CN112280056A - Preparation method of repairable graphene oxide material based on hydrogen bond effect - Google Patents
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Abstract
The invention discloses a preparation method of a repairable graphene oxide material based on a hydrogen bond effect, which belongs to the field of high-molecular self-repairing materials and anticorrosive coatings, and the preparation method comprises the steps of reacting 1, 2-bis (2-aminoethoxy) ethane with 1, 1' -thiocarbonyl diimidazole to obtain an ether-thiourea polymer with a hydrogen bond type thiourea structure; and grafting the ether-thiourea polymer to the surface of the graphene oxide prepared by the optimized Hummers method through amidation reaction to obtain the repairable graphene oxide material based on hydrogen bond effect. The repairable graphene oxide material based on the hydrogen bond effect solves the problem that the mechanical property and the self-healing effect of the hydrogen bond self-healing material are generally rejected. The hydrogen bond type thiourea structure endows the material with better self-healing capability, and greatly enhances the mechanical property of the material by matching with the characteristics of excellent mechanical property, gas barrier property and the like of the graphene oxide.
Description
Technical Field
The invention relates to the field of polymer self-repairing materials and anticorrosive coatings, in particular to a preparation method of a repairable graphene oxide material based on hydrogen bond action.
Background
The polymer material is widely applied to the high and new technical fields of aviation, aerospace, electronics, machinery and the like due to excellent performance of the polymer material, however, certain structural damage occurs along with the influence of mechanical load, use environment and the like in the use process of the material, microcracks are generated, the performance of the material is greatly reduced, and the use safety and sustainability of the material are influenced. In view of this situation, research into self-healing polymers (SHPs) has been carried out, which contributes to improvement in reliability and long-term durability of materials.
Self-repairing methods of polymer materials are roughly divided into two categories, namely external self-repairing and intrinsic self-repairing. The self-repairing of the material is realized by the aid of an external repairing agent, but the self-repairing times are limited by the encapsulated repairing dosage. The intrinsic self-repairing is to repair damage in the polymer through reversible chemical reaction and macromolecular diffusion, without considering the compatibility of an additional substance and a group, and can realize multiple self-repairing of cracks and even broken materials. The intrinsic self-repairing types according to different reaction types are classified into reversible covalent bond self-repairing and reversible non-covalent bond self-repairing. Reversible non-covalent bond self-repair is repair by utilizing various non-covalent bonds formed between functional groups of polymer chains at a fracture interface to be reconnected. Among them, hydrogen bond is the simplest non-covalent bond acting force, which has high orientation, selectivity and dynamic reversibility, and can realize reversible formation and destruction at lower temperature without any external stimulus or additive. Wittmer et al used 1- (2-aminoethyl) imidazolidinone (UD ETA) as a chain terminating molecule and used to form a hydrogen bond network to obtain a self-healing polyurethane urea-based material, which makes the polymer material have good self-healing properties when the hydrogen bond undergoes non-covalent bond "cross-linking". (Wittmer A, Brinkmann, Stenzel V, eta l. motion-medium in theory of chemistry and catalysis and polyurethane polymers [ J ]. JPOLYMSCIPolchem,2018,56(5): 537-548.) in order to enhance the mechanical properties of the material, Graphene Oxide (GO) has received great attention as a novel nanomaterial appearing in the 21 st century. Due to the sufficient oxygen-containing groups on the surface, the graphene oxide and a plurality of organic polymers can be well compatible, and the carbonyl and carboxyl at the edge enable the graphene oxide to be highly hydrophilic, have an ultra-large specific surface area and gas barrier property, so that the graphene oxide becomes a research hotspot in the field of anticorrosive coatings. In addition, graphene oxide can also be used as a cross-linking agent of a polymer containing hydrogen bonds, Chen and the like react a small amount of acyl-chlorinated graphene oxide with a prepolymer of which the branched chain is terminated by amino groups, and a self-repairing elastomer with a net structure is obtained by utilizing the hydrogen bonds formed between the amino groups, so that the application of the graphene oxide in the self-repairing polymer has a great