CN109679102B - Dynamic thermal-reversible remodelable graphene/polysiloxane nanocomposite and preparation method thereof - Google Patents
Dynamic thermal-reversible remodelable graphene/polysiloxane nanocomposite and preparation method thereof Download PDFInfo
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Abstract
The invention provides a dynamic thermoreversible and remodelable graphene/polysiloxane nanocomposite and a preparation method thereof. The dynamic thermoreversible and remodelable graphene/polysiloxane nanocomposite material prepared by the method does not need any external repairing agent, can realize dynamic thermoreversible transformation of a crosslinking system and remodeling and molding only through heat treatment, has a simple synthesis process, has the dynamic thermoreversible property, and can be remodelable and molded repeatedly.
Description
Technical Field
The invention relates to the field of graphene/polysiloxane nanocomposite materials and preparation thereof, in particular to a graphene/polysiloxane nanocomposite material which is dynamic and thermally reversible and can be repeatedly remodeled and a preparation method thereof.
Background
As a novel intelligent structure functional material, the self-repairing polymer material can realize self-repairing of microcracks of the material through simulating the mechanism of organism damage healing, and further damage to the microcracks is avoided, so that the service life of the material is prolonged. At present, there are many approaches for self-repairing polymer materials, and most researches are currently made to introduce dynamic covalent bonds into a polymer material system by a certain means so as to achieve the effect of self-repairing. The so-called dynamic covalent bonds, that is to say capable of being reversibly broken and formed under suitable conditions, combine the advantages of the reversibility of the non-covalent nature of supramolecules with the robustness of covalent bonds, which makes them widely used. Compared with the traditional polysiloxane nanocomposite, the graphene/polysiloxane nanocomposite constructed based on the dynamic covalent bond has great difference in many aspects such as preparation method, structure and performance, and becomes a hot field for the research of the current polysiloxane nanocomposite.
Disclosure of Invention
The invention overcomes the defects in the prior art, and provides the graphene/polysiloxane nanocomposite material which can realize dynamic thermal reversibility and repeated remodeling and molding under the condition of heat treatment, and the material not only has good dynamic thermal reversibility, but also can be repeatedly remodeled and molded.
The purpose of the invention is realized by the following technical scheme.
A graphene/polysiloxane nano composite material capable of being dynamically thermally reversible and remodeled and a preparation method thereof are disclosed, glycidyl furfuryl ether and bismaleimide are reacted under an anaerobic condition to obtain a substance containing a diepoxy functional group, the substance containing the diepoxy functional group is used as a cross-linking agent to react with aminopropyl-terminated polysiloxane or side amino polysiloxane and graphene nano particles under the anaerobic condition, so that the epoxy functional group and the amino functional group in the aminopropyl-terminated polysiloxane or side amino polysiloxane are subjected to chemical reaction to form a cross-linked three-dimensional network system, and specifically:
the bismaleimide is one of substances containing two or more maleimide structures, such as N, N ' - (4,4 ' -methylenediphenyl) bismaleimide, N ' - (1, 4-phenylene) bismaleimide, 1, 4-bis (maleimide) butane, 1, 2-bis (maleimide) ethane, and the like.
The side chain of the aminopropyl terminated polysiloxane is methyl, vinyl, phenyl or fluorocarbon, and the number average molecular weight of the aminopropyl terminated polysiloxane is 1000-10000; the amino group molar content (mol%) of the side aminopropyl polysiloxane is 1-10.
The mass fraction of the added graphene nano particles is 1-10%.
Inert shielding gas is used to provide oxygen-free conditions for the reaction system, such as nitrogen, helium or argon.
