CN112480339B - Preparation method of graphene-based epoxy copolymer for protecting silicate cultural relics - Google Patents
Preparation method of graphene-based epoxy copolymer for protecting silicate cultural relics Download PDFInfo
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Abstract
The invention discloses a preparation method of a graphene-based epoxy copolymer for protecting silicate cultural relics, which comprises the following steps: step 1: dispersing graphene oxide in tetrahydrofuran to obtain a graphene dispersion liquid; and 2, step: sequentially adding triethylamine and 4-dimethylaminopyridine into the graphene dispersion liquid to obtain a mixed liquid A, adding 4-chloromethyl phenyl trichlorosilane into the mixed liquid A, reacting, and performing post-treatment to obtain a graphene-based initiator GO-g-Cl; and 3, step 3: and dispersing the graphene-based initiator GO-g-Cl in N, N-dimethylformamide to obtain a mixed solution B, sequentially adding cuprous chloride, N,N,N',N,'N'' -pentamethyldiethylenetriamine, methyl methacrylate and glycidyl methacrylate into the mixed solution B in a nitrogen protection atmosphere, carrying out thermal reaction, and carrying out post-treatment to obtain the graphene-based epoxy copolymer GO-g- (PMMA-co-PGMA). The invention can solve the problem that the existing silicate cultural relic protection material has poor weather resistance.
Description
Technical Field
The invention belongs to the technical field of silicate cultural relic protection materials, and particularly relates to a preparation method of a graphene-based epoxy copolymer for protecting silicate cultural relics.
Background
Silicate materials are widely applied to architectural decoration and the like, and cultural relics taking the silicate materials as raw materials are widely distributed in China and form an important component of historical cultural heritage. However, most silicate cultural relics are affected by natural factors for a long time and have the phenomena of efflorescence, falling off and the like, so that a proper material is urgently needed for effectively protecting the silicate cultural relics. However, the problem of poor weather resistance is common in the current protective materials.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a preparation method of a graphene-based epoxy copolymer for protecting silicate cultural relics, and aims to solve the problem that the existing silicate cultural relic protection material is poor in weather resistance.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a preparation method of a graphene-based epoxy copolymer for protecting silicate cultural relics comprises the following steps:
step 1: dispersing graphene oxide in tetrahydrofuran to obtain a graphene dispersion liquid;
step 2: sequentially adding triethylamine and 4-dimethylaminopyridine into the graphene dispersion liquid to obtain a mixed liquid A, adding 4-chloromethyl phenyl trichlorosilane into the mixed liquid A, reacting, and performing aftertreatment to obtain a graphene-based initiator GO-g-Cl;
and step 3: and dispersing the graphene-based initiator GO-g-Cl in N, N-dimethylformamide to obtain a mixed solution B, sequentially adding cuprous chloride, N, N, N' -pentamethyldiethylenetriamine, methyl methacrylate and glycidyl methacrylate into the mixed solution B in a nitrogen protection atmosphere, carrying out thermal reaction, and carrying out post-treatment to obtain the graphene-based epoxy copolymer GO-g- (PMMA-co-PGMA).
Further, in the step 1, dispersing graphene oxide in tetrahydrofuran by adopting ultrasonic dispersion, wherein the ultrasonic time is 10-30 min; the concentration of the graphene dispersion liquid is 0.5-2 mg/ml.
Further, in step 2, the mass ratio of the triethylamine, the 4-dimethylaminopyridine and the 4-chloromethylphenyltrichlorosilane is (0.34-0.85): 1: (1.36-2.72).
Further, in step 2, the post-treatment steps are washing, centrifuging and drying.
Further, in the step 2, during washing, the washing solvents are ethanol, distilled water and tetrahydrofuran, and washing is repeated for 1-2 times respectively; when in centrifugation, the rotating speed is 8000-; the drying method is vacuum drying at room temperature for 2-3 days.
Further, in the step 3, dispersing the graphene-based initiator GO-g-Cl in N, N-dimethylformamide by ultrasonic dispersion for 10-30 min; the concentration of the mixed solution B is 0.6-2.5 mg/ml.
Further, in the step 3, the content of the cuprous chloride is 0.04-0.056 mmol;
the content of the N, N, N' -pentamethyldiethylenetriamine is 0.11-0.27 mmol;
the molar ratio of the methyl methacrylate to the glycidyl methacrylate is (10-16): 1.
further, in the step 3, the time of the thermal reaction is 7-24 h; the temperature of the thermal reaction is 90-110 ℃; the post-treatment steps are precipitation, reduced pressure filtration and drying.
