CN115772342A - Preparation method of MXene-graphene modified waterborne polyurethane conductive coating - Google Patents
Preparation method of MXene-graphene modified waterborne polyurethane conductive coating Download PDFInfo
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Abstract
The invention relates to the technical field of conductive coatings, in particular to a preparation method of MXene-graphene modified waterborne polyurethane conductive coating, which comprises the steps of firstly carrying out amination modification on MXene, and then adding graphene oxide dispersion liquid into the modified MXene dispersion liquid to obtain MXene-graphene modified aqueous solution; and then carrying out in-situ polymerization on the MXene-graphene modified aqueous solution and the aqueous polyurethane solution to obtain the MXene-graphene modified aqueous polyurethane conductive coating. The MXene modification enhances the interface compatibility of the composite conductive dispersion liquid and improves the dispersion uniformity. The L-cysteine used in the invention is a green environment-friendly modified material, and has the advantages of low price and no pollution to the environment. The conductive coating prepared by the invention can be used for surface modification treatment of textile materials and high polymer materials, realizes the characteristics of conductivity, heating, electromagnetic interference resistance and the like, and has wide application value.
Description
Technical Field
The invention relates to the technical field of conductive coatings, and particularly relates to a preparation method of an MXene-graphene modified waterborne polyurethane conductive coating.
Background
The conductive coating is a novel functional coating, is applied to various military and civil industrial fields such as textile, electronics, electrical appliances, aviation and the like, and has the functions of static resistance, radiation protection and the like. The waterborne polyurethane has the advantages of wear resistance, corrosion resistance, brightness, softness, elasticity, good mechanical property and the like, and is widely applied to industries such as light textile, leather, coating, wood processing and the like. The hybrid/composite structure of MXene and graphene has excellent conductivity, high biocompatibility, large specific surface area, optical and magnetic characteristics and remarkable thermal and mechanical properties. Compared with the traditional carbon-based conductive coating, the conductive coating has more excellent conductivity; compared with the traditional metal conductive coating, the coating has more excellent interface compatibility and multifunctionality. Therefore, the preparation of the aqueous polyurethane coating containing MXene-graphene has wide application prospect and field.
However, the preparation method of the aqueous polyurethane coating of MXene-graphene in the prior art has the disadvantages of uneven dispersion, high price of adopted materials, pollution and non-conformity with the requirements of environmental protection.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of an MXene-graphene modified waterborne polyurethane conductive coating, so as to solve the problems of uneven dispersion, high price of adopted materials and pollution caused by the existing preparation method.
Based on the aim, the invention provides a preparation method of an MXene-graphene modified waterborne polyurethane conductive coating, which comprises the steps of firstly carrying out amination modification on MXene, and then adding a graphene oxide dispersion liquid into the modified MXene dispersion liquid to obtain an MXene-graphene modified aqueous solution; and then carrying out in-situ polymerization on the MXene-graphene modified aqueous solution and the aqueous polyurethane solution to obtain the MXene-graphene modified aqueous polyurethane conductive coating.
The preparation method of the graphene oxide comprises the following steps:
a1, pre-oxidizing graphite;
a2, stirring and reacting the dried solid powder obtained after pre-oxidation with concentrated sulfuric acid and potassium permanganate at the water bath temperature of 35-40 ℃, and then adding hydrogen peroxide until the solution becomes bright yellow;
and A3, removing metal ions in the bright yellow solution prepared in the step A2, washing and centrifuging to obtain the graphene oxide.
Preferably, the method for pre-oxidizing the graphite in A1 is to mix 3-5 g of crystalline flake graphite with 20-30 ml of concentrated sulfuric acid, add 4-6 g of potassium persulfate and 6-8 g of phosphorus pentoxide under stirring, raise the temperature of a water bath to 80-90 ℃, last 4-5 h, then remove the redundant acid by water washing, and dry at 80-90 ℃ to obtain the graphite.