In the reaction, amino groups are provided by aminopropyl terminated polysiloxane or side amino polysiloxane, epoxy groups are provided by substances with double epoxy functional groups, wherein the molar ratio of glycidyl furfuryl ether, bismaleimide and aminopropyl terminated polysiloxane or side amino polysiloxane is (1-3): (1-2): (1-2), preferably (1-2): 1: 1.
in the specific implementation, the method comprises the following steps:
step 1, placing glycidyl furfuryl ether and bismaleimide in a solvent, uniformly mixing, refluxing for 5-10 days at 60-70 ℃ under an oxygen-free condition, placing in anhydrous ether for precipitation, drying, washing and purifying a precipitate, placing in glacial methanol for precipitation, and drying to obtain a substance containing a diepoxy functional group;
and 2, mixing the substance containing the diepoxy functional group prepared in the step 1 and aminopropyl-terminated polysiloxane or side amino polysiloxane in a solvent, adding graphene nanoparticles, continuously stirring, pouring the mixture into a mold after uniform mixing, and volatilizing and drying under an oxygen-free condition to obtain the dynamic thermoreversible and remodelable graphene/polysiloxane nanocomposite.
The solvent is anhydrous solvent, and volatile organic solvent such as one or more of dichloromethane, chloroform, toluene, xylene, dimethyl sulfoxide, ethyl acetate, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.
Inert shielding gas is used to provide oxygen-free conditions for the reaction system, such as nitrogen, helium or argon.
In the step 1, the precipitate is dried in a vacuum oven at 40-80 ℃ for 24-48h, washed and extracted for 5-10 times by using acetone as a solvent and anhydrous ether as an extractant, the product is precipitated in ice methanol, and the precipitate is placed in the vacuum oven at 40-80 ℃ for 5-10 days.
In the step 2, a substance containing a diepoxy functional group and aminopropyl terminated polysiloxane or side amino polysiloxane are placed in a solvent and are mechanically stirred for 1-3 hours, then are uniformly mixed, graphene nano particles with the mass fraction of 1-10% are added, the mechanical stirring is continued for 1-3 hours, the reaction is carried out for 3-5 days at 50-80 ℃ under the anaerobic condition, and the vacuum drying is carried out for 12-24 hours at 40-80 ℃.
FIG. 1 shows a tool synthesized by the exampleIR spectra of diepoxy-functional materials with DA reversible dynamic bond via glycidyl furfuryl ether and N, N '- (4, 4' -methylenediphenyl) bismaleimide [4+2 ]]The cyclized addition was made at a wave number of 1776cm-1The characteristic infrared absorption peak appears, and the characteristic infrared absorption peak of DA bond is corresponded to.
Fig. 2 is a swelling experiment diagram of the prepared graphene/polysiloxane nanocomposite material prepared in the example, a small piece of the prepared graphene/polysiloxane nanocomposite material sample is cut off and is placed into toluene to be soaked for 48 hours, and a swelling experiment is performed to prove that a crosslinked network system is formed, namely the picture in fig. 2 is obtained, so that successful construction of the crosslinked network in the graphene/polysiloxane nanocomposite material system in the invention is very powerfully proved.
In order to prove that the polysiloxane crosslinked elastomer material has the dynamic thermal reversible property, a small sample is cut and put into xylene, after the sample is placed for 48 hours, the sample is placed for 60 minutes at 130 ℃, and then a thermal dissolving solution can be obtained, fig. 3 is a thermal dissolving schematic diagram of the graphene/polysiloxane nanocomposite material prepared in the embodiment, the graphene/polysiloxane nanocomposite material only swells and does not dissolve from the beginning, and a completely dissolved solution is obtained after thermal treatment.
In order to prove that the graphene/polysiloxane nanocomposite material has remoldable property, a small amount of sample is taken, cut into a plurality of blocks, dissolved in xylene, subjected to heat treatment at 130 ℃ to generate DA reverse reaction to obtain a thermal solution, poured into a corresponding mold, volatilized, and subjected to reaction at 50-80 ℃ for 24 hours to obtain a new molded sample. As shown in fig. 4, the schematic diagram of the graphene/polysiloxane nanocomposite obtained in the present invention is shown after being heated and dissolved to be reshaped.