Further, during precipitation, the precipitation solvent is methanol;
during drying, the drying mode is vacuum drying, the drying temperature is room temperature, and the drying time is 1-3 days.
Compared with the prior art, the invention has at least the following beneficial effects: aiming at the problem of poor weather resistance of the existing silicate cultural relic protection material, the invention introduces graphene with excellent performance, wherein the graphene is formed by sp atoms of carbon atoms2The two-dimensional carbon nanomaterials, which are hexagonal honeycomb lattices composed of hybrid orbitals, are the thinnest and hardest materials discovered to date. The surface and the edge of the graphene have a large number of functional groups such as hydroxyl, carboxyl and the like, and the graphene is very easy to react with polar substances, so that the surface modification and the grafting of polymer monomers are possible. The graphene has a special lamellar structure, can form a compact network in the material, prevents the diffusion of molecules, forms a labyrinth effect, can be used as an excellent physical barrier, prevents the permeation of oxygen and corrosive substances, and improves the aging resistance of the material. The graphene has high toughness, can be infinitely stretched, and is subjected to bending deformation of carbon atoms under the action of external force, so that the graphene has high stability. In addition, the graphene has hydrophobic and oleophobic properties and good glossiness. Methyl Methacrylate (MMA) has continuity, film-forming property, continuity and compatibility, Glycidyl Methacrylate (GMA) is a bifunctional monomer, can provide continuous phase and adhesive property, is better combined with a matrix, and has strong stabilityThe synergistic effect is expected to obtain a long-term weather-resistant protective material with high transparency, high hydrophobicity and high adhesiveness.
According to the invention, graphene is firstly subjected to surface modification, and then atom transfer radical polymerization is initiated by utilizing the surface to polymerize monomers, so that the dispersion of the graphene in a microscopic layer in a polymer matrix is enhanced, the possibility of graphene aggregation is greatly reduced, the phenomenon of stress concentration in the film can be better avoided, and the occurrence of phase separation can be greatly reduced due to the bonding effect of chemical bonds.
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FIG. 1 is a preparation method of graphene-based initiator GO-g-Cl;
FIG. 2 is a preparation method of graphene-based copolymer GO-g- (PMMA-co-PGMA);
FIG. 3 is a transmission electron microscope image of graphene oxide GO;
FIG. 4 is a transmission electron microscope image of graphene-based polymer GO-g- (PMMA-co-PGMA).
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As a specific embodiment of the present invention, a method for preparing a graphene-based epoxy copolymer for protecting silicate cultural relics comprises the following steps:
step 1: preparing graphene oxide by using a Hummers method;
step 2: carrying out ultrasonic dispersion on graphene oxide in tetrahydrofuran uniformly to obtain a graphene dispersion liquid;
preferably, the ultrasonic time is 10-30 min; the concentration of the graphene dispersion liquid is 0.5-2 mg/ml.
And step 3: under the condition of stirring at room temperature, sequentially adding triethylamine and 4-dimethylaminopyridine into the graphene dispersion liquid to obtain a mixed liquid A, then slowly dropwise adding 4-chloromethyl phenyl trichlorosilane into the mixed liquid A for reaction, and carrying out aftertreatment to obtain a graphene-based initiator GO-g-Cl;
preferably, the mass ratio of the triethylamine to the 4-dimethylaminopyridine to the 4-chloromethylphenyltrichlorosilane is (0.34-0.85): 1: (1.36-2.72);
the reaction time is 24 h;
the post-treatment steps comprise washing, centrifuging and drying, and specifically, when washing, washing solvents comprise ethanol, distilled water and tetrahydrofuran, and washing is repeated for 1-2 times respectively; when in centrifugation, the rotating speed is 8000-; the drying method is vacuum drying at room temperature for 2-3 days.
