CN111979774A - Aminated graphene modified polyacrylonitrile active fiber and preparation method and application thereof - Google Patents
Aminated graphene modified polyacrylonitrile active fiber and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an aminated graphene modified polyacrylonitrile active fiber and a preparation method and application thereof, belonging to the technical field of modification of polyacrylonitrile fibersMarked as NH2GNPs/D-PAN. The problems of inertia and difficult modification of the fiber surface are solved, the treated fiber is used for modified asphalt, the defects of poor viscoelastic property, weak deformation resistance and the like of the fiber modified asphalt can be effectively overcome, and the viscoelastic property and the deformation resistance of the obtained modified asphalt are greatly improved.
Description
Technical Field
The invention belongs to the technical field of modification of polyacrylonitrile fibers, and particularly relates to an aminated graphene modified polyacrylonitrile active fiber, and a preparation method and application thereof.
Background
In recent years, fiber and natural asphalt modified asphalt mixtures have been widely applied to high-grade highway construction in China, and the improvement of the comprehensive road performance of the fiber and natural asphalt modified asphalt mixtures is a hot point of attention in engineering and academia. The road asphalt is mainly derived from paraffin base crude oil, so that the asphalt has high sensitivity to temperature, and is easy to cause problems of oil bleeding, deformation and the like, and the fiber has strong adsorption, tackifying, water-resistant stability, reinforcement, crack resistance and other effects on the asphalt, so that the defects of high low-temperature brittleness and poor tensile property of an asphalt mixture can be overcome, the toughness is improved, the anti-fatigue life is prolonged, and the high-temperature stability of the asphalt mixture is improved, so that the addition of the fiber into the asphalt mixture is an important way for solving the problem of asphalt pavement damage.
Many expert scholars are working on improving the performance of asphalt roads by preparing asphalt composites by adding other materials, and the main efforts are focused on developing new asphalt road materials with better mechanical properties. Researches show that the basalt fiber releases the concentrated stress of an interface after being added into asphalt mucilage, so that the stress relaxation capacity of the asphalt is enhanced, and the viscoelastic property and the high-temperature stability of the asphalt can be improved. Research shows that the addition of 0.3% of fiber has obvious retarding effect on asphalt and weakens the segregation of asphalt and aggregate.
At present, the fibers applied to the asphalt cement are various, mainly include mineral fibers, polyacrylonitrile fibers, lignin and the like, and the mineral fibers, the polyacrylonitrile fibers, the lignin and the like can enhance the high-temperature anti-rutting performance and the low-temperature anti-cracking performance of the asphalt cement. However, due to the inertness of the fiber surface, modification is not easy to perform, resulting in less research on adding modified fibers to asphalt, which limits further development of fiber asphalt roads. Researches show that the surface of the carbon fiber is modified by using the dopamine aqueous solution, and octadecylamine is successfully grafted after a layer of polydopamine coating is successfully deposited on the surface of the super-hydrophobic carbon fiber. The Chinese patent application with publication number CN 109206928A discloses a high-temperature resistant modified asphalt for highways and a preparation method thereof, and specifically comprises the following steps: 12 chemical components of epoxy resin, polyester fiber, ethylene bis stearamide, chitosan oligosaccharide, 3-piperazinylpropylmethyldimethoxysilane, n-butyl alcohol, a composite ultraviolet absorbent, an anti-aging agent, 3-glycidoxypropyltriethoxysilane, sulfurized fatty acid ester, sodium diisobutylnaphthalenesulfonate and graphene oxide, and the components are complex and difficult to prepare.
Therefore, a modification method with simple operation needs to be researched to solve the problem of inertness of the fiber surface and improve the performance of the fiber asphalt.
Disclosure of Invention
In order to solve the technical problems, the invention provides an aminated graphene modified polyacrylonitrile active fiber and a preparation method and application thereof2GNPs/D-PAN, NH2the-GNPs/D-PAN is applied to modified asphalt, and the viscoelasticity and the deformation resistance of the obtained modified asphalt are greatly improved.
In order to achieve the purpose, the invention provides the following technical scheme:
an aminated graphene modified polyacrylonitrile active fiber is obtained by adhering a polydopamine coating on the surface of a polyacrylonitrile fiber through the self-polymerization reaction of dopamine, and grafting aminated graphene on the surface of the dopamine modified polyacrylonitrile fiber, wherein the label is NH2GNPs/D-PAN, the tensile strength of the obtained product reaches more than 753Mpa, and the elastic modulus reaches more than 7693 Mpa.