Preferably, the method for modifying MXene by amination comprises the following steps:
b1, stirring and mixing 3-4 g of lithium fluoride and 9M hydrochloric acid until the powder is completely dissolved, adding 2-4 g of MAX powder, and stirring for 48-54 h in a water bath at 35-38 ℃; centrifugally washing the reaction solution by using 1M hydrochloric acid solution for 3-5 times, washing by using 1M lithium chloride aqueous solution for 3-5 times, and washing by using deionized water until the pH value is 7-8; dispersing the precipitate, oscillating, centrifuging, and collecting the upper layer liquid to obtain MXene;
and B2, mixing the L-cysteine aqueous solution with the MXene dispersion liquid, performing ultrasonic dispersion, stirring and reacting for 24-48 h in a nitrogen atmosphere, centrifuging, and collecting precipitate to obtain the L-cysteine modified MXene.
The concentration of the MXene dispersion liquid is 10-12 mg/ml, and the concentration of the L-cysteine aqueous solution is 7-14 mg/ml.
Preferably, the preparation method of the MXene-graphene modified aqueous solution comprises the steps of dropwise adding 10-12 g/ml of graphene oxide dispersion liquid into 10-12 g/ml of modified MXene dispersion liquid under a stirring state, and then carrying out ultrasonic treatment for 10-15 min to obtain the MXene-graphene modified aqueous solution.
Preferably, the method for in-situ polymerization of the MXene-graphene modified aqueous solution and the aqueous polyurethane solution comprises the following steps:
s1, stirring diisocyanate and polytetrahydrofuran under the action of a catalyst at 60-90 ℃ for reaction for 90-180 min to obtain a mixed solution A; wherein the mass ratio of diisocyanate to polytetrahydrofuran is 8-10: 15 to 25;
s2, adding dimethylolpropionic acid and butanediol into the mixed solution A, and stirring and reacting at 70-80 ℃ for 120-150 min to obtain mixed solution B; wherein the mass volume ratio of diisocyanate to dimethylolpropionic acid to butanediol is 8-10 g: 1-2 g:0.5 to 1ml;
s3, cooling the mixed solution B to 45-50 ℃, controlling the cooling time within 30min, continuously adding triethylamine, stirring and reacting for 15-20 min at 45 ℃ to obtain a mixed solution C; wherein the volume ratio of butanediol to triethylamine is 0.5-1: 1 to 2;
s4, adding an MXene-graphene modified aqueous solution into the mixed solution C for emulsification, wherein the mass ratio of the MXene-graphene modified aqueous solution to diisocyanate is (30-60): 8 to 10.
Preferably, the crosslinking and film-forming mechanical properties of the polyurethane are adjusted by the mass R value of the diisocyanate, and the R value ranges from 1.05 to 1.8.
Preferably, the mass fraction of the dimethylolpropionic acid is 4-7%.
Preferably, the mass ratio of the diisocyanate to the polytetrahydrofuran is 1.95 to 2.1.
The invention has the beneficial effects that: the MXene is subjected to amination modification, hydrophilic groups on the surface of the MXene-graphene are subjected to in-situ polymerization with the aqueous polyurethane solution to prepare the MXene-graphene modified aqueous polyurethane conductive dispersion liquid, and the MXene modification enhances the interface compatibility of the composite conductive dispersion liquid and improves the dispersion uniformity. The L-cysteine used in the invention is a green environment-friendly modified material, and has the advantages of low price and no pollution to the environment. The conductive coating prepared by the invention can be used for surface modification treatment of textile materials and high polymer materials, realizes the characteristics of conductivity, heating, electromagnetic interference resistance and the like, and has wide application value.
Drawings
In order to more clearly illustrate the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 is a photograph of a Mexen-graphene modified waterborne polyurethane conductive mixed solution (the solution is yellow);
fig. 2 is a photograph of a blended film prepared from a Mexen-graphene modified waterborne polyurethane conductive solution.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to specific embodiments below.
It is to be noted that technical terms or scientific terms used herein should have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined.