development space. (Hongyang C, Ji anrongL, YanningS, Denglong C, XuelinZ, HuZ, Greensyntheson of a phenol formaldehyde polymer in organic solvents of a nitrile amino catalysis reduction of a phenol formaldehyde polymer with a urea formaldehyde resin, materials of today communications,2020,23: 2352. sup. 4928.) however, Aida et al have recognized that the presence of a large number of hydrogen bonds generally leads to crystallization or aggregation of the polymer material, which all embrittle the material. In response to this phenomenon, they reported an ether-thiourea polymer in which hydrogen bond-type thioureas were able to form a zigzag array, so that these materials not only had good mechanical properties but also were able to achieve self-healing with slight compression. (Yanagisaway, NanY, OkuroK, Aidat. mechanical allobouts, readi lyreproperable polymers, living polymers, cross-linking, science,2018,359(6371):72-76.) As such, Cui et al successfully synthesized self-healing polymers with tunable mechanical strength by combining hydrogen bonding and Zn (I) -imidazole interactions, which polymers exhibited self-healing efficiencies of over 90% under mild conditions. Therefore, the randomly branched polymer with the hydrogen bond network is a self-healing material with a very promising application prospect. (XuruiC, YanS, Jun-PengW, Jun-KuoW, qiong z, TaoQ, GuoLL, Self-healing Polymer switch u. nalbleachanic trenngths hydrogen bonding and Self-healing-ionic azo extractions, Polymer,2019,174: 143. sup. 149.) this experiment prepared a non-covalent bond graphene oxide Polymer composite material that could Self-heal at room temperature, which combined the good bonding properties of network hydrogen bonds, the zigzag array of hydrogen bond-type thiourea, and the high mechanical strength of graphene oxide, the large specific surface area and the easy chemical modification, etc., and it is believed that this material has a great application prospect in the material field of high mechanical strength, good bonding ability.
The invention provides a preparation method of a repairable graphene oxide material based on hydrogen bond action, so that the problems in the prior art, such as material failure caused by microcracks generated by factors such as collision, illumination and the like of a polymer material in the service process, are solved; the mechanical properties and self-healing effect of hydrogen bond self-healing materials are generally exclusive of problems.
Disclosure of Invention
The invention provides a preparation method of a repairable graphene oxide material based on hydrogen bond action to solve the problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a repairable graphene oxide material based on hydrogen bonding comprises the following steps:
s1, dissolving 1.20-1.70g of 1, 2-bis (2-aminoethoxy) ethane in 5-10mL of N, N-dimethylformamide solution, and transferring the dissolved solution to a 50mL single-neck flask;
s2, adding 1.50-2.00g of 1, 1' -thiocarbonyl diimidazole into the single-neck flask in the S1, and dispersing uniformly by ultrasonic oscillation to obtain a uniform solution;
s3, transferring the 50mL single-neck flask which is placed with the uniform solution in the S2 into a constant-temperature oil bath at 25 ℃, and continuously performing magnetic stirring reaction for 24 hours under the condensation reflux;
s4, after the reaction in S3 is stopped, fully dissolving the reactant by using chloroform, slowly dropping the reactant into ether, settling, standing, and removing supernatant to obtain a precipitate product;
s5, centrifuging the precipitated product in the S4 at 200 revolutions per minute by using a centrifuge, collecting insoluble substances, and performing vacuum drying at 105 ℃ for 12 hours to obtain an ether-thiourea polymer;
s6, preparing the graphene oxide, wherein the basic process is divided into a low-temperature reaction stage, a medium-temperature reaction stage and a high-temperature reaction stage;
s7, weighing 8-12mL of N, N-dimethylformamide solution, 10-14mg of graphene oxide prepared in S6 and 1.5-2.5g of ether-thiourea polymer prepared in S5 in a 50mL single-neck flask, and performing ultrasonic dispersion for 2 hours to obtain a uniform solution;
s8, transferring the uniform solution in the S7 into a constant-temperature oil bath kettle at 120 ℃, vacuumizing the system, filling nitrogen for 3 times, condensing, refluxing, and continuously carrying out magnetic stirring reaction for 30 hours;
s9, after the reaction in the S8 is stopped, carrying out suction filtration while the reaction is hot, repeatedly washing the reactant by using N, N-dimethylformamide, washing away the unreacted ether-thiourea polymer, finally taking out the filter paper by using tweezers, lining the bottom with a piece of clean filter paper, and drying in a vacuum drying oven at 80 ℃ to constant weight to obtain the final target repairable graphene oxide material based on the hydrogen bond effect.
