CN111087807A - Graphene modified nylon composite material and preparation method thereof - Google Patents
Graphene modified nylon composite material and preparation method thereof Download PDFInfo
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- CN111087807A CN111087807A CN201911382379.6A CN201911382379A CN111087807A CN 111087807 A CN111087807 A CN 111087807A CN 201911382379 A CN201911382379 A CN 201911382379A CN 111087807 A CN111087807 A CN 111087807A
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Abstract
The invention provides a graphene modified nylon composite material and a preparation method thereof, wherein the preparation method comprises the following steps: dispersing graphene in a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid, performing ultrasonic treatment, stirring, washing, filtering and drying to obtain graphene oxide; carrying out heat treatment on graphene oxide under the protection of inert gas to obtain heat-treated graphene oxide; dissolving the obtained heat-treated graphene oxide and nylon 46 in formic acid, stirring, and then carrying out ultrasonic treatment to obtain a mixed solution; pressurizing and heating the mixed solution, decompressing and cooling to obtain a mixed suspension; and adding deionized water into the mixed suspension, and then washing and drying to obtain the graphene modified nylon composite material. According to the invention, the graphene is subjected to surface treatment, so that the compatibility problem of the graphene and nylon is improved, and the four indexes of the tensile strength, the bending strength and the friction coefficient of the prepared graphene modified nylon composite material are greatly improved compared with those of the traditional nylon material.
Description
Technical Field
The invention relates to the field of nylon materials, and particularly relates to a graphene modified nylon composite material and a preparation method thereof.
Background
Nylon (PA) has excellent mechanical properties, wear resistance, self-lubricating property, oil resistance and stability, and becomes one of the most widely used plastics at home and abroad, the first of the five engineering plastics. The nylon 46(PA46) resin is prepared by polycondensation of monomer butanediamine and monomer adipic acid, has excellent mechanical property and self-lubricating property, and can be applied to wear-resistant parts such as gears, bearings and the like. However, pure PA46 has high friction coefficient, high water absorption and poor dimensional stability, and is difficult to meet the application requirements of some practical conditions. Nylon 46 is added with molybdenum dioxide, silicon carbide, graphite and the like as an anti-wear agent to improve the anti-wear performance, but the modification means generally have the following problems: the wear-resistant agent is mainly made of inorganic materials, and the problem of compatibility of the wear-resistant agent and nylon is difficult to solve. If the addition amount is small, the wear resistance is not obviously improved; if the addition amount is large, the mechanical strength of the composite material is seriously lost.
The graphene has excellent heat conduction, electric conduction and mechanical properties, and is easy to agglomerate due to large specific surface area, and has the problems of poor interface bonding between the graphene and a polymer and poor compatibility with a polymer matrix. Therefore, it is necessary to provide a method for modifying the surface of graphene, and then making the modified graphene compatible with the nylon matrix, so as to improve the wear resistance of the composite material and simultaneously not lose the mechanical strength of the composite material.
Disclosure of Invention
The invention provides a graphene modified nylon composite material and a preparation method thereof, and aims to perform surface treatment on graphene, so that the compatibility problem of the graphene and nylon is solved, and the wear resistance and other mechanical properties of composite nylon are improved.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a graphene modified nylon composite material comprises the following steps:
(1) dispersing graphene in a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid, performing ultrasonic treatment for 12-24 hours, stirring and reacting at 50-80 ℃ for 6-8 hours, and then washing, filtering and drying to obtain graphene oxide;
(2) carrying out heat treatment on the graphene oxide obtained in the step (1) at 400-800 ℃ for 1-2 h under the protection of inert gas to obtain heat-treated graphene oxide;
(3) dissolving the heat-treated graphene oxide obtained in the step (2) and nylon 46 in formic acid, stirring, and then carrying out ultrasonic treatment to obtain a mixed solution; wherein the mass of the heat-treated graphene oxide accounts for 0.1-2.0% of that of the nylon 46;
(4) placing the mixed solution obtained in the step (3) in a reaction kettle with the pressure of 1.5-2.0 MPa and the temperature of 150-160 ℃ for reaction for 3-5 h, and relieving pressure and cooling to obtain mixed suspension;
(5) and (4) adding deionized water into the mixed suspension obtained in the step (4), and then washing and drying to obtain the graphene modified nylon composite material.
Deionized water is added into the mixed solution to separate out the modified nylon 46 in the mixed solution.
Preferably, the volume ratio of concentrated sulfuric acid to concentrated nitric acid in step (1) is 1: 3.
Preferably, the washing endpoint in step (1) is until the washing solution is neutral.
Preferably, the drying in the step (1) is vacuum drying, and the temperature is 50-80 ℃.
Preferably, the inert gas in step (2) comprises nitrogen or argon.
Preferably, the concentration of the formic acid solution in the step (3) is 2-5 mol/L.
Preferably, the pressure relief in the step (4) is carried out at a rate of 0.2-0.5 MPa/min to the normal pressure.
