CN114231017A - Preparation method of modified graphene/polyurethane composite material with high conductivity and high tensile-resistance sensitivity - Google Patents
Preparation method of modified graphene/polyurethane composite material with high conductivity and high tensile-resistance sensitivity Download PDFInfo
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- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims abstract description 18
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Abstract
The invention discloses a preparation method of a modified graphene/polyurethane composite material with high conductivity and high tensile-resistance sensitivity. According to the invention, Octadecylamine (ODA) is used as a modifier to perform functional modification on the surface of graphene oxide to obtain functionalized graphene (GO-ODA) with good conductivity, and then the functionalized graphene and thermoplastic polyurethane are subjected to polymerization reaction to prepare the modified graphene/polyurethane composite material with good conductivity and high tensile-resistance sensitivity. The composite material effectively improves the conductivity and the tensile-resistance sensitivity of the polyurethane composite material, the conductivity can be improved by 7 orders of magnitude, the pull-up performance can be improved by 2 orders of magnitude, and the composite material has a good application prospect in the aspects of pull-electric sensors and intelligent structural materials.
Description
Technical Field
The invention relates to the technical field of polyurethane composite materials, in particular to a preparation method of a modified graphene/polyurethane composite material with high conductivity and high tensile-resistance sensitivity.
Background
With the development of society and the improvement of technology level, people begin to pay more and more attention to the functionalization of traditional materials. For example, part of the antibacterial agent is added into the plastic master batch to meet the requirements of the plastic on antibiosis and mould removal; piezoelectric or photoelectric additives are added into the high polymer material, so that the intelligent requirement of the composite material can be met. Graphene (Graphene) has a unique two-dimensional structure, is a known material with the highest conductivity, and can be widely used as a conductive component for polymer-based conductive composite materials. Thermoplastic Polyurethane (TPU) is a Thermoplastic elastomer with stronger polarity, the change of the performance of the TPU can be realized through the structure and composition design of the TPU, the TPU has good affinity with carbon materials, a composite material with a three-dimensional network structure and better mechanical properties can be prepared, and the research and the application of polyurethane-based conductive composite materials are increasingly concerned by people.
The graphene has poor compatibility with polar polymers such as TPU and the like, so the graphene is easy to agglomerate during compounding. Because Graphene Oxide (GO) is a precursor of graphene, the surface property of the graphene oxide determines that the graphene oxide is better compatible with TPU, but the graphene oxide is poor in conductivity, so that the preparation and application of the TPU-based graphene conductive composite material face great difficulty. At the present stage, researchers make a lot of researches on how to control compatibility of GO and TPU and improve conductivity of the graphene/TPU composite material. According to reports of the rubber industry (2011, 60 and 453), GO can be well compatible with TPU by solution blending and pouring, and the physical properties of the composite material can be greatly improved by the interface combination between TPU and GO. The Chinese invention patent CN201310262841.5 discloses an in-situ preparation method of a graphene and polyurethane composite material, which can be used for preparing plastic products. In view of these reports, the performance achieved mainly in terms of the physical properties of the composite material, including heat and pressure resistance, strength modulus, etc., but it has always been a problem in terms of improving the electrical conductivity of the composite material. Therefore, a novel method for preparing the modified graphene/polyurethane composite material with good conductivity is imperative, and the breakthrough of the method is imperative to obtain considerable economic benefits and bring certain social benefits.
Octadecylamine (ODA), also known as stearylamine, appears as a waxy solid crystal and is a raw material from which surfactants can be prepared. According to the invention, ODA is used as a modifier to functionally modify graphene oxide to prepare functionalized graphene (GO-ODA) with good conductivity, and finally the functionalized graphene (GO-ODA) and polyurethane are subjected to polymerization reaction to obtain a modified graphene/polyurethane composite material with good conductivity and high tensile-resistance sensitivity.