Preferably, in the S4, the reactant is fully dissolved by chloroform, then slowly dropped into ether, settled and stood, and the process of removing the supernatant liquid is repeated for 3-4 times.
Preferably, in the S3, before the condensation reflux, a 50mL single-neck flask needs to be vacuumized and filled with nitrogen for 3 times.
Preferably, the specific process for preparing the graphene oxide in S6 is as follows: and (3) a low-temperature reaction stage: adding 90mL of concentrated sulfuric acid into a dry 1000mL beaker, and cooling to 0 ℃ in an ice water bath; adding 3.0g of crystalline flake graphite under stirring, and stirring at 100 revolutions per minute for 5 minutes to uniformly disperse the crystalline flake graphite; then adding 1.5g of sodium nitrate, stirring uniformly, slowly adding 15g of potassium permanganate, controlling the stirring speed to be 200 r/min, controlling the reaction temperature to be 0-5 ℃, and reacting for 1 hour under the conditions; a medium-temperature reaction stage: integrally moving the reactant beaker and the stirrer into a constant-temperature water bath kettle at 35 ℃, and stirring and reacting for 1 hour when the temperature of the reactant rises to 35 ℃; a high-temperature reaction stage: after the medium-temperature reaction is finished, slowly and continuously adding 150mL of deionized water into a beaker under continuous stirring, controlling the reaction temperature at 90 ℃, and stirring for reaction for 30 minutes; after the reaction is finished, adding deionized water (warm water) to 500mL, controlling the temperature to be 45 ℃, slowly adding a small amount of 30% hydrogen peroxide (for removing unreacted potassium permanganate) until no bubbles are generated, filtering while hot, repeatedly washing with 5% hydrochloric acid solution, washing with deionized water until suction filtration cannot be performed; centrifuging and separating for several times at 9500 rpm with a centrifuge, and continuously measuring pH value until pH is close to 7; and finally, freeze drying to obtain the dried graphene oxide.
Preferably, in the step S9, the reactant is repeatedly washed with N, N-dimethylformamide 3 to 5 times.
Compared with the prior art, the invention provides a preparation method of a repairable graphene oxide material based on hydrogen bond action, which has the following beneficial effects:
1. the invention has the beneficial effects that: the repairable graphene oxide material which integrates good self-healing performance and mechanical performance and is based on hydrogen bond effect is obtained, the graphene oxide is mainly used as a matrix, the ether-thiourea polymer is used as a load, and the material synthesized by the method has a hydrogen bond type thiourea structure with a zigzag array and interacts with functional groups on the graphene oxide, so that the material has good self-healing performance and the mechanical performance of the material is enhanced. The material is simple in preparation process, easy in raw material obtaining and has the possibility of actual production.