In the step (4), the cooling is carried out at a rate of 0.3-0.5 ℃/min to 80-100 ℃, and then the cooling is carried out at a rate of 2-3 ℃/min to room temperature.
Preferably, the drying temperature in the step (5) is 50-80 ℃, and the time is 1-3 h.
The invention also provides the graphene modified nylon composite material prepared by the method.
The scheme of the invention has the following beneficial effects:
according to the preparation method of the graphene modified nylon composite material, provided by the invention, graphene is subjected to oxidation treatment by using mixed acid of concentrated sulfuric acid and concentrated nitric acid, and the surface of the graphene is oxidized to generate functional groups such as hydroxyl and carboxyl, so that the dispersibility of the graphene in a PA46 matrix and the binding property with the matrix are improved.
And then, carrying out heat treatment on the graphene oxide, and realizing regulation of the type, the content, the stripping degree and the like of functional groups on the surface layer of the graphene under the regulation of thermal action and atmosphere control, so that the characteristic of the heat-treated graphene oxide as a conductive wear-resistant material is ensured, and the compatibility of the graphene and a matrix is further improved.
And then dissolving the heat-treated graphene oxide and nylon in formic acid, and then performing pressurization and heating treatment, and then performing gradual pressure relief and cooling treatment. The first stage of gradual cooling is slow cooling, so that nylon dissolved in a solvent can be uniformly separated out by taking graphene oxide as a nucleation center and forms chemical combination with the graphene oxide, and the enhancement effect of the graphene oxide is improved; the second stage is a rapid cooling stage, so that the nylon powder separated out by taking the graphene oxide as a nucleation center can grow up rapidly, and the enhancement effect of the graphene oxide is further improved.
The four indexes of the tensile strength, the bending strength and the friction coefficient of the graphene modified nylon composite material prepared by the method are greatly improved compared with those of the traditional nylon material. Wherein the tensile strength reaches 275 MPa; the bending strength reaches 292 MPa; the coefficient of friction was a minimum of 0.2348.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
Example 1
A preparation method of a graphene modified nylon composite material comprises the following steps:
(1) dispersing graphene in an acid solution formed by mixing concentrated sulfuric acid and concentrated nitric acid according to a volume ratio of 1:3, performing ultrasonic treatment for 12 hours, stirring and reacting at the temperature of 80 ℃ for 8 hours, washing until a washing liquid is neutral, filtering, and performing vacuum drying at the temperature of 60 ℃ to obtain graphene oxide;
(2) carrying out heat treatment on the graphene oxide obtained in the step (1) at 800 ℃ for 1h under the protection of nitrogen gas to obtain heat-treated graphene oxide;
(3) dissolving the heat-treated graphene oxide obtained in the step (2) and nylon 46 in formic acid with the concentration of 2mol/L, stirring, and then carrying out ultrasonic treatment to obtain a mixed solution; wherein the mass of the heat-treated graphene oxide accounts for 0.1% of that of the nylon 46;
(4) placing the mixed solution obtained in the step (3) in a reaction kettle with the pressure of 2.0MPa and the temperature of 150 ℃ for reaction for 3 hours, and relieving pressure and cooling to obtain mixed suspension; the pressure release speed is 0.2 MPa/min; the cooling is divided into two steps, wherein the first step is cooling to 100 ℃ at the speed of 0.3 ℃/min, and then cooling to room temperature at the speed of 2 ℃/min;
(5) and (4) adding deionized water into the mixed suspension obtained in the step (4), then washing, and drying for 3 hours at the temperature of 60 ℃ to obtain the graphene modified nylon composite material.
The obtained graphene modified nylon composite material was subjected to mechanical property tests, and the results are shown in table 1.
Example 2
A preparation method of a graphene modified nylon composite material comprises the following steps:
(1) dispersing graphene in an acid solution formed by mixing concentrated sulfuric acid and concentrated nitric acid according to a volume ratio of 1:3, performing ultrasonic treatment for 24 hours, stirring and reacting for 6 hours at a temperature of 60 ℃, then washing until a washing liquid is neutral, then filtering, and performing vacuum drying at a temperature of 50 ℃ to obtain graphene oxide;
(2) carrying out heat treatment on the graphene oxide obtained in the step (1) at 600 ℃ for 1.5h under the protection of nitrogen gas to obtain heat-treated graphene oxide;
(3) dissolving the heat-treated graphene oxide obtained in the step (2) and nylon 46 in formic acid with the concentration of 3mol/L, stirring, and then carrying out ultrasonic treatment to obtain a mixed solution; wherein the mass of the heat-treated graphene oxide accounts for 1.0% of that of the nylon 46;
(4) placing the mixed solution obtained in the step (3) in a reaction kettle with the pressure of 1.5MPa and the temperature of 160 ℃ for reaction for 4 hours, and relieving pressure and cooling to obtain mixed suspension; the pressure release speed is 0.5 MPa/min; the cooling is divided into two steps, wherein the first step is to cool the mixture to 90 ℃ at the speed of 0.5 ℃/min and then cool the mixture to room temperature at the speed of 3 ℃/min;
(5) and (4) adding deionized water into the mixed suspension obtained in the step (4), then washing, and drying for 2 hours at 50 ℃ to obtain the graphene modified nylon composite material.