Disclosure of Invention
In order to functionalize a thermoplastic polyurethane material and overcome the defects that a graphene/polyurethane composite material is low in conductivity and difficult to stretch and other morphological changes in a power-on state, the invention aims to provide a preparation method of a modified graphene/polyurethane composite material with high conductivity and high stretch-resistance sensitivity.
The purpose of the invention is realized by the following scheme: a preparation method of a modified graphene/polyurethane composite material with high conductivity and high stretch-resistance sensitivity is characterized in that octadecylamine ODA is used as a modifier to perform functional modification on the surface of graphene oxide to obtain functionalized graphene GO-ODA with good conductivity, and then the functionalized graphene GO-ODA and thermoplastic polyurethane are subjected to polymerization reaction to prepare the modified graphene/polyurethane composite material with good conductivity and high stretch-resistance sensitivity, and the preparation method comprises the following steps:
a. preparing graphene oxide GO: preparing graphene oxide by using commercially available graphite powder as a raw material and adopting a modified Hummers method, namely quantitative NaNO3Adding the graphite powder and the potassium permanganate solution into concentrated sulfuric acid, adding a certain amount of graphite powder and the potassium permanganate solution in proportion after the graphite powder and the potassium permanganate solution are completely dissolved, further reacting to obtain a bright yellow system solution with a certain concentration, and filtering and drying to obtain graphene oxide GO;
b. preparing functionalized graphene GO-ODA: weighing a certain amount of graphene oxide GO prepared in the step a, dissolving the graphene oxide GO into an N, N-dimethyl formamide DMF solvent after freeze drying, and adding SOCl2Then heated in a water bath at 70 deg.C, condensed and refluxed for 5 hours, and then distilled under reduced pressure at 60 deg.C to remove excess SOCl2Then, n-butanol is used for filtering and washing, ODA is added, and the adding mass ratio of GO to ODA is 1: 5-10, using n-butyl alcohol as a solvent, and carrying out condensation refluxPerforming suction filtration and washing on the reaction product by using n-butyl alcohol, and performing vacuum drying at 60 ℃ to obtain GO-ODA for later use after 48 hours;
c. preparing a modified polyurethane composite material: weighing a certain mass of GO-ODA prepared in the step b, dispersing the GO-ODA into DMF (dimethyl formamide), carrying out ultrasonic treatment for 3 hours, and then adding TPU (thermoplastic polyurethane) into the dispersion liquid, wherein the input mass ratio of GO-ODA to TPU is 0.01-0.05: 1, magnetically stirring for 2 hours at normal temperature, and finally drying the mixed solution to obtain a modified GO-ODA/TPU composite material;
d. forming the thermal reduction composite material: and carrying out hot press molding on the prepared composite material at a certain temperature by using a vacuum film pressing machine, and pressing the composite material into a composite film with a certain thickness, thereby finally obtaining the modified graphene/polyurethane composite film with better conductivity.
According to the invention, graphene oxide is modified by octadecylamine to obtain functionalized graphene (GO-ODA), and the functionalized graphene is used as an additive to be added into a thermoplastic polyurethane high polymer material to obtain a modified graphene/polyurethane composite material with high conductivity and high tensile-resistance sensitivity. The material has good application prospect in the aspects of pull-electric sensors, intelligent electronic materials and the like.
In the process of preparing the graphene oxide by the modified Hummers method, the concentration of a graphene oxide solution is controlled to be 2-3 mg/ml.
The vacuum film pressing hot press molding condition is controlled as follows: the hot pressing temperature is 180-250 DEG CoAnd C, hot pressing pressure is 4-10 MPa, and hot pressing time is 30-60 min.
The thickness of the vacuum lamination is controlled to be less than 1.0 mm.
According to the invention, the ODA is adopted as a surface modifier to functionally modify the graphene oxide, so that the functionalized graphene GO-ODA with good conductivity is prepared, and finally the functionalized graphene GO-ODA is added into polyurethane to carry out polymerization reaction, so that the modified graphene/polyurethane composite material with good conductivity and high tensile-resistance sensitivity is obtained.