And 4, step 4: carrying out ultrasonic treatment on graphene-based initiator GO-g-Cl until the graphene-based initiator GO-g-Cl is uniformly dispersed in N, N-dimethylformamide to obtain a mixed solution B, sequentially adding cuprous chloride, N, N, N' -pentamethyldiethylenetriamine, methyl methacrylate and glycidyl methacrylate into the mixed solution B in a nitrogen protection atmosphere, carrying out thermal reaction, and carrying out post-treatment to obtain graphene-based epoxy copolymer GO-g- (PMMA-co-PGMA);
preferably, the nitrogen protection atmosphere is vacuumized and nitrogen is introduced for 3 to 5 times at room temperature; the ultrasonic treatment time is 10-30 min; the concentration of the mixed solution B is 0.6-2.5 mg/ml;
the content of cuprous chloride is 0.04-0.056 mmol;
the content of N, N, N' -pentamethyldiethylenetriamine is 0.11-0.27 mmol;
the molar ratio of methyl methacrylate to glycidyl methacrylate is (10-16): 1;
the thermal reaction time is 7-24 h; the temperature of the thermal reaction is 90-110 ℃;
the post-treatment comprises the steps of precipitation, reduced pressure filtration and drying, and specifically, during precipitation, the precipitation solvent is methanol; during drying, the drying mode is vacuum drying, the drying temperature is room temperature, and the drying time is 1-3 days;
the cuprous chloride, the methyl methacrylate and the glycidyl methacrylate in the invention are respectively purified cuprous chloride, purified methyl methacrylate and purified glycidyl methacrylate.
Example 1:
firstly, preparing Graphene Oxide (GO) by adopting a Hummers method;
A) placing graphite powder, sodium nitrate and a proper amount of concentrated sulfuric acid into a three-neck flask, and mixing in an ice-water bath;
B) slowly adding potassium permanganate under magnetic stirring, and stirring for 48 h;
C) slowly adding hydrogen peroxide, adding deionized water, completely oxidizing, filtering, and washing with hydrochloric acid; drying in a vacuum drying oven at 60 deg.C, and storing for use.
The structure of the graphene oxide prepared in the above-mentioned manner is observed by a transmission electron microscope, and fig. 3 shows a micrograph of the graphene oxide prepared in example 1 of the present invention.
Placing GO obtained in the first step of reaction and Tetrahydrofuran (THF) in a round-bottom flask, performing ultrasonic treatment for 10min until GO is uniformly dispersed, wherein the concentration of a dispersion liquid is 0.5mg/ml, adding Triethylamine (TEA) and 4-Dimethylaminopyridine (DMAP) under the condition of magnetic stirring, then slowly dropwise adding 4-chloromethyl phenyl trichlorosilane (the mass ratio of triethylamine to 4-dimethylaminopyridine to 4-chloromethyl phenyl trichlorosilane is 0.34: 1: 2.72), reacting for 24h at room temperature, washing a product with ethanol for 2 times, washing with distilled water for 2 times, washing with THF for 1 time, centrifuging for 15min at the rotating speed of 8000r/min, and performing vacuum drying for 2 days at room temperature to constant weight to obtain a solid product of the chlorine-containing graphene-based initiator GO-g-Cl.
Thirdly, adding the chlorine-containing graphene-based initiator GO-g-Cl and N, N-dimethylformamide obtained in the previous step into a reaction bottle, performing ultrasonic treatment for 10min until the GO-g-Cl is uniformly dispersed, introducing nitrogen gas under vacuum at room temperature, repeating the introduction for 4 times, adding purified CuCl (0.04mmol), N, N, N' -pentamethyldiethylenetriamine (0.11mmol, PMDETA) in this order under a nitrogen atmosphere, and refining purified Methyl Methacrylate (MMA) and Glycidyl Methacrylate (GMA) (mixed monomer molar ratio MMA: GMA is 16: 1, the reaction is carried out in an oil bath at the temperature of 90 ℃ for 24 hours, the product is precipitated in methanol, the pressure is reduced and the filtration is carried out, and the vacuum drying is carried out for 3 days at the room temperature, thus obtaining the white solid product graphene-based epoxy copolymer GO-g- (PMMA-co-PGMA).
The graphene-based epoxy copolymer GO-g- (PMMA-co-PGMA) structure prepared by the method is observed by a transmission electron microscope; referring to FIG. 4, a micrograph of graphene oxide based polymer GO-g- (PMMA-co-PGMA) prepared according to example 1 of the present invention is shown.
