CN114479328A - Preparation method of acetal polymer-graphene composite material - Google Patents
Preparation method of acetal polymer-graphene composite material Download PDFInfo
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Abstract
The invention provides a preparation method of an acetal polymer-graphene composite material, and belongs to the field of composite materials. Firstly, preparing graphene oxide and graphene quantum dot water dispersion liquid; and then uniformly dispersing the acetal polymer into a polymer precursor, and carrying out in-situ polymerization on the acetal polymer and aldehyde liquid to prepare the acetal polymer-graphene composite material. The quantum dots in the preparation method can provide an acid catalyst in the polymerization reaction, so that a large amount of acid liquor is prevented from being introduced in the conventional reaction, the cost of acid treatment is saved, and the prepared composite material has high storage stability and is not deteriorated after being placed for a long time; the method has simple process flow and is beneficial to large-scale industrial production; the acetal polymer-graphene composite material prepared by the invention has good uniformity, and after a small amount of graphene is added, the comprehensive properties of the composite material, such as strength, thermal stability, ultraviolet resistance and the like, are further improved, and the application prospect of the acetal polymer material is further expanded.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a preparation method of an acetal polymer-graphene composite material.
Background
Acetal polymer materials, because of their good flexibility, adhesion, solubility, light resistance, water resistance, high wear resistance, cold resistance and moldability, and high tensile strength and impact strength, have been widely used in the fields of laminated safety glass, adhesives, ceramic decal paper, aluminum foil paper, electrical materials, glass fiber reinforced plastic products, fabric treating agents, etc., it can be said that acetal polymer materials have become an indispensable synthetic resin material.
However, in the preparation of conventional acetal polymer materials, a large amount of acid needs to be added as a catalyst for the reaction, which causes two major problems: 1. the acetal polymer material can keep viscosity during the reaction process, so that acid is contained in the product and is difficult to remove, the storage stability of the material is influenced, and the subsequent processing and application of the material are further influenced; 2. the acid treatment process is time and labor consuming, increasing the cost of industrial production.
Disclosure of Invention
The invention aims to provide a preparation method of an acetal polymer-graphene composite material, wherein a large amount of acid solution is not introduced in the process of preparing the acetal polymer-graphene composite material, so that the introduction of a large amount of acid solution in conventional reaction is avoided, the cost of acid treatment is saved, and the composite material is stable in storage and does not deteriorate after being placed for a long time. The method has simple process flow and is suitable for large-scale production. In addition, the composite material has the performances of higher strength, thermal stability, tensile resistance, ultraviolet resistance and the like.
In order to achieve the above object, the present invention provides the following technical solutions: uniformly dispersing graphene oxide and graphene oxide quantum dots in a polymer precursor to form a precursor mixed material with the pH of 2-5, and carrying out acetal polymerization on the precursor mixed material and aldehyde liquid to obtain the polymer-graphene composite material; the mass of the graphene oxide and the graphene oxide quantum dots accounts for 0.1-1% of the total mass of the composite material.
Further, the pH value of the mixed material is adjusted by adjusting the proportion of the graphene oxide and the graphene oxide quantum dots, and the proportion of the graphene oxide and the graphene oxide quantum dots is 6: 4-9: 1.
Furthermore, the size of the graphene oxide is 5-10 μm.
Further, the aldehyde liquid is one or more of formaldehyde, acetaldehyde, n-butyl aldehyde and other aldehyde compounds with the mass fraction of 37-40%.
Further, the polymer precursor is polyvinyl alcohol, phenol and other organic compounds with alcoholic hydroxyl groups.
Further, the graphene oxide quantum dots are obtained by the following method: adding 0.1-1.5 mL of ammonia water and 0.1-1.5 mL of hydrogen peroxide into 30mL of graphene oxide aqueous dispersion with the concentration of 1-5 mg/mL, diluting to 150-200 mL, placing in a reaction kettle, reacting at the temperature of 120-180 ℃ for 8-12 h, and purifying to prepare graphene quantum dot aqueous dispersion; the concentration of the ammonia water is 25%, and the concentration of the hydrogen peroxide is 30%.