The composite material effectively improves the conductivity and the tensile-resistance sensitivity of the polyurethane composite material, the conductivity can be improved by 7 orders of magnitude, the pull-up performance can be improved by 2 orders of magnitude, and the composite material has a good application prospect in the aspects of pull-electric sensors and intelligent structural materials.
Drawings
FIG. 1 is a scanning electron microscope spectrogram of GO-ODA/TPU composite materials with different GO-ODA contents, wherein a picture a and b picture are microscopic morphology pictures when the GO-ODA addition amount is 1 wt% and 2 wt%, respectively.
Detailed Description
The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
Example 1
A modified graphene/polyurethane composite material with high conductivity and high stretch-resistance sensitivity is prepared by performing functional modification on the surface of graphene oxide by taking octadecylamine ODA as a modifier to obtain functionalized graphene GO-ODA with good conductivity, and then performing polymerization reaction on the functionalized graphene GO-ODA and thermoplastic polyurethane to prepare the modified graphene/polyurethane composite material with good conductivity and high stretch-resistance sensitivity, wherein the modified graphene/polyurethane composite material is prepared by the following steps:
a. preparing graphene oxide GO: preparing graphene oxide by using commercially available graphite powder as a raw material and adopting a modified Hummers method, namely quantitative NaNO3Adding the graphite powder and the potassium permanganate solution into concentrated sulfuric acid, adding a certain amount of graphite powder and the potassium permanganate solution in proportion after the graphite powder and the potassium permanganate solution are completely dissolved, further reacting to obtain a bright yellow system solution with the concentration of 2.0 mg/ml, and filtering and drying to obtain graphene oxide GO;
b. preparing functionalized graphene GO-ODA: b, dissolving 1.0 g of graphene oxide GO prepared in the step a into 500 ml of N, N-dimethyl formamide DMF solvent after freeze drying, and adding 5 ml of SOCl2Then heated in a water bath at 70 deg.C, condensed and refluxed for 5 hours, and then distilled under reduced pressure at 60 deg.C to remove excess SOCl2Then filtering and washing with n-butyl alcohol, adding 10 g of ODA, using the n-butyl alcohol as a solvent, condensing and refluxing for 48 hours, finally carrying out suction filtration and washing on a reaction product with the n-butyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain GO-ODA for later use;
c. preparing a modified polyurethane composite material: weighing 5 g of GO-ODA prepared in the step b, dispersing the GO-ODA into DMF (dimethyl formamide), carrying out ultrasonic treatment for 3 hours, then adding 500 g of TPU (thermoplastic polyurethane) into the dispersion liquid, carrying out magnetic stirring for 2 hours at normal temperature, and finally drying the mixed liquid to obtain a modified GO-ODA/TPU composite material, wherein a microscopic view is shown in figure 1;
d. forming the thermal reduction composite material: c, hot-pressing the composite material prepared in the step c at 200 ℃ by using a vacuum film pressing machine, wherein the hot-pressing pressure is 4-10 MPa, and the hot-pressing time is 60 min; finally, the modified graphene/polyurethane composite membrane with the thickness of 0.6 mm and good conductivity is obtained.