The invention has the beneficial effects that: the Diels-Alder dynamic reversible covalent bond is similar to the general covalent bond at a lower temperature (less than 100 ℃), the reverse reaction can be induced at a higher temperature (110-. The method for preparing the graphene/polysiloxane nanocomposite material which is dynamic and thermally reversible and can be repeatedly reshaped has the advantages of easily available raw materials, simple synthetic process, no need of special conditions and equipment, easily controlled forming process and easy application to industry.
Drawings
FIG. 1 is an infrared spectrum of a diepoxy-functional substance containing DA bonds synthesized in example 1 of the present invention;
FIG. 2 is a graph showing a swelling experiment of the graphene/polysiloxane nanocomposite obtained in example 1 of the present invention;
FIG. 3 is a schematic thermal dissolution diagram of the graphene/polysiloxane nanocomposite prepared in example 1 of the present invention;
fig. 4 is a remodeling and forming diagram of the graphene/polysiloxane nanocomposite material prepared in example 1 of the present invention after being heated and dissolved.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
Synthesis of matter containing a diepoxy functional group: uniformly mixing 0.02mol of glycidyl furfuryl ether and 0.01mol of N, N '- (4, 4' -methylene diphenyl) bismaleimide in 200ml of anhydrous tetrahydrofuran in terms of mole number, transferring the mixture into a 500ml three-neck flask, arranging a magnetic stirring and reflux condenser tube, refluxing for 7 days at 66 ℃ under the protection of nitrogen, then pouring the pre-product into 500ml of anhydrous diethyl ether for precipitation, placing the precipitate in a 40 ℃ vacuum oven for 48 hours, and removing residual solvent; and then dissolving the dried product in 50ml of acetone, purifying by using 500ml of anhydrous ether as a precipitator, repeatedly washing and purifying for 5 times, precipitating and separating out the finally obtained product in ice methanol, placing in a vacuum oven at 40 ℃ for 7 days, and sealing and storing for later use after the residual solvent is completely removed.
Preparing a dynamic thermoreversible and remodelable graphene/polysiloxane nanocomposite material: taking 0.002mol of the prepared matter containing the diepoxy functional group and 0.001mol of aminopropyl terminated polysiloxane (Mw is about 10000) in terms of mole number, stirring for 2 hours in 200ml of dichloromethane, adding 0.1000g of graphene (mass fraction is 1 wt%) after the materials are uniformly mixed, continuing stirring for 2 hours, pouring the solution into a polytetrafluoroethylene mold after the materials are completely and uniformly mixed, naturally volatilizing to remove the solvent, reacting the mold at 60 ℃ for 5 days under the protection of nitrogen, and then carrying out vacuum drying at 40 ℃ for 24 hours to finally obtain the graphene/polysiloxane nanocomposite.
Example 2
Synthesis of matter containing a diepoxy functional group: uniformly mixing 0.02mol of glycidyl furfuryl ether and 0.01mol of N, N '- (4, 4' -methylene diphenyl) bismaleimide in 200ml of anhydrous tetrahydrofuran in terms of mole number, transferring the mixture into a 500ml three-neck flask, arranging a magnetic stirring and reflux condenser tube, refluxing for 7 days at 66 ℃ under the protection of nitrogen, then pouring the pre-product into 500ml of anhydrous diethyl ether for precipitation, placing the precipitate in a 40 ℃ vacuum oven for 48 hours, and removing residual solvent; and then dissolving the dried product in 50ml of acetone, purifying by using 500ml of anhydrous ether as a precipitator, repeatedly washing and purifying for 5 times, precipitating and separating out the finally obtained product in ice methanol, placing in a vacuum oven at 40 ℃ for 7 days, and sealing and storing for later use after the residual solvent is completely removed.