The invention provides a preparation method of an aminated graphene modified polyacrylonitrile active fiber, which specifically comprises the following steps:
(1) adding graphene oxide into aqueous solution, and adding ethylenediamine orHexamethylenediamine reacts under the conditions of constant temperature and stirring, and after the reaction is finished, the product, namely the aminated graphene is obtained by vacuum filtration, is dried for later use and is marked as NH2-GNPs；
(2) Putting polyacrylonitrile fiber into a lotion for ultrasonic treatment, washing the lotion with absolute ethyl alcohol or deionized water, and drying to obtain pretreated fiber for later use;
(3) placing the pretreated fiber in a dopamine solution for reaction at room temperature, taking out after the reaction is finished, cleaning with absolute ethyl alcohol, and drying to obtain the dopamine-modified polyacrylonitrile fiber marked as D-PAN;
(4) reacting NH2dissolving-GNPs in Tris-HCl buffer solution, adding D-PAN, reacting under constant temperature and stirring conditions, repeatedly washing with absolute ethyl alcohol after reaction is finished, and drying to obtain the aminated graphene modified polyacrylonitrile active fiber marked as NH2-GNPs/D-PAN。
Further, in the step (1), the mass ratio of the graphene oxide to the ethylenediamine to the water is 0.5-1.0:0.5-1.5: 400-600; the mass ratio of the graphene oxide to the hexamethylene diamine to the water is 0.5-1.0:0.5-1.5:400-600 in sequence.
Further, in the step (2), the lotion is acetone or toluene solution.
Further, in step (3), the dopamine solution is prepared by the following method: adding dopamine hydrochloride into 0.01-0.05mol/L trihydroxymethyl aminomethane water solution until the pH value of the solution is 8-9; the reaction time is 12-24 h. By adding Tris, dopamine hydrochloride can be dissolved, and dopamine is deprotonated, thereby improving solubility.
Further, the reaction is carried out under the conditions of constant temperature and stirring, and in the step (1), the reaction is carried out for 10 to 24 hours under the condition of constant temperature heating to 80 to 90 ℃ and magnetic stirring; in the step (4), the reaction is carried out for 1 to 3 hours by heating to 80 to 100 ℃ at constant temperature and stirring by magnetic force.
Further, the NH2The mass ratio of-GNPs, Tris-HCl buffer solution and D-PAN is 0.01-0.02:100-200: 1-1.5.
The invention provides application of an aminated graphene modified polyacrylonitrile active fiber, which is characterized in that dried NH is added2-GNPs/D-PAN is mixed into the asphalt to be uniformly dispersed in the asphalt, thus obtaining NH2-GNPs/D-PAN modified bitumen.
Further, NH is reacted2When the-GNPs/D-PAN is mixed into the asphalt, the temperature is kept constant at 150 ℃ and 200 ℃, and the fiber is dispersed at the rotating speed of 350rpm and 450rpm, so that the fiber is uniformly dispersed in the asphalt.
Further, the dried NH2The content of-GNPs/D-PAN is 1-3% of the total mass of the asphalt.
In the invention, the Tris-HCl buffer solution is prepared by adding HCL into a Tris (hydroxymethyl) aminomethane solution with the concentration of 0.05mol/L until the pH value is 8.5.
The graphene oxide, the ethylenediamine, the hexamethylenediamine, the polyacrylonitrile fiber, the acetone, the toluene, the absolute ethyl alcohol, the dopamine, the Tris (hydroxymethyl) aminomethane and the HCl used in the invention are all purchased from chemical raw material companies at home and abroad and can be directly used.
The reaction principle of the invention is as follows:
firstly, dopamine molecules are oxidized and self-polymerized to generate polydopamine, the polydopamine is adhered to the surface of a fiber, then primary amine functional groups are grafted on graphene oxide modified by hexamethylene diamine or ethylene diamine, and primary amine is easy to generate Michael addition and Schiff base reaction with the polydopamine, so that aminated graphene is grafted on a polydopamine coating on the surface of the fiber.
The invention has the following beneficial effects:
1. in the reaction process, dopamine is added, is adhered to the surface of the polyacrylonitrile fiber, is rapidly deposited and gathered on the surface of the polyacrylonitrile fiber to form a polydopamine coating, has lasting stability, and can be used as a tie to increase the binding force between the polyacrylonitrile fiber and the aminated graphene; the deposited polydopamine layer also has functional groups such as hydroxyl, imino and the like, provides a large amount of active groups for further functionalization and is easy to react with NH2The amine groups in the-GNPs are reacted with Schiff bases or the like to further promote NH2GNPs are grafted onto the surface of polyacrylonitrile fiber with high efficiency.
2. In the reaction process, graphene oxide is added and is aminated to successfully graft polydopamine on the surface of the fiber, so that the surface roughness of the fiber is increased. Reacting NH2The increase in the roughness of the surface of the fibers when the-GNPs/D-PAN are incorporated in the asphalt results in NH2The contact area of the GNPs/D-PAN and the asphalt is increased, and meanwhile, the introduction of the aminated graphene improves the interlaminar shear strength of the fiber and plays a role in mechanical meshing of the asphalt.
Drawings
FIG. 1 is a graph showing the complex shear modulus G of fiber pitches of application example 4 and comparative example 1 of the present invention*(10Hz) vs. temperature.
FIG. 2 is a graph showing the complex shear modulus G of fiber pitches of application example 5 and comparative example 2 of the present invention*(10Hz) vs. temperature.