Example 2
A modified graphene/polyurethane composite material with high conductivity and high tensile-resistance sensitivity is prepared by the following steps, which are the same as the steps a, b and d in the example 1:
a. preparing graphene oxide GO: preparing graphene oxide by using commercially available graphite powder as a raw material and adopting a modified Hummers method, namely quantitative NaNO3Adding the graphite powder and the potassium permanganate solution into concentrated sulfuric acid, adding a certain amount of graphite powder and the potassium permanganate solution in proportion after the graphite powder and the potassium permanganate solution are completely dissolved, further reacting to obtain a bright yellow system solution with the concentration of 2.0 mg/ml, and filtering and drying to obtain graphene oxide GO;
b. preparing functionalized graphene GO-ODA: b, dissolving 1.0 g of graphene oxide GO prepared in the step a into 500 ml of N, N-dimethyl formamide DMF solvent after freeze drying, and adding 5 ml of SOCl2Then heated in a water bath at 70 deg.C, condensed and refluxed for 5 hours, and then distilled under reduced pressure at 60 deg.C to remove excess SOCl2Then filtering and washing with n-butyl alcohol, adding 10 g of ODA, using the n-butyl alcohol as a solvent, condensing and refluxing for 48 hours, finally carrying out suction filtration and washing on a reaction product with the n-butyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain GO-ODA for later use;
c. preparing a modified polyurethane composite material: weighing 2.5 g of GO-ODA prepared in the step b, dispersing the GO-ODA into DMF (dimethyl formamide), carrying out ultrasonic treatment for 3 hours, then adding 500 g of TPU (thermoplastic polyurethane) into the dispersion liquid, carrying out magnetic stirring for 2 hours at normal temperature, and finally drying the mixed liquid to obtain a modified GO-ODA/TPU composite material, wherein a microscopic view is shown in figure 1;
d. forming the thermal reduction composite material: c, hot-pressing the composite material prepared in the step c at 200 ℃ by using a vacuum film pressing machine, wherein the hot-pressing pressure is 4-10 MPa, and the hot-pressing time is 60 min; finally, the modified graphene/polyurethane composite membrane with the thickness of 0.6 mm and good conductivity is obtained.
Example 3
A modified graphene/polyurethane composite material with high conductivity and high tensile-resistance sensitivity is prepared by the following steps, which are the same as the steps a and d in the example 1:
a. preparing graphene oxide GO: preparing graphene oxide by using commercially available graphite powder as a raw material and adopting a modified Hummers method, namely quantitative NaNO3Adding the graphite powder and the potassium permanganate solution into concentrated sulfuric acid, adding a certain amount of graphite powder and the potassium permanganate solution in proportion after the graphite powder and the potassium permanganate solution are completely dissolved, further reacting to obtain a bright yellow system solution with the concentration of 2.0 mg/ml, and filtering and drying to obtain graphene oxide GO;
b. preparing functionalized graphene GO-ODA: b, dissolving 2.0 g of graphene oxide GO prepared in the step a into 500 ml of N, N-dimethyl formamide DMF solvent after freeze drying, and adding 5 ml of SOCl2Then heated in a water bath at 70 deg.C, condensed and refluxed for 5 hours, and then distilled under reduced pressure at 60 deg.C to remove excess SOCl2Then filtering and washing with n-butyl alcohol, adding 10 g of ODA, using the n-butyl alcohol as a solvent, condensing and refluxing for 48 hours, finally carrying out suction filtration and washing on a reaction product with the n-butyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain GO-ODA for later use;
c. preparing a modified polyurethane composite material: weighing 5 g of GO-ODA prepared in the step b, dispersing the GO-ODA into DMF (dimethyl formamide), carrying out ultrasonic treatment for 3 hours, then adding 250 g of TPU (thermoplastic polyurethane) into the dispersion liquid, carrying out magnetic stirring for 2 hours at normal temperature, and finally drying the mixed liquid to obtain a modified GO-ODA/TPU composite material, wherein a microscopic view is shown in figure 1;
d. forming the thermal reduction composite material: c, hot-pressing the composite material prepared in the step c at 200 ℃ by using a vacuum film pressing machine, wherein the hot-pressing pressure is 4-10 MPa, and the hot-pressing time is 60 min; finally, the modified graphene/polyurethane composite membrane with the thickness of 0.6 mm and good conductivity is obtained.