Drawings
Fig. 1 is a nuclear magnetic resonance hydrogen spectrum of an ether-thiourea polymer with a hydrogen bond thiourea structure prepared by the preparation method of the repairable graphene oxide material based on hydrogen bonding;
fig. 2 is an infrared spectrum of a repairable graphene oxide material based on hydrogen bonding according to the preparation method of the repairable graphene oxide material based on hydrogen bonding of the present invention;
fig. 3 is a scanning electron microscope photograph of graphene oxide of a preparation method of a repairable graphene oxide material based on hydrogen bonding and the repairable graphene oxide material based on hydrogen bonding according to the present invention;
fig. 4 is a synthesis route diagram of a repairable graphene oxide material based on hydrogen bonding in the preparation method of the repairable graphene oxide material based on hydrogen bonding according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
Example 1:
dissolving 1, 2-bis (2-aminoethoxy) ethane 1.55g in N, N-dimethylformamide solution 5mL, adding into a 50mL single-neck flask, adding 1, 1' -thiocarbonyldiimidazole 1.78g, and performing ultrasonic dispersion to obtain uniform solution; transferring the flask into a constant-temperature oil bath kettle at 25 ℃, vacuumizing the system, filling nitrogen for 3 times, condensing, refluxing, and continuously carrying out magnetic stirring reaction for 24 hours; after the reaction is stopped, fully dissolving the reactant by using chloroform, slowly dripping the reactant into ether, settling, standing, removing supernatant, dissolving the precipitate by using chloroform, settling by using ether again, standing, and repeating the operation for 2-3 times; after the product was centrifuged at 200 rpm by a centrifuge, insoluble materials were collected and vacuum-dried at 105 ℃ for 12 hours to obtain an ether-thiourea polymer. The graphene oxide is prepared according to an improved Hummers method, and the basic process is divided into a low-temperature reaction stage, a medium-temperature reaction stage and a high-temperature reaction stage. The specific process operation is as follows: and (3) a low-temperature reaction stage: in a dry 1000mL beaker, 90mL of concentrated sulfuric acid was added and cooled to 0 ℃ in an ice water bath. Adding 3.0g of crystalline flake graphite under stirring, and stirring at 100 revolutions per minute for 5 minutes to uniformly disperse the crystalline flake graphite; then adding 1.5g of sodium nitrate, stirring uniformly, slowly adding 15g of potassium permanganate, controlling the stirring speed to be 200 r/min, controlling the reaction temperature to be 0-5 ℃, and reacting for 1 hour under the conditions; a medium-temperature reaction stage: integrally moving the reactant beaker and the stirrer into a constant-temperature water bath kettle at 35 ℃, and stirring and reacting for 1 hour when the temperature of the reactant rises to 35 ℃; a high-temperature reaction stage: after the medium-temperature reaction is finished, slowly and continuously adding 150mL of deionized water into a beaker under continuous stirring, controlling the reaction temperature at 90 ℃, and stirring for reaction for 30 minutes; after the reaction is finished, adding deionized water (warm water) to 500mL, controlling the temperature to be 45 ℃, slowly adding a small amount of 30% hydrogen peroxide (for removing unreacted potassium permanganate) until no bubbles are generated, filtering while hot, repeatedly washing with 5% hydrochloric acid solution, washing with deionized water until suction filtration cannot be performed; centrifuging and separating for several times at 9500 rpm with a centrifuge, and continuously measuring pH value until pH is close to 7; and finally, freeze drying to obtain the dried graphene oxide. Weighing 10mL of DMF, 10mg of graphene oxide and 2g of ether-thiourea polymer in a 50mL single-neck flask, and performing ultrasonic dispersion for 2 hours to obtain a uniform solution; transferring the flask into a constant-temperature oil bath kettle at 120 ℃, vacuumizing the system, filling nitrogen for 3 times, condensing, refluxing, and continuously carrying out magnetic stirring reaction for 30 hours; and after the reaction is stopped, carrying out suction filtration while the reaction is hot, repeatedly washing the reactant by using N, N-dimethylformamide, washing away unreacted ether-thiourea polymer, finally taking out the filter paper by using tweezers, lining the filter paper on the bottom together by using a piece of clean filter paper, and drying the filter paper in a vacuum drying oven at the temperature of 80 ℃ until the weight is constant to obtain the final target product.
