of an electromagnetic shielding composite material.
The invention has the beneficial effects that:
(1) the invention discloses an EVA/polypyrrole/MXene composite material and a preparation method and application thereof, wherein MXene nanosheets are modified by adopting an in-situ polymerization polypyrrole method, so that the problems that pure polypyrrole is easy to agglomerate in the polymerization process and the MXene nanosheets are stacked and aggregated are solved, the obtained polypyrrole/MXene is used as a conductive filler, and the conductive filler is introduced into EVA by blending, so that the problems that the preparation process for preparing an electromagnetic shielding material in the prior art is complex, the weight is large, the environmental tolerance is poor, and the processing deformation to a certain degree is difficult to bear are solved.
(2) The invention also discloses the EVA/polypyrrole/MXene composite material prepared by the preparation method, the method for modifying the MXene nanosheets by adopting the in-situ polymerization polypyrrole method is different from the traditional method for initiating polymerization of polypyrrole by adding an initiator, the method is completed by adding polypyrrole monomers into the MXene dispersion liquid under the condition of stirring at room temperature for 12-24 hours, pyrrole molecules are protonated by utilizing the characteristic that the MXene nanosheets have acidity, so that a chain growth reaction is induced, and the polypyrrole long chain is finally formed. The conductive polypyrrole formed by polymerization is distributed in a place where the MXene nanosheets are easy to oxidize, so that the conductive polypyrrole can play a role in passivation protection, and the structural stability of the MXene nanosheets is effectively improved.
(3) The invention also discloses application of the EVA/polypyrrole/MXene composite material in preparation of an electromagnetic shielding composite material. The introduction of polypyrrole can not only protect MXene nanosheets, but also enhance the interaction force between the MXene nanosheets and the substrate; meanwhile, more reflecting interfaces and loss functional groups can be provided for electromagnetic waves, and the electromagnetic shielding performance is improved. When the thickness of the EVA/polypyrrole/MXene composite material is 2mm, the electromagnetic shielding performance can reach 40 dB.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An EVA/polypyrrole/MXene composite material and a preparation method thereof comprise the following steps:
(1) dispersing MXene in deionized water, and performing ultrasonic treatment for 1h to obtain MXene dispersion liquid;
(2) dissolving pyrrole monomer in 2mL of isopropanol solution, then dropwise adding the solution into 6mL of methyl naphthalene dispersion liquid, stirring and reacting at room temperature for 12-24 h to obtain a polypyrrole/MXene mixed solution, and freeze-drying to obtain polypyrrole/MXene powder;
(3) drying the EVA microspheres in an oven at 45 ℃ for 3h, and then uniformly mixing the EVA microspheres, polypyrrole/MXene powder and a crosslinking agent to obtain a powder mixture; mixing the obtained powder in a torque rheometer to obtain a master batch; the technological parameters of the raw materials in the torque rheometer for mixing processing are as follows: the temperature is 50-100 ℃, the rotating speed is 10-50 rpm, and the time is 2-8 min.
(4) And hot-pressing the obtained master batch in a hot press for molding, and cooling and demolding to obtain the EVA/polypyrrole/MXene composite material. The technological parameters of hot-press molding are as follows: the temperature is 160-200 ℃, the pressure is 10-30 MPa, and the time is 8-20 min.
Wherein the MXene nano-sheet is Ti3C2Tx。
Wherein the mass ratio of the mole fraction of the pyrrole to MXene is 1 (0.5-2.5).
Wherein the weight ratio of the EVA microspheres to the polypyrrole/MXene powder to the cross-linking agent is 100 (1-10) to 0.1-2.
Wherein the crosslinking agent is triallyl isocyanurate or dicumyl peroxide.
The invention will be further illustrated with reference to specific examples:
example 1:
(1) mixing Ti3C2Tx is dispersed in deionized water, and ultrasonic treatment is carried out for 1h to obtain MXene dispersion liquid;
(2) dissolving 0.005moL of pyrrole monomer in 2mL of isopropanol solution, then dropwise adding the solution into 6mL of 0.005mg/mL of MXene dispersion liquid, stirring and reacting at room temperature for 12h to obtain a polypyrrole/MXene mixed solution, and freeze-drying to obtain polypyrrole/MXene powder;
(3) drying the EVA microspheres in an oven at 45 ℃ for 3 hours, and then uniformly mixing 100 parts of EVA microspheres, 5 parts of polypyrrole/MXene powder and 0.4 part of triallyl isocyanurate to obtain a powder mixture; mixing the obtained powder in a torque rheometer to obtain a master batch; the technological parameters of the raw materials in the torque rheometer for mixing processing are as follows: the temperature was 60 ℃, the rotation speed was 10rpm, and the time was 3 min.
(4) And hot-pressing the obtained master batch in a hot press for molding, and cooling and demolding to obtain the EVA/polypyrrole/MXene composite material. The technological parameters of hot-press molding are as follows: the temperature is 160 ℃, the pressure is 10MPa, and the time is 8 min.
Example 2:
(1) mixing Ti3C2Tx is dispersed in deionized water, and ultrasonic treatment is carried out for 1h to obtain MXene dispersion liquid;
(2) dissolving 0.009moL of pyrrole monomer in 2mL of isopropanol solution, then dropwise adding the solution into 6mL of MXene dispersion liquid with the concentration of 0.0108mg/mL, stirring and reacting for 15 hours at room temperature to obtain a polypyrrole/MXene mixed solution, and freeze-drying to obtain polypyrrole/MXene powder;
(3) drying the EVA microspheres in an oven at 45 ℃ for 3 hours, and then uniformly mixing 100 parts of EVA microspheres, 4 parts of polypyrrole/MXene powder and 0.5 part of dicumyl peroxide to obtain a powder mixture; mixing the obtained powder in a torque rheometer to obtain a master batch; the technological parameters of the raw materials in the torque rheometer for mixing processing are as follows: the temperature was 50 ℃, the rotation speed was 15rpm, and the time was 2 min.