Comparative example
A graphene/polyurethane composite material is prepared by the following steps:
a. preparing graphene oxide GO: preparing graphene oxide by using commercially available graphite powder as a raw material and adopting a modified Hummers method, namely quantitative NaNO3Adding the graphite powder and the potassium permanganate solution into concentrated sulfuric acid, adding a certain amount of graphite powder and the potassium permanganate solution in proportion after the graphite powder and the potassium permanganate solution are completely dissolved, further reacting to obtain a bright yellow system solution with the concentration of 2.0 mg/ml, and filtering and drying to obtain graphene oxide GO;
b. preparing a polyurethane composite material: weighing 5 g of prepared GO, dispersing the GO into DMF, carrying out ultrasonic treatment for 3 hours, then adding 250 g of TPU into the dispersion liquid, carrying out magnetic stirring for 2 hours at normal temperature, and finally drying the mixed liquid to obtain a GO/TPU composite material;
c. forming the thermal reduction composite material: hot-pressing the prepared GO/TPU composite material at 200 ℃ by using a vacuum film pressing machine, wherein the hot-pressing pressure is 4-10 MPa, and the hot-pressing time is 60 min; finally obtaining the graphene/polyurethane composite membrane with the thickness of 0.6 mm.
FIG. 1 is a scanning electron microscope spectrogram of GO-ODA/TPU composite materials with different GO-ODA contents, wherein a picture and b picture are microscopic morphology pictures when the addition amount of GO-ODA is 1 wt% and 2 wt%, respectively, and it can be seen from the pictures that when the addition amount of GO-ODA reaches 2.0 wt%, the GO-ODA/TPU composite film tends to be flatter, which shows that the addition of modified graphene makes the conductive network structure more stable.
TABLE 1 comparison of the conductivity properties of GO-ODA/TPU composites with different GO-ODA contents
With the addition of the modified graphene material, the electrical conductivity of the GO-ODA/TPU composite material is remarkably improved. As can be seen from Table 1, when the mass fraction of GO-ODA reaches 2.0%, the electrical conductivity of the GO-ODA/TPU composite film reaches 4.4X 10-5S/cm, compared with the conductivity of pure TPU, the conductivity is improved by 7 orders of magnitude.
Claims (7)
1. A preparation method of a modified graphene/polyurethane composite material with high conductivity and high stretch-resistance sensitivity is characterized in that octadecylamine ODA is used as a modifier to perform functional modification on the surface of graphene oxide to obtain functionalized graphene GO-ODA with good conductivity, and then the functionalized graphene GO-ODA and thermoplastic polyurethane are subjected to polymerization reaction to prepare the modified graphene/polyurethane composite material with good conductivity and high stretch-resistance sensitivity, and the preparation method comprises the following steps:
a. preparing graphene oxide GO: preparing graphene oxide by using commercially available graphite powder as a raw material and adopting a modified Hummers method, namely quantitative NaNO3Adding the graphite powder and the potassium permanganate solution into concentrated sulfuric acid, adding a certain amount of graphite powder and the potassium permanganate solution in proportion after the graphite powder and the potassium permanganate solution are completely dissolved, further reacting to obtain a bright yellow system solution with a certain concentration, and filtering and drying to obtain graphene oxide GO;
b. preparing functionalized graphene GO-ODA: weighing a certain amount of graphene oxide GO prepared in the step a, dissolving the graphene oxide GO into an N, N-dimethyl formamide DMF solvent after freeze drying, and adding SOCl2Then heated in a water bath at 70 deg.C, condensed and refluxed for 5 hours, and then distilled under reduced pressure at 60 deg.C to remove excess SOCl2Then, n-butanol is used for filtering and washing, ODA is added, and the adding mass ratio of GO to ODA is 1: 5-10, using n-butyl alcohol as a solvent, condensing and refluxing for 48 hours, finally performing suction filtration and washing on a reaction product by using n-butyl alcohol, and performing vacuum drying at 60 ℃ to obtain GO-ODA for later use;
c. preparing a modified polyurethane composite material: weighing a certain mass of GO-ODA prepared in the step b, dispersing the GO-ODA into DMF (dimethyl formamide), carrying out ultrasonic treatment for 3 hours, and then adding TPU (thermoplastic polyurethane) into the dispersion liquid, wherein the input mass ratio of GO-ODA to TPU is 0.01-0.05: 1, magnetically stirring for 2 hours at normal temperature, and finally drying the mixed solution to obtain a modified GO-ODA/TPU composite material;
d. forming the thermal reduction composite material: and carrying out hot press molding on the prepared composite material at a certain temperature by using a vacuum film pressing machine, and pressing the composite material into a composite film with a certain thickness, thereby finally obtaining the modified graphene/polyurethane composite film with better conductivity.