Example (b): 1
Graphene oxide preparation
Controlling the water temperature in the water bath to be 20 ℃, sequentially adding 3g of crystalline flake graphite and 20ml of concentrated sulfuric acid into a three-neck round-bottom flask, starting an electric stirring instrument to stir, sequentially and slowly adding 4g of potassium persulfate and 6g of phosphorus pentoxide, and raising the water bath temperature to 80 ℃ for 4 hours. And then adding the prepared solution into distilled water to wash away excessive acid, placing the solution in an oven to be dried at 80 ℃, and finishing pre-oxidation. And (3) oxidation: the dried solid powder and 130ml of concentrated sulfuric acid are weighed and added into a round bottom flask, the temperature of the water bath is adjusted to be below 15 ℃, 16g of potassium permanganate (slowly added) is added, the temperature of the water bath is increased to 35 ℃, and the mixture is stirred for two hours. The solution was added to 1200ml of distilled water and hydrogen peroxide was added (stirred) until the solution became bright yellow. And pouring the solution into a hydrochloric acid solution with the concentration of 8% to remove metal ions in the solution, washing the solution with distilled water for 3 times, and centrifuging the solution for two times to obtain the graphene oxide.
Preparation and functional modification of Mexen
3g of lithium fluoride and 30ml of hydrochloric acid (9M) were added to a 100ml centrifuge tube (PP material) and stirred until the powder was completely dissolved, 2g of MAX powder was added and stirred in a 35 ℃ water bath for 48 hours. And (3) centrifugally washing the reaction solution by using a 1M hydrochloric acid solution for 3 times, washing the reaction solution by using a 1M lithium chloride aqueous solution for 3 times, and washing the reaction solution by using deionized water until the pH value is 7. Dispersing the precipitate with 100ml deionized water, shaking with vortex mixer for 5min to completely strip MXene, centrifuging in 20 deg.C water bath for 10min at 3000rpm, and collecting the upper layer liquid to obtain MXene (Ti) 3 C 2 T x )。
0.5g of L-cysteine powder is dissolved in 50ml of deionized water, 50ml of MXene deionized water dispersion liquid (10 mg/ml) is added, ultrasonic dispersion is carried out for 5min, and the mixture is stirred and reacted for 24h at room temperature under the nitrogen atmosphere. And centrifugally washing the solution by using deionized water for 3-5 times, and collecting precipitates to obtain the L-cysteine modified MXene (fMX).
Preparation of MXene-graphene modified aqueous solution
The MXene-graphene composite solution is prepared by an electrostatic self-assembly process. Dropwise adding the graphene oxide (10 g/ml) dispersion liquid into the modified MXene (10 g/ml) dispersion liquid under the stirring state, wherein the total amount is 10ml, and carrying out ultrasonic treatment on the mixture for 10min to obtain the MXene-graphene modified aqueous solution.
graphene-Mexen modified waterborne polyurethane conductive dispersion liquid
8g of diisocyanate and 15g of polytetrahydrofuran are stirred and reacted for 90min at 60 ℃ under the action of 0.5g of dibutyltin dilaurate serving as a catalyst, and the stirring speed is 400r/min; adding 1g of dimethylolpropionic acid with the mass fraction of 4% and 0.5ml of butanediol, stirring and reacting for 120min at 70 ℃, wherein the stirring speed is 400r/min; cooling to 45 ℃ after 20min, continuously adding 1ml of triethylamine, stirring and reacting for 15min at 45 ℃, wherein the stirring speed is 400r/min, and the viscosity of the solution is adjusted by acetone in the period; adding 3ml (10 g/ml) of MXene-graphene modified aqueous solution for emulsification (solid content is calculated according to the solid content of polyurethane), and stirring at the rotating speed of 1000r/min for 30min.
Wherein, the mechanical properties of polyurethane crosslinking and film forming are adjusted by the mass R value of diisocyanate, and the R value range is 1.05.
Example 2
Graphene oxide preparation
Controlling the water temperature in a water bath kettle to be 25 ℃, sequentially adding 5g of crystalline flake graphite and 30ml of concentrated sulfuric acid into the three-neck round-bottom flask, starting an electric stirring instrument to stir, sequentially and slowly adding 4-6 g of potassium persulfate and 7g of phosphorus pentoxide, raising the water bath temperature to 90 ℃, and continuing for 5 hours. And then adding the prepared solution into distilled water to wash away excessive acid, placing the solution in an oven to be dried at 90 ℃, and finishing pre-oxidation. And (3) oxidation: dried solid powder and 150ml of concentrated sulfuric acid are weighed and added into a round-bottom flask, the temperature of a water bath is adjusted to be below 25 ℃, 18g of potassium permanganate (added slowly) is added, the temperature of the water bath is increased to 40 ℃, and the mixture is stirred for two hours. The solution was added to 1400ml of distilled water and hydrogen peroxide was added (stirred) until the solution became bright yellow. And pouring the solution into a hydrochloric acid solution with the concentration of 10% to remove metal ions in the solution, washing the solution with distilled water for 5 times, and centrifuging the solution for two times to obtain the graphene oxide.