Preparing a dynamic thermoreversible and remodelable graphene/polysiloxane nanocomposite material: taking 0.002mol of the prepared matter containing the diepoxy functional group and 0.001mol of aminopropyl terminated polysiloxane (Mw is about 10000) in terms of mole number, stirring for 2 hours in 200ml of dichloromethane, adding 0.2000g of graphene (mass fraction is 2 wt%) after the materials are uniformly mixed, continuing stirring for 2 hours, pouring the solution into a polytetrafluoroethylene mold after the materials are completely and uniformly mixed, naturally volatilizing to remove the solvent, reacting the mold at 60 ℃ for 5 days under the protection of nitrogen, and then carrying out vacuum drying at 40 ℃ for 24 hours to finally obtain the graphene/polysiloxane nanocomposite.
Example 3
Synthesis of matter containing a diepoxy functional group: uniformly mixing 0.02mol of glycidyl furfuryl ether and 0.01mol of N, N '- (4, 4' -methylene diphenyl) bismaleimide in 200ml of anhydrous tetrahydrofuran in terms of mole number, transferring the mixture into a 500ml three-neck flask, arranging a magnetic stirring and reflux condenser tube, refluxing for 7 days at 66 ℃ under the protection of nitrogen, then pouring the pre-product into 500ml of anhydrous diethyl ether for precipitation, placing the precipitate in a 40 ℃ vacuum oven for 48 hours, and removing residual solvent; and then dissolving the dried product in 50ml of acetone, purifying by using 500ml of anhydrous ether as a precipitator, repeatedly washing and purifying for 5 times, precipitating and separating out the finally obtained product in ice methanol, placing in a vacuum oven at 40 ℃ for 7 days, and sealing and storing for later use after the residual solvent is completely removed.
Preparing a dynamic thermoreversible and remodelable graphene/polysiloxane nanocomposite material: taking 0.002mol of the prepared matter containing the diepoxy functional group and 0.001mol of aminopropyl terminated polysiloxane (Mw is about 10000) in terms of mole number, stirring for 2 hours in 200ml of dichloromethane, adding 0.3000g of graphene (mass fraction is 3 wt%) after the materials are uniformly mixed, continuing stirring for 2 hours, pouring the solution into a polytetrafluoroethylene mold after the materials are completely and uniformly mixed, naturally volatilizing to remove the solvent, reacting the mold at 60 ℃ for 5 days under the protection of nitrogen, and then carrying out vacuum drying at 40 ℃ for 24 hours to finally obtain the graphene/polysiloxane nanocomposite.
Example 4
Synthesis of matter containing a diepoxy functional group: uniformly mixing 0.02mol of glycidyl furfuryl ether and 0.01mol of N, N '- (4, 4' -methylene diphenyl) bismaleimide in 200ml of anhydrous tetrahydrofuran in terms of mole number, transferring the mixture into a 500ml three-neck flask, arranging a magnetic stirring and reflux condenser tube, refluxing for 7 days at 66 ℃ under the protection of nitrogen, then pouring the pre-product into 500ml of anhydrous diethyl ether for precipitation, placing the precipitate in a 40 ℃ vacuum oven for 48 hours, and removing residual solvent; and then dissolving the dried product in 50ml of acetone, purifying by using 500ml of anhydrous ether as a precipitator, repeatedly washing and purifying for 5 times, precipitating and separating out the finally obtained product in ice methanol, placing in a vacuum oven at 40 ℃ for 7 days, and sealing and storing for later use after the residual solvent is completely removed.
Preparing a dynamic thermoreversible and remodelable graphene/polysiloxane nanocomposite material: taking 0.002mol of the prepared matter containing the diepoxy functional group and 0.001mol of aminopropyl terminated polysiloxane (Mw is about 10000) in terms of mole number, stirring for 2 hours in 200ml of dichloromethane, adding 0.4000g of graphene (mass fraction is 4 wt%) after the materials are uniformly mixed, continuing stirring for 2 hours, pouring the solution into a polytetrafluoroethylene mold after the materials are completely and uniformly mixed, naturally volatilizing to remove the solvent, reacting the mold at 60 ℃ for 5 days under the protection of nitrogen, and then carrying out vacuum drying at 40 ℃ for 24 hours to finally obtain the graphene/polysiloxane nanocomposite.