2. The method for preparing the modified graphene/polyurethane composite material with high conductivity and high tensile-resistance sensitivity according to claim 1, wherein in the modified Hummers method for preparing graphene oxide, the concentration of a graphene oxide solution is controlled to be 2-3 mg/ml.
3. The method for preparing the modified graphene/polyurethane composite material with high conductivity and high stretch-resistance sensitivity as claimed in claim 1, wherein the conditions of the vacuum lamination hot press molding are controlled as follows: the hot pressing temperature is 180-250 ℃, the hot pressing pressure is 4-10 MPa, and the hot pressing time is 30-60 min.
4. The method for preparing a modified graphene/polyurethane composite material with high conductivity and high stretch-resistance sensitivity according to claim 1, wherein the thickness of the vacuum pressed film is controlled to be less than 1.0 mm.
5. The method for preparing the modified graphene/polyurethane composite material with high conductivity and high tensile-resistance sensitivity according to any one of claims 1 to 4, wherein the method comprises the following steps:
a. preparing graphene oxide GO: preparing graphene oxide by using commercially available graphite powder as a raw material and adopting a modified Hummers method, namely quantitative NaNO3Adding the graphite powder and the potassium permanganate solution into concentrated sulfuric acid, adding a certain amount of graphite powder and the potassium permanganate solution in proportion after the graphite powder and the potassium permanganate solution are completely dissolved, further reacting to obtain a bright yellow system solution with the concentration of 2.0 mg/ml, and filtering and drying to obtain graphene oxide GO;
b. preparing functionalized graphene GO-ODA: b, dissolving 1.0 g of graphene oxide GO prepared in the step a into 500 ml of N, N-dimethyl formamide DMF solvent after freeze drying, and adding 5 ml of SOCl2Then heated in a water bath at 70 deg.C, condensed and refluxed for 5 hours, and then distilled under reduced pressure at 60 deg.C to remove excess SOCl2Then filtering and washing by using n-butyl alcohol, adding 10 g of ODA, using the n-butyl alcohol as a solvent, condensing and refluxing for 48 hours, and finally obtaining the reaction productCarrying out suction filtration and washing on the product by using n-butyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain GO-ODA for later use;
c. preparing a modified polyurethane composite material: weighing 5 g of GO-ODA prepared in the step b, dispersing the GO-ODA into DMF (dimethyl formamide), carrying out ultrasonic treatment for 3 hours, then adding 500 g of TPU (thermoplastic polyurethane) into the dispersion liquid, carrying out magnetic stirring for 2 hours at normal temperature, and finally drying the mixed liquid to obtain a modified GO-ODA/TPU composite material;
d. forming the thermal reduction composite material: c, hot-pressing the composite material prepared in the step c at 200 ℃ by using a vacuum film pressing machine, wherein the hot-pressing pressure is 4-10 MPa, and the hot-pressing time is 60 min; finally, the modified graphene/polyurethane composite membrane with the thickness of 0.6 mm and good conductivity is obtained.