Preparation and functional modification of Mexen
4g of lithium fluoride and 40ml of hydrochloric acid (9M) are added to a 120ml centrifuge tube (PP material) and stirred until the powder is completely dissolved, 4g of MAX powder is added and stirred for 54h in a 38 ℃ water bath. And (3) centrifugally washing the reaction solution for 5 times by using a 1M hydrochloric acid solution, washing the reaction solution for 5 times by using a 1M lithium chloride aqueous solution, and washing the reaction solution by using deionized water until the pH value is 8. Dispersing the precipitate with 120ml deionized water, shaking with vortex mixer for 10min to fully strip MXene, centrifuging in 30 deg.C water bath for 15min at 4000rpm, and collecting the upper layer liquid to obtain MXene (Ti) 3 C 2 T x )。
0.7g of L-cysteine powder is dissolved in 70ml of deionized water, 70ml of MXene deionized water dispersion liquid (12 mg/ml) is added, ultrasonic dispersion is carried out for 10min, and the mixture is stirred and reacted for 48h at room temperature under the nitrogen atmosphere. The precipitate was collected by centrifugation and washing the above solution 5 times with deionized water to obtain L-cysteine-modified MXene (fMX).
Preparation of MXene-graphene modified aqueous solution
The MXene-graphene composite solution is prepared by an electrostatic self-assembly process. Dropwise adding the graphene oxide (12 g/ml) dispersion liquid into the modified MXene (12 g/ml) dispersion liquid under the stirring state, wherein the total amount is 15ml, and carrying out ultrasonic treatment on the mixture for 10min to obtain the MXene-graphene modified aqueous solution.
graphene-Mexen modified waterborne polyurethane conductive dispersion liquid
10g of diisocyanate and 25g of polytetrahydrofuran are stirred and reacted for 180min at 90 ℃ under the action of 1g of dibutyltin dilaurate serving as a catalyst, and the stirring speed is 500r/min; adding 2g of 7 mass percent dimethylolpropionic acid and 1ml of butanediol, stirring and reacting at 80 ℃ for 150min, wherein the stirring speed is 500r/min; cooling to 50 ℃, controlling the cooling time within 30min, continuously adding 2ml of triethylamine, stirring and reacting for 20min at 45 ℃, wherein the stirring speed is 500r/min, and the viscosity of the solution is adjusted by acetone in the process; adding 5ml (12 g/ml) of MXene-graphene modified aqueous solution for emulsification (solid content is calculated according to the solid content of polyurethane), and stirring at the rotating speed of 1200r/min for 60min.
Wherein, the mechanical properties of polyurethane crosslinking and film forming are adjusted by the mass R value of diisocyanate, and the R value range is 1.8.
Example 3
The method comprises the following steps: graphene oxide preparation
Controlling the water temperature in the water bath to be 20 ℃, sequentially adding 4g of crystalline flake graphite and 25ml of concentrated sulfuric acid into a three-neck round-bottom flask, starting an electric stirring instrument to stir, sequentially and slowly adding 5g of potassium persulfate and 7g of phosphorus pentoxide, raising the water bath temperature to 80-90 ℃, and continuing for 4 hours. Then adding the prepared solution into distilled water to wash off redundant acid, placing the solution in an oven to be dried at 85 ℃, and finishing pre-oxidation. And (3) oxidation: dried solid powder and 135ml of concentrated sulfuric acid are weighed and added into a round-bottom flask, the temperature of a water bath is adjusted to be below 20 ℃, 16g of potassium permanganate (added slowly) is added, the temperature of the water bath is increased to 35 ℃, and the mixture is stirred for two hours. The solution was added to 1200ml of distilled water and hydrogen peroxide was added (stirred) until the solution became bright yellow. And pouring the solution into a hydrochloric acid solution with the concentration of 9% to remove metal ions in the solution, washing the solution with distilled water for 4 times, and centrifuging the solution for two times to obtain the graphene oxide.