Example 5
Synthesis of matter containing a diepoxy functional group: uniformly mixing 0.02mol of glycidyl furfuryl ether and 0.01mol of N, N '- (4, 4' -methylene diphenyl) bismaleimide in 200ml of anhydrous tetrahydrofuran in terms of mole number, transferring the mixture into a 500ml three-neck flask, arranging a magnetic stirring and reflux condenser tube, refluxing for 7 days at 66 ℃ under the protection of nitrogen, then pouring the pre-product into 500ml of anhydrous diethyl ether for precipitation, placing the precipitate in a 40 ℃ vacuum oven for 48 hours, and removing residual solvent; and then dissolving the dried product in 50ml of acetone, purifying by using 500ml of anhydrous ether as a precipitator, repeatedly washing and purifying for 5 times, precipitating and separating out the finally obtained product in ice methanol, placing in a vacuum oven at 40 ℃ for 7 days, and sealing and storing for later use after the residual solvent is completely removed.
Preparing a dynamic thermoreversible and remodelable graphene/polysiloxane nanocomposite material: taking 0.002mol of the prepared matter containing the diepoxy functional group and 0.001mol of aminopropyl terminated polysiloxane (Mw is about 10000) in terms of mole number, stirring for 2 hours in 200ml of dichloromethane, adding 0.5000g of graphene (mass fraction is 5 wt%) after the materials are uniformly mixed, continuing stirring for 2 hours, pouring the solution into a polytetrafluoroethylene mold after the materials are completely and uniformly mixed, naturally volatilizing to remove the solvent, reacting the mold at 60 ℃ for 5 days under the protection of nitrogen, and then carrying out vacuum drying at 40 ℃ for 24 hours to finally obtain the graphene/polysiloxane nanocomposite.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (14)
1. A dynamic thermoreversible remodelable graphene/polysiloxane nanocomposite, characterized in that: reacting glycidyl furfuryl ether with bismaleimide under an anaerobic condition to obtain a substance containing a diepoxy functional group, and reacting the substance containing the diepoxy functional group with aminopropyl-terminated polysiloxane or side amino polysiloxane and graphene nanoparticles under an anaerobic condition by taking the substance containing the diepoxy functional group as a cross-linking agent to enable an epoxy functional group to chemically react with amino functional groups in the aminopropyl-terminated polysiloxane or side amino polysiloxane to form a cross-linked three-dimensional network system; wherein the molar ratio of the glycidyl furfuryl ether, the bismaleimide and the aminopropyl terminated polysiloxane or the side amino polysiloxane is (1-3): (1-2): (1-2), the mass fraction of the added graphene nanoparticles is 1-10%.
2. The dynamically thermoreversibly remodelable graphene/polysiloxane nanocomposite material according to claim 1, wherein: the bismaleimide is one of N, N ' - (4,4 ' -methylene diphenyl) bismaleimide, N ' - (1, 4-phenylene) bismaleimide, 1, 4-bis (maleimide) butane and 1, 2-bis (maleimide) ethane.
3. The dynamically thermoreversibly remodelable graphene/polysiloxane nanocomposite material according to claim 1, wherein: the side chain of the aminopropyl terminated polysiloxane is methyl, vinyl, phenyl or fluorocarbon, and the number average molecular weight of the aminopropyl terminated polysiloxane is 1000-10000; the amino molar content of the side amino polysiloxane is 1-10 mol%.
4. The dynamically thermoreversibly remodelable graphene/polysiloxane nanocomposite material according to claim 1, wherein: inert protective gas is used for providing an anaerobic condition for the reaction system; in the reaction, amino groups are provided by aminopropyl terminated polysiloxane or side amino polysiloxane, epoxy groups are provided by substances with double epoxy functional groups, wherein the molar ratio of glycidyl furfuryl ether, bismaleimide and aminopropyl terminated polysiloxane or side amino polysiloxane is (1-2): 1: 1.
5. the dynamically thermoreversibly remodelable graphene/polysiloxane nanocomposite material according to claim 4, wherein: the inert protective gas is nitrogen, helium or argon.