Further, after mixing graphene oxide, graphene quantum dots and water, adding 100 parts by mass of a polymer precursor, heating and stirring at 70-100 ℃ until the polymer precursor is completely dissolved, adding 50-100 parts by mass of aldehyde liquid after cooling, stirring for half an hour, carrying out in-situ polymerization at 70-100 ℃ for 30 min-3 h, cooling to room temperature, filtering, and drying to obtain the acetal polymer-graphene composite material.
The invention has the beneficial effects that:
according to the preparation method, the graphene oxide and the quantum dot water dispersion liquid can provide a catalyst, so that the introduction of a large amount of acid in the conventional acetal reaction is avoided, and the cost of subsequent acid treatment is saved. And the composite material is stable to store and does not deteriorate after being placed for a long time.
According to the invention, the graphene oxide aqueous dispersion is prepared, the proportion of hydroxyl, carboxyl and other oxygen-containing functional groups in the small-sized graphene oxide is further improved, wherein the hydroxyl and the carboxyl can be respectively used as functional groups and catalysts for polymerization reaction, so that the graphene oxide can be uniformly dispersed and stably exist in the reaction process and the product; and the large-size graphene oxide can participate in the reaction, and simultaneously the two-dimensional structure of the graphene is kept as far as possible, so that the improvement of the comprehensive performance of the composite material is promoted.
According to the invention, graphene oxide is further oxidized and cut to prepare the graphene quantum dot water dispersion liquid, the carboxyl proportion in the structure is further improved, the hydrogen ion concentration in the subsequent polymerization reaction can be further adjusted by adjusting the addition amount of the graphene oxide, and the catalytic efficiency is improved. In addition, due to the small size and the stable structure of the graphene quantum dots, the graphene quantum dots can be uniformly dispersed in the composite material, and the thermal stability of the composite material is improved.
In the acetal polymer graphene composite material prepared by the invention, due to the unique two-dimensional structure of graphene oxide, the strength, stretch resistance, flame retardance, ultraviolet resistance and other properties of the composite material can be improved by adding the graphene oxide into the acetal polymer material.
The method has simple process flow and high production efficiency, and is suitable for large-scale production.
Drawings
Fig. 1 is an SEM image of graphene oxide prepared in example 1;
fig. 2 is a TEM high resolution image of the graphene oxide quantum dot prepared in example 1;
fig. 3 is a graph comparing the uv absorption of the polyvinyl butyral-graphene composite prepared in example 1 with that of the polyvinyl butyral prepared in comparative example 1.
Fig. 4 is a thermogravimetric comparison of the polyvinyl butyral-graphene composite prepared in example 1 with the polyvinyl butyral prepared in comparative example 1.
Fig. 5 is a graph comparing the uv absorption of the polyvinyl formal-graphene composite material prepared in example 2 with that of the polyvinyl formal prepared in comparative example 2.
Fig. 6 is a thermogravimetric comparison graph of the polyvinyl formal-graphene composite material prepared in example 2 and the polyvinyl formal prepared in comparative example 2.
Fig. 7 is a pictorial representation of the polyvinyl butyral-graphene composite prepared in example 1 after being left for 2 months;
FIG. 8 is a pictorial representation of the polyvinyl butyral prepared in comparative example 1 after storage for 2 months;
fig. 9 is a diagram of a polyvinyl formal-graphene composite material prepared in example 2 after being left for 2 months;
FIG. 10 is a diagram showing a sample of polyvinyl formal prepared in comparative example 2 after being left for 2 months;
fig. 11 is a diagram of a polyvinyl butyral-graphene composite material prepared in comparative example 3 placed in a solvent.
Detailed Description
In the present invention, all the raw material components are commercially available products well known to those skilled in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the 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.