Step two: preparation and functional modification of Mexen
4g of lithium fluoride and 35ml of hydrochloric acid (9M) are added into a centrifuge tube (PP material) of 110ml and stirred until the powder is completely dissolved, 3g of MAX powder is added, and the mixture is stirred for 48 to 54 hours in a water bath at 37 ℃. And (3) centrifuging and washing the reaction solution for 4 times by using a 1M hydrochloric acid solution, washing the reaction solution for 4 times by using a 1M lithium chloride aqueous solution, and washing the reaction solution by using deionized water until the pH value is 7. Dispersing the precipitate with 100ml deionized water, shaking with vortex mixer for 7min to fully strip MXene, centrifuging at 25 deg.C water bath for 13min at 3500rpm, and collecting the upper layer liquid to obtain MXene (Ti) 3 C 2 T x )。
0.6g of L-cysteine powder is dissolved in 60ml of deionized water, 60ml of MXene deionized water dispersion liquid (11 mg/ml) is added, ultrasonic dispersion is carried out for 7min, and the mixture is stirred and reacted for 30h at room temperature under the nitrogen atmosphere. The precipitate was collected by centrifugation and washed 4 times with deionized water to give L-cysteine-modified MXene (fMX).
Step three: preparation of MXene-graphene modified aqueous solution
The MXene-graphene composite solution is prepared by an electrostatic self-assembly process. Dropwise adding the graphene oxide (12 g/ml) dispersion liquid into the modified MXene (12 g/ml) dispersion liquid under the stirring state, wherein the total amount is 10ml, and carrying out ultrasonic treatment on the mixture for 10min to obtain the MXene-graphene modified aqueous solution.
Step four: graphene-Mexen modified waterborne polyurethane conductive dispersion liquid
9g of diisocyanate and 20g of polytetrahydrofuran are stirred and reacted for 160min at 80 ℃ under the action of 1g of dibutyltin dilaurate serving as a catalyst, and the stirring speed is 450r/min; adding 2g of dimethylolpropionic acid with the mass fraction of 5% and 1ml of butanediol, stirring and reacting for 130min at the temperature of 80 ℃, wherein the stirring speed is 400-500 r/min; cooling to 45-50 ℃, controlling the cooling time within 30min, continuously adding 1-2 ml of triethylamine, stirring and reacting for 20min at 45 ℃, wherein the stirring speed is 450r/min, and adjusting the viscosity of the solution by acetone in the process; adding 4ml (12 g/ml) of MXene-graphene modified aqueous solution for emulsification (solid content is calculated according to the solid content of polyurethane), and stirring at the rotating speed of 1100r/min for 30-60 min.
Wherein, the mechanical properties of polyurethane crosslinking and film forming are adjusted by the mass R value of diisocyanate, and the R value range is 1.7.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also technical features in the above embodiments or in different embodiments may be combined, steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The present invention is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalents, improvements, and the like that may be made without departing from the spirit or scope of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the MXene-graphene modified waterborne polyurethane conductive coating is characterized by comprising the steps of firstly carrying out amination modification on MXene, and then adding a graphene oxide dispersion liquid into the modified MXene dispersion liquid to obtain an MXene-graphene modified aqueous solution; and then carrying out in-situ polymerization on the MXene-graphene modified aqueous solution and the aqueous polyurethane solution to obtain the MXene-graphene modified aqueous polyurethane conductive coating.
2. The preparation method of the MXene-graphene modified waterborne polyurethane conductive coating as claimed in claim 1, wherein the preparation method of graphene oxide comprises the following steps:
a1, pre-oxidizing graphite;
a2, stirring and reacting the dried solid powder obtained after pre-oxidation with concentrated sulfuric acid and potassium permanganate at the water bath temperature of 35-40 ℃, and then adding hydrogen peroxide until the solution becomes bright yellow;
and A3, removing metal ions in the bright yellow solution prepared in the step A2, washing and centrifuging to obtain the graphene oxide.