6. The method for preparing the modified graphene/polyurethane composite material with high conductivity and high tensile-resistance sensitivity according to any one of claims 1 to 4, wherein the method comprises the following steps:
a. preparing graphene oxide GO: preparing graphene oxide by using commercially available graphite powder as a raw material and adopting a modified Hummers method, namely quantitative NaNO3Adding the graphite powder and the potassium permanganate solution into concentrated sulfuric acid, adding a certain amount of graphite powder and the potassium permanganate solution in proportion after the graphite powder and the potassium permanganate solution are completely dissolved, further reacting to obtain a bright yellow system solution with the concentration of 2.0 mg/ml, and filtering and drying to obtain graphene oxide GO;
b. preparing functionalized graphene GO-ODA: b, dissolving 1.0 g of graphene oxide GO prepared in the step a into 500 ml of N, N-dimethyl formamide DMF solvent after freeze drying, and adding 5 ml of SOCl2Then heated in a water bath at 70 deg.C, condensed and refluxed for 5 hours, and then distilled under reduced pressure at 60 deg.C to remove excess SOCl2Then filtering and washing with n-butyl alcohol, adding 10 g of ODA, using the n-butyl alcohol as a solvent, condensing and refluxing for 48 hours, finally carrying out suction filtration and washing on a reaction product with the n-butyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain GO-ODA for later use;
c. preparing a modified polyurethane composite material: weighing 2.5 g of GO-ODA prepared in the step b, dispersing the GO-ODA into DMF (dimethyl formamide), carrying out ultrasonic treatment for 3 hours, then adding 500 g of TPU (thermoplastic polyurethane) into the dispersion liquid, carrying out magnetic stirring for 2 hours at normal temperature, and finally drying the mixed liquid to obtain a modified GO-ODA/TPU composite material;
d. forming the thermal reduction composite material: c, hot-pressing the composite material prepared in the step c at 200 ℃ by using a vacuum film pressing machine, wherein the hot-pressing pressure is 4-10 MPa, and the hot-pressing time is 60 min; finally, the modified graphene/polyurethane composite membrane with the thickness of 0.6 mm and good conductivity is obtained.
7. The method for preparing the modified graphene/polyurethane composite material with high conductivity and high tensile-resistance sensitivity according to any one of claims 1 to 4, wherein the method comprises the following steps:
a. preparing graphene oxide GO: preparing graphene oxide by using commercially available graphite powder as a raw material and adopting a modified Hummers method, namely quantitative NaNO3Adding the graphite powder and the potassium permanganate solution into concentrated sulfuric acid, adding a certain amount of graphite powder and the potassium permanganate solution in proportion after the graphite powder and the potassium permanganate solution are completely dissolved, further reacting to obtain a bright yellow system solution with the concentration of 2.0 mg/ml, and filtering and drying to obtain graphene oxide GO;
b. preparing functionalized graphene GO-ODA: b, dissolving 2.0 g of graphene oxide GO prepared in the step a into 500 ml of N, N-dimethyl formamide DMF solvent after freeze drying, and adding 5 ml of SOCl2Then heated in a water bath at 70 deg.C, condensed and refluxed for 5 hours, and then distilled under reduced pressure at 60 deg.C to remove excess SOCl2Then filtering and washing with n-butyl alcohol, adding 10 g of ODA, using the n-butyl alcohol as a solvent, condensing and refluxing for 48 hours, finally carrying out suction filtration and washing on a reaction product with the n-butyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain GO-ODA for later use;
c. preparing a modified polyurethane composite material: weighing 5 g of GO-ODA prepared in the step b, dispersing the GO-ODA into DMF (dimethyl formamide), carrying out ultrasonic treatment for 3 hours, then adding 250 g of TPU (thermoplastic polyurethane) into the dispersion liquid, carrying out magnetic stirring for 2 hours at normal temperature, and finally drying the mixed liquid to obtain a modified GO-ODA/TPU composite material, wherein a microscopic view is shown in figure 1;
d. forming the thermal reduction composite material: c, hot-pressing the composite material prepared in the step c at 200 ℃ by using a vacuum film pressing machine, wherein the hot-pressing pressure is 4-10 MPa, and the hot-pressing time is 60 min; finally, the modified graphene/polyurethane composite membrane with the thickness of 0.6 mm and good conductivity is obtained.
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