Example 1
Step 1: respectively adding 25g of potassium permanganate into 500 mL of pre-cooled 93% sulfuric acid, stirring and dissolving, adding 5g of natural graphite, oxidizing for 24 h at 41 ℃, adding 10 mL of hydrogen peroxide, and centrifugally washing to prepare graphene oxide aqueous dispersion;
step 2: preparing the graphene oxide aqueous dispersion obtained in the step 1 into a concentration of 2 mg/mL, taking 30mL, adding 0.4mL of ammonia water and hydrogen peroxide into the graphene oxide aqueous dispersion, diluting to 165mL, reacting at the temperature of 120 ℃ for 12h, and purifying to prepare the graphene quantum dot aqueous dispersion. The size of the obtained quantum dots is 5-6 nm.
And step 3: mixing 0.8 g of graphene oxide prepared in the steps 1 and 2 with 0.2 g of graphene quantum dots to obtain a mixed solution with the pH value of 5, then adding 100 g of polyvinyl alcohol, heating and stirring at 85 ℃ until the polyvinyl alcohol is completely dissolved, adding 70 mL of n-butyl aldehyde into the mixed solution after cooling, stirring for half an hour, carrying out in-situ polymerization reaction at the temperature of 80 ℃ for 3 hours, cooling to room temperature, and filtering, washing and drying to obtain the polyvinyl butyral-graphene composite material;
an SEM image of the graphene oxide prepared in example 1 is shown in FIG. 1, and it can be seen that the size of the prepared graphene oxide is 5-10 μm;
a TEM high resolution image of the graphene oxide quantum dot prepared in example 1 is shown in fig. 2, and it can be seen that the size of the prepared graphene quantum dot is 5-6 nm.
The ultraviolet resistance of the prepared polyvinyl butyral-graphene composite material is shown in fig. 3, and it can be seen from the figure that compared with the polyvinyl butyral material prepared in comparative example 1, the absorption value of the composite material in an ultraviolet region is obviously increased, which indicates that the composite material has higher ultraviolet resistance;
the tensile resistance of the prepared polyvinyl butyral-graphene composite material is shown in table 1, and as shown in the table, compared with the polyvinyl butyral material prepared in comparative example 1, the composite material has higher tensile strength and elongation at break, which indicates that the composite material has higher tensile resistance;
the thermal stability of the polyvinyl butyral-graphene composite material is shown in fig. 4, and it can be seen from the graph that the thermal weight loss ratio of the composite material is 14% and the thermal weight loss ratio of the polyvinyl butyral material prepared in comparative example 1 is 17% under the same temperature rise range, which indicates that the composite material has higher thermal stability.
A physical diagram of the polyvinyl butyral-graphene composite material after being placed for 1 month is shown in fig. 7, and it can be seen from the physical diagram that graphene in the prepared composite material is uniformly dispersed in the composite material.
Example 2
Step 1: respectively adding 22 g of potassium permanganate into 500 mL of pre-cooled 85% sulfuric acid, stirring and dissolving, adding 5g of natural graphite, oxidizing for 24 h at 45 ℃, adding 13 mL of hydrogen peroxide, and centrifugally washing to prepare a graphene oxide aqueous dispersion; SEM analysis shows that the size of the obtained graphene is 5-10 mu m;
step 2: preparing the graphene oxide aqueous dispersion obtained in the step 1 into a solution with a concentration of 3 mg/mL, taking 30mL, adding 1mL of ammonia water and hydrogen peroxide into the solution, diluting the solution to 180mL, reacting the solution at 150 ℃ for 10 hours, and purifying the solution to prepare the graphene quantum dot aqueous dispersion. The TEM high resolution image shows that the size of the prepared graphene quantum dot is 5-6 nm.