3. The method for preparing the MXene-graphene modified waterborne polyurethane conductive coating of claim 2, wherein the method for pre-oxidizing graphite in A1 comprises the steps of mixing 3-5 g of crystalline flake graphite with 20-30 ml of concentrated sulfuric acid, adding 4-6 g of potassium persulfate and 6-8 g of phosphorus pentoxide under stirring, raising the temperature of a water bath to 80-90 ℃ for 4-5 h, washing with water to remove excess acid, and drying at 80-90 ℃ to obtain the MXene-graphene modified waterborne polyurethane conductive coating.
4. The preparation method of the MXene-graphene modified waterborne polyurethane conductive coating as claimed in claim 1, wherein the method for modifying MXene by amination comprises the following steps:
b1, stirring and mixing 3-4 g of lithium fluoride and 9M hydrochloric acid until the powder is completely dissolved, adding 2-4 g of MAX powder, and stirring for 48-54 h in a water bath at 35-38 ℃; centrifugally washing the reaction solution by using 1M hydrochloric acid solution for 3-5 times, washing by using 1M lithium chloride aqueous solution for 3-5 times, and washing by using deionized water until the pH value is 7-8; dispersing the precipitate, oscillating, centrifuging, and collecting the upper layer liquid to obtain MXene;
and B2, mixing the L-cysteine aqueous solution with the MXene dispersion liquid, performing ultrasonic dispersion, stirring and reacting for 24-48 h in a nitrogen atmosphere, centrifuging, and collecting precipitate to obtain the L-cysteine modified MXene.
5. The preparation method of the MXene-graphene modified waterborne polyurethane conductive coating as claimed in claim 4, wherein the concentration of the MXene dispersion liquid is 10-12 mg/ml, and the concentration of the L-cysteine aqueous solution is 7-14 mg/ml.
6. The preparation method of the MXene-graphene modified waterborne polyurethane conductive coating as claimed in claim 1, wherein the preparation method of the MXene-graphene modified aqueous solution is to dropwise add 10-12 g/ml of graphene oxide dispersion liquid into 10-12 g/ml of modified MXene dispersion liquid under a stirring state, and then perform ultrasonic treatment for 10-15 min to obtain the MXene-graphene modified aqueous solution.
7. The preparation method of the MXene-graphene modified waterborne polyurethane conductive coating as claimed in claim 1, wherein the method for in-situ polymerization of the MXene-graphene modified aqueous solution and the waterborne polyurethane solution comprises the following steps:
s1, stirring diisocyanate and polytetrahydrofuran under the action of a catalyst at 60-90 ℃ for reaction for 90-180 min to obtain a mixed solution A; wherein the mass ratio of diisocyanate to polytetrahydrofuran is 8-10: 15 to 25;
s2, adding dimethylolpropionic acid and butanediol into the mixed solution A, and stirring and reacting at 70-80 ℃ for 120-150 min to obtain mixed solution B; wherein the mass volume ratio of diisocyanate to dimethylolpropionic acid to butanediol is 8-10 g: 1-2 g:0.5 to 1ml;
s3, cooling the mixed solution B to 45-50 ℃, controlling the cooling time within 30min, continuously adding triethylamine, stirring and reacting for 15-20 min at 45 ℃ to obtain a mixed solution C; wherein the volume ratio of butanediol to triethylamine is 0.5-1: 1-2;
s4, adding an MXene-graphene modified aqueous solution into the mixed solution C for emulsification, wherein the mass ratio of the MXene-graphene modified aqueous solution to diisocyanate is 30-60: 8 to 10.
8. The preparation method of the MXene-graphene modified waterborne polyurethane conductive coating as claimed in claim 7, wherein the mechanical properties of polyurethane crosslinking and film formation are adjusted by the mass R value of diisocyanate, and the R value range is 1.05-1.8.
9. The preparation method of the MXene-graphene modified waterborne polyurethane conductive coating as claimed in claim 7, wherein the mass fraction of the dimethylolpropionic acid is 4-7%.
10. The preparation method of the MXene-graphene modified waterborne polyurethane conductive coating according to claim 7, wherein the mass ratio of the diisocyanate to the polytetrahydrofuran is 1.95-2.1.
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