Example 2:
dissolving 1, 2-bis (2-aminoethoxy) ethane 1.55g in N, N-dimethylformamide solution 5mL, adding into a 50mL single-neck flask, adding 1, 1' -thiocarbonyldiimidazole 1.78g, and performing ultrasonic dispersion to obtain uniform solution; transferring the flask into a constant-temperature oil bath kettle at 25 ℃, vacuumizing the system, filling nitrogen for 3 times, condensing, refluxing, and continuously carrying out magnetic stirring reaction for 24 hours; after the reaction is stopped, fully dissolving the reactant by using chloroform, slowly dripping the reactant into ether, settling, standing, removing supernatant, dissolving the precipitate by using chloroform, settling by using ether again, standing, and repeating the operation for 2-3 times; after the product was centrifuged at 200 rpm by a centrifuge, insoluble materials were collected and vacuum-dried at 105 ℃ for 12 hours to obtain an ether-thiourea polymer. The graphene oxide is prepared according to an improved Hummers method, and the basic process is divided into a low-temperature reaction stage, a medium-temperature reaction stage and a high-temperature reaction stage. The specific process operation is as follows: and (3) a low-temperature reaction stage: in a dry 1000mL beaker, 90mL of concentrated sulfuric acid was added and cooled to 0 ℃ in an ice water bath. Adding 3.0g of crystalline flake graphite under stirring, and stirring at 100 revolutions per minute for 5 minutes to uniformly disperse the crystalline flake graphite; then adding 1.5g of sodium nitrate, stirring uniformly, slowly adding 15g of potassium permanganate, controlling the stirring speed to be 200 r/min, controlling the reaction temperature to be 0-5 ℃, and reacting for 1 hour under the conditions; a medium-temperature reaction stage: integrally moving the reactant beaker and the stirrer into a constant-temperature water bath kettle at 35 ℃, and stirring and reacting for 1 hour when the temperature of the reactant rises to 35 ℃; a high-temperature reaction stage: after the medium-temperature reaction is finished, slowly and continuously adding 150mL of deionized water into a beaker under continuous stirring, controlling the reaction temperature at 90 ℃, and stirring for reaction for 30 minutes; after the reaction is finished, adding deionized water (warm water) to 500mL, controlling the temperature to be 45 ℃, slowly adding a small amount of 30% hydrogen peroxide (for removing unreacted potassium permanganate) until no bubbles are generated, filtering while hot, repeatedly washing with 5% hydrochloric acid solution, washing with deionized water until suction filtration cannot be performed; centrifuging and separating for several times at 9500 rpm with a centrifuge, and continuously measuring pH value until pH is close to 7; and finally, freeze drying to obtain the dried graphene oxide. Weighing 10mL of DMF, 10mg of graphene oxide and 1.25g of ether-thiourea polymer in a 50mL single-neck flask, and performing ultrasonic dispersion for 2 hours to obtain a uniform solution; transferring the flask into a constant-temperature oil bath kettle at 120 ℃, vacuumizing the system, filling nitrogen for 3 times, condensing, refluxing, and continuously carrying out magnetic stirring reaction for 30 hours; and after the reaction is stopped, carrying out suction filtration while the reaction is hot, repeatedly washing the reactant by using N, N-dimethylformamide, washing away unreacted ether-thiourea polymer, finally taking out the filter paper by using tweezers, lining the filter paper on the bottom together by using a piece of clean filter paper, and drying the filter paper in a vacuum drying oven at the temperature of 80 ℃ until the weight is constant to obtain the final target product.
Example 3:
dissolving 1, 2-bis (2-aminoethoxy) ethane 1.55g in N, N-dimethylformamide solution 5mL, adding into a 50mL single-neck flask, adding 1, 1' -thiocarbonyldiimidazole 1.78g, and performing ultrasonic dispersion to obtain uniform solution; transferring the flask into a constant-temperature oil bath kettle at 25 ℃, vacuumizing the system, filling nitrogen for 3 times, condensing, refluxing, and continuously carrying out magnetic stirring reaction for 24 hours; after the reaction is stopped, fully dissolving the reactant by using chloroform, slowly dripping the reactant into ether, settling, standing, removing supernatant, dissolving the precipitate by using chloroform, settling by using ether again, standing, and repeating the operation for 2-3 times; after the product was centrifuged at 200 rpm by a centrifuge, insoluble materials were collected and vacuum-dried at 105 ℃ for 12 hours to obtain an ether-thiourea polymer. The graphene oxide is prepared according to an improved Hummers method, and the basic process is divided into a low-temperature reaction stage, a medium-temperature reaction stage and a high-temperature reaction stage. The specific process operation is as follows: and (3) a low-temperature reaction stage: in a dry 1000mL beaker, 90mL of concentrated sulfuric acid was added and cooled to 0 ℃ in an ice water bath. Adding 3.0g of crystalline flake graphite under stirring, and stirring at 100 revolutions per minute for 5 minutes to uniformly disperse the crystalline flake graphite; then adding 1.5g of sodium nitrate, stirring uniformly, slowly adding 15g of potassium permanganate, controlling the stirring speed to be 200 r/min, controlling the reaction temperature to be 0-5 ℃, and reacting for 1 hour under the conditions; a medium-temperature reaction stage: integrally moving the reactant beaker and the stirrer into a constant-temperature water bath kettle at 35 ℃, and stirring and reacting for 1 hour when the temperature of the reactant rises to 35 ℃; a high-temperature reaction stage: after the medium-temperature reaction is finished, slowly and continuously adding 150mL of deionized water into a beaker under continuous stirring, controlling the reaction temperature at 90 ℃, and stirring for reaction for 30 minutes; after the reaction is finished, adding deionized water (warm water) to 500mL, controlling the temperature to be 45 ℃, slowly adding a small amount of 30% hydrogen peroxide (for removing unreacted potassium permanganate) until no bubbles are generated, filtering while hot, repeatedly washing with 5% hydrochloric acid solution, washing with deionized water until suction filtration cannot be performed; centrifuging and separating for several times at 9500 rpm with a centrifuge, and continuously measuring pH value until pH is close to 7; and finally, freeze drying to obtain the dried graphene oxide. Weighing 10mL of DMF, 10mg of graphene oxide and 1g of ether-thiourea polymer in a 50mL single-neck flask, and performing ultrasonic dispersion for 2 hours to obtain a uniform solution; transferring the flask into a constant-temperature oil bath kettle at 120 ℃, vacuumizing the system, filling nitrogen for 3 times, condensing, refluxing, and continuously carrying out magnetic stirring reaction for 30 hours; and after the reaction is stopped, carrying out suction filtration while the reaction is hot, repeatedly washing the reactant by using N, N-dimethylformamide, washing away unreacted ether-thiourea polymer, finally taking out the filter paper by using tweezers, lining the filter paper on the bottom together by using a piece of clean filter paper, and drying the filter paper in a vacuum drying oven at the temperature of 80 ℃ until the weight is constant to obtain the final target product.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (5)
1. A preparation method of a repairable graphene oxide material based on hydrogen bonding is characterized by comprising the following steps:
s1, dissolving 1.20-1.70g of 1, 2-bis (2-aminoethoxy) ethane in 5-10mL of N, N-dimethylformamide solution, and transferring the dissolved solution to a 50mL single-neck flask;
s2, adding 1.50-2.00g of 1, 1' -thiocarbonyl diimidazole into the single-neck flask in the S1, and dispersing uniformly by ultrasonic oscillation to obtain a uniform solution;
s3, transferring the 50mL single-neck flask which is placed with the uniform solution in the S2 into a constant-temperature oil bath at 25 ℃, and continuously performing magnetic stirring reaction for 24 hours under the condensation reflux;
s4, after the reaction in S3 is stopped, fully dissolving the reactant by using chloroform, slowly dropping the reactant into ether, settling, standing, and removing supernatant to obtain a precipitate product;
s5, centrifuging the precipitated product in the S4 at 200 revolutions per minute by using a centrifuge, collecting insoluble substances, and performing vacuum drying at 105 ℃ for 12 hours to obtain an ether-thiourea polymer;
s6, preparing the graphene oxide, wherein the basic process is divided into a low-temperature reaction stage, a medium-temperature reaction stage and a high-temperature reaction stage;
s7, weighing 8-12mL of N, N-dimethylformamide solution, 10-14mg of graphene oxide prepared in S6 and 1.5-2.5g of ether-thiourea polymer prepared in S5 in a 50mL single-neck flask, and performing ultrasonic dispersion for 2 hours to obtain a uniform solution;
s8, transferring the uniform solution in the S7 into a constant-temperature oil bath kettle at 120 ℃, vacuumizing the system, filling nitrogen for 3 times, condensing, refluxing, and continuously carrying out magnetic stirring reaction for 30 hours;
s9, after the reaction in the S8 is stopped, carrying out suction filtration while the reaction is hot, repeatedly washing the reactant by using N, N-dimethylformamide, washing away the unreacted ether-thiourea polymer, finally taking out the filter paper by using tweezers, lining the bottom with a piece of clean filter paper, and drying in a vacuum drying oven at 80 ℃ to constant weight to obtain the final target repairable graphene oxide material based on the hydrogen bond effect.