And step 3: mixing 0.45 g of graphene oxide prepared in the steps 1 and 2 with 0.05g of graphene quantum dots to obtain a mixed solution with the pH value of 3, adding 100 g of polyvinyl alcohol, heating and stirring at 90 ℃ for 2 hours until the polyvinyl alcohol is completely dissolved, adding 80mL of formaldehyde solution with the mass fraction of 37% after cooling, stirring for half an hour, carrying out in-situ polymerization at the temperature of 85 ℃ for 2 hours, cooling to room temperature, filtering, washing and drying to obtain a polyvinyl formal-graphene composite material;
the ultraviolet resistance of the prepared polyvinyl formal-graphene composite material is shown in fig. 5, and it can be seen from the figure that compared with the polyvinyl formal material prepared in the proportion 2, the absorption value of the composite material in an ultraviolet region is obviously increased, which indicates that the composite material has higher ultraviolet resistance;
the tensile resistance of the prepared polyvinyl formal-graphene composite material is shown in table 2, and it can be seen from the table that the composite material has higher tensile strength and elongation at break than the polyvinyl formal material prepared in comparative example 2, which indicates that the composite material has higher tensile resistance;
the thermal stability of the polyvinyl formal-graphene composite material is shown in fig. 6, and it can be seen from the graph that the thermal weight loss ratio of the composite material is 11% and the thermal weight loss ratio of the polyvinyl formal material prepared in comparative example 2 is 17% under the same temperature rise range, which indicates that the composite material has higher thermal stability.
A physical diagram of the polyvinyl formal-graphene composite material after being placed for 1 month is shown in fig. 9, and it can be seen from the diagram that graphene in the prepared composite material is uniformly dispersed in the composite material.
Example 3
Step 1: respectively adding 9g of potassium permanganate into 300 mL of pre-cooled 90% sulfuric acid, stirring and dissolving, adding 3g of natural graphite, oxidizing for 24 h at 40 ℃, adding 6 mL of hydrogen peroxide, and centrifugally washing to prepare graphene oxide aqueous dispersion; the size of the obtained graphene oxide is 8-10 mu m.
Step 2: preparing the graphene oxide aqueous dispersion obtained in the step 1 into a concentration of 1 mg/mL, taking 30mL, adding 0.1mL of ammonia water and hydrogen peroxide into the graphene oxide aqueous dispersion, diluting to 150mL, reacting at the temperature of 120 ℃ for 12h, and purifying to prepare the graphene quantum dot aqueous dispersion. The TEM high resolution image shows that the size of the prepared graphene quantum dot is 5-6 nm.
And step 3: mixing 0.6 g of graphene oxide prepared in the steps 1 and 2 with 0.4 g of graphene quantum dot water dispersion to obtain a mixed solution with the pH value of 2, adding 100 g of phenol, uniformly stirring, adding 100 mL of formaldehyde solution with the mass fraction of 37%, stirring for half an hour, carrying out in-situ polymerization at the temperature of 85 ℃ for 3 hours, cooling to room temperature, filtering, washing and drying to obtain a phenolic resin-graphene composite material;
comparative example 1
Preparation of polyvinyl butyral:
step 1: adding 20 g of polyvinyl alcohol into 200 mL of water, stirring at 80 ℃ until the polyvinyl alcohol is completely dissolved, and cooling to room temperature to obtain a polyvinyl alcohol solution;
step 2: adding 20 mL of n-butyl aldehyde into the polyvinyl alcohol solution, adding a hydrochloric acid solution, adjusting the pH value of the solution to 2, stirring for half an hour, reacting for 2 hours in a water bath condition at 80 ℃, cooling to room temperature, filtering, washing and drying to obtain a polyvinyl butyral material;
the physical diagram of the prepared polyvinyl butyral material after being placed for 2 months is shown in fig. 8. As can be seen, a black material is produced on the surface of the material, which indicates that the polyvinyl butyral prepared by using acid as a catalyst has poor storage stability and is easy to deteriorate after being placed for a long time.
Comparative example 2
Preparation of polyvinyl formal:
step 1: adding 20 g of polyvinyl alcohol into 200 mL of water, stirring at 80 ℃ until the polyvinyl alcohol is completely dissolved, and cooling to room temperature to obtain a polyvinyl alcohol solution;
step 2: adding 20 mL of formaldehyde with the mass fraction of 37% into the polyvinyl alcohol solution, adding a hydrochloric acid solution, adjusting the pH value of the solution to 3, stirring for half an hour, reacting for 2 hours in a water bath condition at 80 ℃, cooling to room temperature, filtering, washing and drying to obtain a polyvinyl formal material;
FIG. 10 is a schematic representation of a polyvinyl formal material prepared in comparative example 2. As can be seen, part of the polyvinyl formal material has changed from white to black, because the acid in the material has not been washed clean, which causes the material to deteriorate.