(4) And hot-pressing the obtained master batch in a hot press for molding, and cooling and demolding to obtain the EVA/polypyrrole/MXene composite material. The technological parameters of hot-press molding are as follows: the temperature is 170 ℃, the pressure is 20MPa, and the time is 9 min.
Example 3:
(1) mixing Ti3C2Tx is dispersed in deionized water, and ultrasonic treatment is carried out for 1h to obtain MXene dispersion liquid;
(2) dissolving 0.012moL of pyrrole monomer in 2mL of isopropanol solution, then dropwise adding the solution into 6mL of MXene dispersion liquid with the concentration of 0.018mg/mL, stirring and reacting for 16h at room temperature to obtain a polypyrrole/MXene mixed solution, and freeze-drying to obtain polypyrrole/MXene powder;
(3) drying the EVA microspheres in an oven at 45 ℃ for 3 hours, and then uniformly mixing 100 parts of EVA microspheres, 6 parts of polypyrrole/MXene powder and 1.7 parts of dicumyl peroxide to obtain a powder mixture; mixing the obtained powder in a torque rheometer to obtain a master batch; the technological parameters of the raw materials in the torque rheometer for mixing processing are as follows: the temperature was 70 ℃, the rotation speed was 30rpm, and the time was 4 min.
(4) And hot-pressing the obtained master batch in a hot press for molding, and cooling and demolding to obtain the EVA/polypyrrole/MXene composite material. The technological parameters of hot-press molding are as follows: the temperature is 180 ℃, the pressure is 15MPa, and the time is 10 min.
Example 4:
(1) mixing Ti3C2Tx is dispersed in deionized water, and ultrasonic treatment is carried out for 1h to obtain MXene dispersion liquid;
(2) dissolving 0.015moL of pyrrole monomer in 2mL of isopropanol solution, then dropwise adding the solution into 6mL of MXene dispersion liquid with the concentration of 0.0216mg/mL, stirring and reacting for 18h at room temperature to obtain a polypyrrole/MXene mixed solution, and freeze-drying to obtain polypyrrole/MXene powder;
(3) drying the EVA microspheres in an oven at 45 ℃ for 3 hours, and then uniformly mixing 100 parts of EVA microspheres, 8 parts of polypyrrole/MXene powder and 1.3 parts of triallyl isocyanurate to obtain a powder mixture; mixing the obtained powder in a torque rheometer to obtain a master batch; the technological parameters of the raw materials in the torque rheometer for mixing processing are as follows: the temperature was 80 ℃, the rotation speed was 25rpm, and the time was 5 min.
(4) And hot-pressing the obtained master batch in a hot press for molding, and cooling and demolding to obtain the EVA/polypyrrole/MXene composite material. The technological parameters of hot-press molding are as follows: the temperature is 175 deg.C, the pressure is 20MPa, and the time is 15 min.
Example 5:
(1) mixing Ti3C2Tx is dispersed in deionized water, and ultrasonic treatment is carried out for 1h to obtain MXene dispersion liquid;
(2) dissolving 0.007moL of pyrrole monomer in 2mL of isopropanol solution, then dropwise adding the solution into 6mL of 0.014mg/mL of MXene dispersion liquid, stirring and reacting for 20 hours at room temperature to obtain a polypyrrole/MXene mixed solution, and freeze-drying to obtain polypyrrole/MXene powder;
(3) drying the EVA microspheres in an oven at 45 ℃ for 3 hours, and then uniformly mixing 100 parts of EVA microspheres, 9 parts of polypyrrole/MXene powder and 1 part of dicumyl peroxide to obtain a powder mixture; mixing the obtained powder in a torque rheometer to obtain a master batch; the technological parameters of the raw materials in the torque rheometer for mixing processing are as follows: the temperature was 85 ℃, the rotation speed was 35rpm, and the time was 7 min.
(4) And hot-pressing the obtained master batch in a hot press for molding, and cooling and demolding to obtain the EVA/polypyrrole/MXene composite material. The technological parameters of hot-press molding are as follows: the temperature is 155 ℃, the pressure is 20MPa, and the time is 12 min.
Example 6:
(1) mixing Ti3C2Tx is dispersed in deionized water, and ultrasonic treatment is carried out for 1h to obtain MXene dispersion liquid;
(2) dissolving 0.003moL of pyrrole monomer in 2mL of isopropanol solution, then dropwise adding the solution into 6mL of MXene dispersion liquid with the concentration of 0.0075mg/mL, stirring and reacting for 24 hours at room temperature to obtain a polypyrrole/MXene mixed solution, and freeze-drying to obtain polypyrrole/MXene powder;
(3) drying the EVA microspheres in an oven at 45 ℃ for 3 hours, and then uniformly mixing 100 parts of EVA microspheres, 10 parts of polypyrrole/MXene powder and 2 parts of triallyl isocyanurate to obtain a powder mixture; mixing the obtained powder in a torque rheometer to obtain a master batch; the technological parameters of the raw materials in the torque rheometer for mixing processing are as follows: the temperature was 100 ℃, the rotation speed was 50rpm, and the time was 8 min.
(4) And hot-pressing the obtained master batch in a hot press for molding, and cooling and demolding to obtain the EVA/polypyrrole/MXene composite material. The technological parameters of hot-press molding are as follows: the temperature is 200 deg.C, the pressure is 30MPa, and the time is 20 min.
It is noted that, in the present application, relational terms such as first, second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.