2. The preparation method of the repairable graphene oxide material based on hydrogen bonding as claimed in claim 1, wherein: in the S4, the reactant is fully dissolved by chloroform and then slowly dropped into ether, and the process of settling, standing and removing supernatant liquid is repeated for 3-4 times.
3. The preparation method of the repairable graphene oxide material based on hydrogen bonding as claimed in claim 1, wherein: in the S3, a 50mL single-neck flask was evacuated and purged with nitrogen 3 times before being refluxed.
4. The preparation method of the repairable graphene oxide material based on hydrogen bonding as claimed in claim 1, wherein: the specific process for preparing the graphene oxide in the S6 is as follows: and (3) a low-temperature reaction stage: adding 90mL of concentrated sulfuric acid into a dry 1000mL beaker, and cooling to 0 ℃ in an ice water bath; adding 3.0g of crystalline flake graphite under stirring, and stirring at 100 revolutions per minute for 5 minutes to uniformly disperse the crystalline flake graphite; then adding 1.5g of sodium nitrate, stirring uniformly, slowly adding 15g of potassium permanganate, controlling the stirring speed to be 200 r/min, controlling the reaction temperature to be 0-5 ℃, and reacting for 1 hour under the conditions; a medium-temperature reaction stage: integrally moving the reactant beaker and the stirrer into a constant-temperature water bath kettle at 35 ℃, and stirring and reacting for 1 hour when the temperature of the reactant rises to 35 ℃; a high-temperature reaction stage: after the medium-temperature reaction is finished, slowly and continuously adding 150mL of deionized water into a beaker under continuous stirring, controlling the reaction temperature at 90 ℃, and stirring for reaction for 30 minutes; after the reaction is finished, adding deionized water (warm water) to 500mL, controlling the temperature to be 45 ℃, slowly adding a small amount of 30% hydrogen peroxide (for removing unreacted potassium permanganate) until no bubbles are generated, filtering while hot, repeatedly washing with 5% hydrochloric acid solution, washing with deionized water until suction filtration cannot be performed; centrifuging and separating for several times at 9500 rpm with a centrifuge, and continuously measuring pH value until pH is close to 7; and finally, freeze drying to obtain the dried graphene oxide.
5. The preparation method of the repairable graphene oxide material based on hydrogen bonding as claimed in claim 1, wherein: in the S9, the reactant is repeatedly washed by N, N-dimethylformamide for 3-5 times.
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| CN107337927A (en) * | 2017-07-02 | 2017-11-10 | 东华大学 | A kind of graphene oxide with self-repair function/polyamic acid hydrogel and preparation method thereof |
| CN108997750A (en) * | 2018-09-28 | 2018-12-14 | 东北林业大学 | A kind of preparation method of graphene oxide self-healing polymers |
| CN111333870A (en) * | 2020-04-06 | 2020-06-26 | 刘云晖 | Self-repairable chitosan hydrogel and preparation method thereof |
| CN111363123A (en) * | 2020-04-06 | 2020-07-03 | 刘云晖 | Self-repairable epoxy resin and preparation method thereof |
| CN111363119A (en) * | 2020-04-06 | 2020-07-03 | 刘云晖 | Preparation method of self-repairable polyurethane |
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| CN107337927A (en) * | 2017-07-02 | 2017-11-10 | 东华大学 | A kind of graphene oxide with self-repair function/polyamic acid hydrogel and preparation method thereof |
| CN108997750A (en) * | 2018-09-28 | 2018-12-14 | 东北林业大学 | A kind of preparation method of graphene oxide self-healing polymers |
| CN111333870A (en) * | 2020-04-06 | 2020-06-26 | 刘云晖 | Self-repairable chitosan hydrogel and preparation method thereof |
| CN111363123A (en) * | 2020-04-06 | 2020-07-03 | 刘云晖 | Self-repairable epoxy resin and preparation method thereof |
| CN111363119A (en) * | 2020-04-06 | 2020-07-03 | 刘云晖 | Preparation method of self-repairable polyurethane |
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Application publication date: 20210129 |