Example 2:
firstly, preparing Graphene Oxide (GO) by adopting a Hummers method;
placing GO obtained in the first step of reaction and Tetrahydrofuran (THF) in a round-bottom flask, performing ultrasonic treatment for 20min until GO is uniformly dispersed, wherein the concentration of a dispersion liquid is 1.2mg/ml, adding Triethylamine (TEA) and 4-Dimethylaminopyridine (DMAP) under the condition of magnetic stirring, then slowly dropwise adding 4-chloromethyl phenyl trichlorosilane (the mass ratio of triethylamine to 4-dimethylaminopyridine to 4-chloromethyl phenyl trichlorosilane is 0.85: 1: 1.36) by using an injector, reacting for 24h at room temperature, washing the product by using ethanol for 1 time, washing the product for 2 times by using distilled water, washing the THF for 2 times, centrifuging for 7min at the rotating speed of 10000r/min, and performing vacuum drying for 2 days at room temperature to constant weight to obtain a solid product of the chlorine-containing graphene-based initiator GO-g-Cl.
Thirdly, adding the chlorine-containing graphene-based initiator GO-g-Cl and N, N-dimethylformamide obtained in the previous step into a reaction bottle, carrying out ultrasonic treatment for 15min until the GO-g-Cl is uniformly dispersed, introducing nitrogen gas under vacuum at room temperature, repeating the introduction for 5 times, adding purified CuCl (0.048mmol), N, N, N' -pentamethyldiethylenetriamine (0.25mmol, PMDETA) in this order under a nitrogen atmosphere, and refining purified Methyl Methacrylate (MMA) and Glycidyl Methacrylate (GMA) (mixed monomer molar ratio MMA: GMA is 13: 1, the reaction is carried out in an oil bath at 100 ℃ for 10h at constant temperature, the product is precipitated in methanol, the pressure is reduced and the filtration is carried out, and the vacuum drying is carried out for 1 day at room temperature, thus obtaining the white solid product graphene-based epoxy copolymer GO-g- (PMMA-co-PGMA).
Example 3:
firstly, preparing Graphene Oxide (GO) by adopting a Hummers method;
placing GO obtained in the first step of reaction and Tetrahydrofuran (THF) in a round-bottom flask, performing ultrasonic treatment for 15min until GO is uniformly dispersed, wherein the concentration of a dispersion solution is 1mg/ml, adding Triethylamine (TEA) and 4-Dimethylaminopyridine (DMAP) under the condition of magnetic stirring, then slowly dropwise adding 4-chloromethyl phenyl trichlorosilane (the mass ratio of triethylamine to 4-dimethylamino pyridine to 4-chloromethyl phenyl trichlorosilane is 0.6: 1: 2.04), reacting for 24h at room temperature, washing the product with ethanol for 2 times, washing with distilled water for 1 time, washing with THF for 1 time, centrifuging for 11min at the rotating speed of 9000r/min, and performing vacuum drying for 3 days at room temperature to constant weight to obtain a solid product, namely the chlorine-containing graphene-based initiator GO-g-Cl.
Thirdly, adding the chlorine-containing graphene-based initiator GO-g-Cl and N, N-dimethylformamide obtained in the previous step into a reaction bottle, performing ultrasonic treatment for 20min until the GO-g-Cl is uniformly dispersed, introducing nitrogen gas under vacuum at room temperature, repeating the introduction for 5 times, adding purified CuCl (0.056mmol), N, N, N' -pentamethyldiethylenetriamine (0.27mmol, PMDETA) in this order under a nitrogen atmosphere, and refining purified Methyl Methacrylate (MMA) and Glycidyl Methacrylate (GMA) (mixed monomer molar ratio MMA: GMA is 15: 1, the reaction is carried out in an oil bath at the temperature of 95 ℃ for 24 hours, the product is precipitated in methanol, the pressure is reduced and the filtration is carried out, and the vacuum drying is carried out for 2 days at the room temperature, thus obtaining the white solid product graphene-based epoxy copolymer GO-g- (PMMA-co-PGMA).
Example 4:
firstly, preparing Graphene Oxide (GO) by adopting a Hummers method;
placing GO obtained in the first step of reaction and Tetrahydrofuran (THF) in a round-bottom flask, performing ultrasonic treatment for 30min until GO is uniformly dispersed, wherein the concentration of a dispersion liquid is 2mg/ml, adding Triethylamine (TEA) and 4-Dimethylaminopyridine (DMAP) under the condition of magnetic stirring, then slowly dropwise adding 4-chloromethyl phenyl trichlorosilane (the mass ratio of triethylamine to 4-dimethylamino pyridine to 4-chloromethyl phenyl trichlorosilane is 0.85: 1: 2.72), reacting for 24h at room temperature, washing the product with ethanol for 2 times, washing with distilled water for 2 times, washing with THF for 1 time, centrifuging for 7min at the rotating speed of 10000r/min, and performing vacuum drying for 2 days at room temperature to constant weight to obtain a solid product, namely the chlorine-containing graphene-based initiator GO-g-Cl.