The obtained graphene modified nylon composite material was subjected to mechanical property tests, and the results are shown in table 1.
Example 3
A preparation method of a graphene modified nylon composite material comprises the following steps:
(1) dispersing graphene in an acid solution formed by mixing concentrated sulfuric acid and concentrated nitric acid according to a volume ratio of 1:3, performing ultrasonic treatment for 20 hours, stirring and reacting at 50 ℃ for 7 hours, washing until a washing liquid is neutral, filtering, and performing vacuum drying at 80 ℃ to obtain graphene oxide;
(2) carrying out heat treatment on the graphene oxide obtained in the step (1) at 400 ℃ for 2h under the protection of nitrogen gas to obtain heat-treated graphene oxide;
(3) dissolving the heat-treated graphene oxide obtained in the step (2) and nylon 46 in formic acid with the concentration of 5mol/L, stirring, and performing ultrasonic treatment to obtain a mixed suspension; wherein the mass of the heat-treated graphene oxide accounts for 2.0% of that of the nylon 46;
(4) placing the mixed suspension obtained in the step (3) in a reaction kettle with the pressure of 1.6MPa and the temperature of 150 ℃ for reaction for 5 hours, and decompressing and cooling to obtain a mixed solution; the pressure release speed is 0.3 MPa/min; the cooling is divided into two steps, wherein the first step is to cool the mixture to 100 ℃ at the speed of 0.4 ℃/min and then cool the mixture to room temperature at the speed of 2 ℃/min;
(5) and (4) adding deionized water into the mixed solution obtained in the step (4), then washing, and drying for 1h at 80 ℃ to obtain the graphene modified nylon composite material.
The obtained graphene modified nylon composite material was subjected to mechanical property tests, and the results are shown in table 1.
TABLE 1 mechanical Properties test results of examples 1 to 3
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a graphene modified nylon composite material is characterized by comprising the following steps:
(1) dispersing graphene in a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid, performing ultrasonic treatment for 12-24 hours, stirring and reacting at 50-80 ℃ for 6-8 hours, and then washing, filtering and drying to obtain graphene oxide;
(2) carrying out heat treatment on the graphene oxide obtained in the step (1) at 400-800 ℃ for 1-2 h under the protection of inert gas to obtain heat-treated graphene oxide;
(3) dissolving the heat-treated graphene oxide obtained in the step (2) and nylon 46 in formic acid, stirring, and then carrying out ultrasonic treatment to obtain a mixed solution; wherein the mass of the heat-treated graphene oxide accounts for 0.1-2.0% of that of the nylon 46;
(4) placing the mixed solution obtained in the step (3) in a reaction kettle with the pressure of 1.5-2.0 MPa and the temperature of 150-160 ℃ for reaction for 3-5 h, and relieving pressure and cooling to obtain mixed suspension;
(5) and (4) adding deionized water into the mixed suspension obtained in the step (4), and then washing and drying to obtain the graphene modified nylon composite material.
2. The method according to claim 1, wherein the volume ratio of concentrated sulfuric acid to concentrated nitric acid in step (1) is 1: 3.
3. The method according to claim 1, wherein the washing in the step (1) is terminated when the washing solution is neutral.
4. The method according to claim 1, wherein the drying in step (1) is vacuum drying at a temperature of 50-80 ℃.
5. The method according to claim 1, wherein the inert gas in the step (2) includes nitrogen or argon.
6. The method according to claim 1, wherein the concentration of the formic acid solution in the step (3) is 2 to 5 mol/L.
7. The method according to claim 1, wherein the pressure in step (4) is released to the normal pressure at a rate of 0.2 to 0.5 MPa/min.
8. The method according to claim 1, wherein the cooling in step (4) is performed by cooling to 80-100 ℃ at a rate of 0.3-0.5 ℃/min, and then cooling to room temperature at a rate of 2-3 ℃/min.
9. The preparation method according to claim 1, wherein the drying temperature in the step (5) is 50-80 ℃ and the drying time is 1-3 h.
10. A graphene-modified nylon composite material, which is prepared by the method of any one of claims 1 to 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116144168A (en) * | 2022-10-21 | 2023-05-23 | 华侨大学 | Reduced graphene oxide/alcohol-soluble nylon composite master batch and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116144168A (en) * | 2022-10-21 | 2023-05-23 | 华侨大学 | Reduced graphene oxide/alcohol-soluble nylon composite master batch and preparation method and application thereof |
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Application publication date: 20200501 |