6. A preparation method of a dynamic thermoreversible and remodelable graphene/polysiloxane nanocomposite is characterized by comprising the following steps: the method comprises the following steps:
step 1, placing glycidyl furfuryl ether and bismaleimide in a solvent, uniformly mixing, refluxing for 5-10 days at 60-70 ℃ under an oxygen-free condition, placing in anhydrous ether for precipitation, drying, washing and purifying a precipitate, placing in glacial methanol for precipitation, and drying to obtain a substance containing a diepoxy functional group;
and 2, mixing the substance containing the diepoxy functional group prepared in the step 1 and aminopropyl-terminated polysiloxane or side amino polysiloxane in a solvent, adding graphene nanoparticles, continuously stirring, pouring the mixture into a mold after uniform mixing, reacting under an oxygen-free condition, volatilizing and drying to obtain the dynamic thermoreversible and remodelable graphene/polysiloxane nanocomposite.
7. The method for preparing a dynamically thermoreversibly remodelable graphene/polysiloxane nanocomposite material according to claim 6, wherein the method comprises the following steps: the solvent is anhydrous volatile organic solvent.
8. The method for preparing a dynamically thermoreversibly remodelable graphene/polysiloxane nanocomposite material according to claim 7, wherein: the anhydrous volatile organic solvent is one or more mixed solvents of dichloromethane, trichloromethane, toluene, xylene, dimethyl sulfoxide, ethyl acetate, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
9. The method for preparing a dynamically thermoreversibly remodelable graphene/polysiloxane nanocomposite material according to claim 6, wherein the method comprises the following steps: inert shielding gas is used to provide oxygen-free conditions for the reaction system.
10. The method for preparing a dynamically thermoreversibly remodelable graphene/polysiloxane nanocomposite material according to claim 9, wherein: the inert protective gas adopts nitrogen, helium or argon.
11. The method for preparing a dynamically thermoreversibly remodelable graphene/polysiloxane nanocomposite material according to claim 6, wherein the method comprises the following steps: in step 1, amino groups are provided by aminopropyl terminated polysiloxane or pendant amino polysiloxane, epoxy groups are provided by diepoxy functional materials, and the molar ratio of glycidyl furfuryl ether, bismaleimide and aminopropyl terminated polysiloxane or pendant amino polysiloxane is (1-3): (1-2): (1-2); drying the precipitate in a vacuum oven at 40-80 deg.C for 24-48h, washing and extracting with acetone as solvent and anhydrous ether as extractant for 5-10 times, precipitating with glacial methanol, and standing in a vacuum oven at 40-80 deg.C for 5-10 days.
12. The method for preparing a dynamically thermoreversibly remodelable graphene/polysiloxane nanocomposite material according to claim 11, wherein: the molar ratio of the glycidyl furfuryl ether, the bismaleimide and the aminopropyl terminated polysiloxane or the pendant amino polysiloxane is (1-2): 1: 1.
13. the method for preparing a dynamically thermoreversibly remodelable graphene/polysiloxane nanocomposite material according to claim 6, wherein the method comprises the following steps: in the step 2, a substance containing a diepoxy functional group and aminopropyl terminated polysiloxane or side amino polysiloxane are placed in a solvent and mechanically stirred for 1-3 hours to be uniformly mixed, then graphene nano particles with the mass fraction of 1-10% are added, the mechanical stirring is continued for 1-3 hours, the reaction is carried out for 3-5 days at 50-80 ℃ under the anaerobic condition, and the vacuum drying is carried out for 12-24 hours at 40-80 ℃.
14. Use of a dynamically thermoreversibly remodelable graphene/polysiloxane nanocomposite material according to any one of claims 1 to 5 in the preparation of a reworkable nanocomposite material, wherein: the Diels-Alder dynamic reversible covalent bond in the graphene/polysiloxane nano composite material induces reverse reaction at the temperature of 110-130 ℃, and after annealing treatment, the bond can be formed again.
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