Thirdly, adding the chlorine-containing graphene-based initiator GO-g-Cl and N, N-dimethylformamide obtained in the previous step into a reaction bottle, performing ultrasonic treatment for 30min until the GO-g-Cl is uniformly dispersed, introducing nitrogen gas under vacuum at room temperature, repeating the introduction for 3 times, adding purified CuCl (0.04mmol), N, N, N' -pentamethyldiethylenetriamine (0.2mmol, PMDETA) in this order under a nitrogen atmosphere, and refining purified Methyl Methacrylate (MMA) and Glycidyl Methacrylate (GMA) (mixed monomer molar ratio MMA: GMA is 10: 1, the reaction is carried out for 7h in an oil bath at the temperature of 110 ℃, the product is precipitated in methanol, the pressure is reduced and the filtration is carried out, and the vacuum drying is carried out for 3 days at the room temperature, thus obtaining the white solid product graphene-based epoxy copolymer GO-g- (PMMA-co-PGMA).
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that the following descriptions are only illustrative and not restrictive, and that the scope of the present invention is not limited to the above embodiments: any person skilled in the art can modify or easily conceive the technical solutions described in the foregoing embodiments or equivalent substitutes for some technical features within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being included therein. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (1)
1. A preparation method of a graphene-based epoxy copolymer for protecting silicate cultural relics is characterized by comprising the following steps:
step 1: dispersing graphene oxide in tetrahydrofuran by adopting ultrasonic dispersion, wherein the ultrasonic time is 10-30min, so as to obtain a graphene dispersion liquid, and the concentration of the graphene dispersion liquid is 0.5-2 mg/ml;
and 2, step: sequentially adding triethylamine and 4-dimethylaminopyridine into the graphene dispersion liquid to obtain a mixed liquid A, adding 4-chloromethyl phenyl trichlorosilane into the mixed liquid A for reaction, washing, centrifuging and drying to obtain a graphene-based initiator GO-g-Cl; the mass ratio of the triethylamine to the 4-dimethylaminopyridine to the 4-chloromethylphenyltrichlorosilane is (0.34-0.85): 1: (1.36-2.72); when washing, the washing solvent is ethanol, distilled water and tetrahydrofuran, and washing is repeated for 1-2 times respectively; when in centrifugation, the rotating speed is 8000-; the drying mode is vacuum drying for 2-3 days at room temperature;
and step 3: adopting ultrasonic dispersion to disperse the graphene-based initiator GO-g-Cl is dispersed in N, N-dimethylformamide for 10-30min to obtain mixed solution B, the concentration of the mixed solution B is 0.6-2.5mg/ml, cuprous chloride, N, N, N ', N', N '' -pentamethyldiethylenetriamine, methyl methacrylate and glycidyl methacrylate are sequentially added into the mixed solution B in the nitrogen protection atmosphere, thermal reaction is carried out, and post treatment is carried out to obtain graphene-based epoxy copolymer GO-g-(PMMA-co-PGMA); the content of the cuprous chloride is 0.04-0.056 mmol; the content of the N, N, N ', N', N '' -pentamethyldiethylenetriamine is 0.11 to 0.27 mmol; the molar ratio of the methyl methacrylate to the glycidyl methacrylate is (10-16): 1; the thermal reaction time is 7-24 h; the temperature of the thermal reaction is 90-110 ℃; the post-treatment comprises the steps of precipitation, reduced pressure filtration and drying; during precipitation, the precipitation solvent is methanol; during drying, the drying mode is vacuum drying, the drying temperature is room temperature, and the drying time is 1-3 days.
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|---|---|---|---|---|
| CN108084379A (en) * | 2017-12-21 | 2018-05-29 | 西安交通大学 | For the preparation method of POSS Quito arm block copolymer of historical relic bonding protection |
| CN109228778A (en) * | 2018-09-07 | 2019-01-18 | 中国科学院上海硅酸盐研究所 | The vertex-gluing graph method of silicate cultural relic |
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| CN108084379A (en) * | 2017-12-21 | 2018-05-29 | 西安交通大学 | For the preparation method of POSS Quito arm block copolymer of historical relic bonding protection |
| CN109228778A (en) * | 2018-09-07 | 2019-01-18 | 中国科学院上海硅酸盐研究所 | The vertex-gluing graph method of silicate cultural relic |
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