Table 1: tensile Property test data for the polyvinyl butyral-graphene composite prepared in example 1 and the polyvinyl butyral prepared in comparative example 1
| Sample numbering | Tensile strength | Elongation at break |
| Comparative example 1 | 12.47 | 488.8623 |
| Example 1 | 17.16 | 514.2134 |
Table 2: tensile property test data of the polyvinyl formal-graphene composite material prepared in example 2 and the polyvinyl formal prepared in comparative example 1
| Sample numbering | Tensile strength | Elongation at break |
| Comparative example 2 | 15.36 | 257.1115 |
| Example 2 | 25.53 | 306.2790 |
Comparative example 3
Step 1: respectively adding 9g of potassium permanganate into 300 mL of pre-cooled 90% sulfuric acid, stirring and dissolving, adding 3g of natural graphite, oxidizing for 24 h at 40 ℃, adding 6 mL of hydrogen peroxide, and centrifugally washing to prepare graphene oxide aqueous dispersion; the size of the obtained graphene oxide is 5-10 μm.
And 3, step 3: adding 100 g of polyvinyl alcohol into the aqueous dispersion containing 1 g of graphene oxide prepared in the steps 1 and 2, heating to dissolve the polyvinyl alcohol, adding 100 mL of a butyraldehyde solution with the mass fraction of 37%, uniformly stirring, adding a dilute hydrochloric acid solution to enable the pH of the solution to be 3, carrying out in-situ polymerization reaction at the temperature of 85 ℃ for 3 hours, cooling to room temperature, and filtering, washing and drying to obtain a polyvinyl butyral-graphene composite material;
fig. 11 is a physical diagram of the polyvinyl butyral-graphene composite prepared in comparative example 3 placed in a solvent. It can be seen from the figure that if hydrochloric acid is used as a reaction catalyst, the composite material is easy to turn yellow in the subsequent processing process, and the processability of the material is affected.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The preparation method of the acetal polymer-graphene composite material is characterized by uniformly dispersing graphene oxide and graphene oxide quantum dots in a polymer precursor to form a precursor mixed material with the pH of 2-5, and carrying out acetal polymerization on the precursor mixed material and aldehyde liquid to obtain the polymer-graphene composite material; the mass of the graphene oxide and the graphene oxide quantum dots accounts for 0.1-1% of the total mass of the composite material.
2. The method according to claim 1, wherein the pH of the mixed material is adjusted by adjusting the ratio of the graphene oxide to the graphene oxide quantum dots, wherein the ratio of the graphene oxide to the graphene oxide quantum dots is 6: 4-9: 1.
3. The method according to claim 1, wherein the graphene oxide has a size of 5 to 10 μm.
4. The method according to claim 1, wherein the aldehyde liquid is one or more of formaldehyde, acetaldehyde, n-butyraldehyde and other aldehyde compounds with a mass fraction of 37% -40%.
5. The method of claim 1, wherein the polymer precursor is polyvinyl alcohol, phenol, and other organic compounds having alcoholic hydroxyl groups.
6. The method of claim 1, wherein the graphene oxide quantum dots are obtained by: adding 0.1-1.5 mL of ammonia water and 0.1-1.5 mL of hydrogen peroxide into 30mL of graphene oxide aqueous dispersion with the concentration of 1-5 mg/mL, diluting to 150-200 mL, placing in a reaction kettle, reacting at the temperature of 120-180 ℃ for 8-12 h, and purifying to prepare graphene quantum dot aqueous dispersion; the concentration of the ammonia water is 25%, and the concentration of the hydrogen peroxide is 30%.
7. The method as claimed in claim 1, wherein the acetal polymer-graphene composite material is obtained by mixing graphene oxide, graphene quantum dots and water, adding 100 parts by mass of a polymer precursor, heating and stirring at 70-100 ℃ until the polymer precursor is completely dissolved, adding 50-100 parts by mass of aldehyde solution after cooling, stirring for half an hour, carrying out in-situ polymerization at 70-100 ℃ for 30 min-3 h, cooling to room temperature, filtering, and drying.
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