FIG. 3 is a graph showing the complex shear modulus G of fiber pitches of application example 6 and comparative example 3 of the present invention*(10Hz) vs. temperature.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Preparation of example 1
The preparation method of the aminated graphene modified polyacrylonitrile active fiber comprises the following steps:
(1) weighing 0.2g of graphene oxide in 100mL of aqueous solution, adding 0.2mL of ethylenediamine, heating the magnetic stirrer at the constant temperature of 80 ℃ for reaction for 10h, and performing vacuum filtration to obtain a product marked as NH2Putting GNPs into a 60 ℃ oven for 8 hours for later use;
(2) putting polyacrylonitrile fiber into acetone solution, performing ultrasonic treatment for 2h to remove sizing agent on the fiber surface, washing with anhydrous ethanol, and drying in a 60 deg.C oven for 12 h;
(3) placing the pretreated fiber in a dopamine solution to react for 24 hours at room temperature, taking out after the reaction is finished, repeatedly cleaning the fiber by absolute ethyl alcohol and distilled water, and placing the fiber in a 60 ℃ drying oven to dry for 12 hours to obtain the dopamine-modified polyacrylonitrile fiber, wherein the label of the polyacrylonitrile fiber is D-PAN; the preparation method of the dopamine solution comprises the following steps: 0.1211g of Tris per 100mL of water was added, and dopamine hydrochloride was added to a pH of 8.0;
(4) 0.01g of NH2-GNPs are dissolved in Tris-HCl buffer solution, 1g of D-PAN is added, the mixture is reacted for 1 hour in a constant-temperature magnetic stirrer at the temperature of 80 ℃, absolute ethyl alcohol and distilled water are repeatedly used for cleaning after the reaction is finished in the reaction process, the mixture is placed in a drying oven at the temperature of 60 ℃ for drying for 12 hours, and the aminated graphene modified polyacrylonitrile active fiber is prepared, and the label is NH2-GNPs/D-PAN; the Tris-HCl buffer may be prepared by dissolving 0.6057g of Tris in 100mL of water and titrating the solution to pH 8.5 with 1mol of HCl solution.
The tensile strength of the product obtained by detection is 753Mpa, and the elastic modulus is 7593 Mpa.
Preparation of example 2
The preparation method of the aminated graphene modified polyacrylonitrile active fiber comprises the following steps:
(1) weighing 0.2g of graphene oxide in 100mL of aqueous solution, adding 0.2mL of ethylenediamine, heating the magnetic stirrer at the constant temperature of 85 ℃ for reaction for 12h, and performing vacuum filtration to obtain a product marked as NH2Putting GNPs into a 60 ℃ oven for 8 hours for later use;
(2) putting polyacrylonitrile fiber into toluene solution, performing ultrasonic treatment for 2h to remove sizing agent on the fiber surface, washing with absolute ethanol, and drying in a 60 ℃ oven for 12 h;
(3) placing the pretreated fiber in a dopamine solution to react for 24 hours at room temperature, taking out after the reaction is finished, repeatedly cleaning the fiber by using absolute ethyl alcohol, and placing the fiber in a 60 ℃ drying oven to dry for 12 hours to obtain the dopamine-modified polyacrylonitrile fiber, wherein the label of the polyacrylonitrile fiber is D-PAN; the preparation method of the dopamine solution comprises the following steps: 0.1211g of Tris per 100mL of water was added, and dopamine hydrochloride was added to a pH of 8.5;
(4) 0.01g of NH2dissolving-GNPs in Tris-HCl buffer solution, adding 1g of D-PAN, reacting in a constant-temperature magnetic stirrer at 90 ℃ for 2h, repeatedly cleaning with absolute ethyl alcohol after the reaction is finished, drying in a drying oven at 60 ℃ for 12h to prepare the aminated graphene modified polyacrylonitrile active fiber, wherein the label is NH2-GNPs/D-PAN; the Tris-HCl buffer solution is prepared by dissolving 0.6057g of Tris in 100mThe solution was titrated with 1mol HCl solution in L water to pH 8.5.
The tensile strength of the product obtained by detection is 755MPa, and the elastic modulus is 7594 MPa.
Preparation of example 3
The preparation method of the aminated graphene modified polyacrylonitrile active fiber comprises the following steps:
(1) weighing 0.2g of graphene oxide in 100mL of aqueous solution, adding 0.2mL of ethylenediamine, heating the magnetic stirrer at a constant temperature of 90 ℃ for reaction for 10h, and performing vacuum filtration to obtain a product marked as NH2Putting GNPs into a 60 ℃ oven for 8 hours for later use;
(2) putting polyacrylonitrile fiber into acetone solution, performing ultrasonic treatment for 2h to remove sizing agent on the fiber surface, washing with anhydrous ethanol, and drying in a 60 deg.C oven for 12 h;
(3) placing the pretreated fiber in a dopamine solution to react for 24 hours at room temperature, taking out after the reaction is finished, repeatedly cleaning the fiber by absolute ethyl alcohol and distilled water, and placing the fiber in a 60 ℃ drying oven to dry for 12 hours to obtain the dopamine-modified polyacrylonitrile fiber, wherein the label of the polyacrylonitrile fiber is D-PAN; the preparation method of the dopamine solution comprises the following steps: 0.1211g of Tris per 100mL of water was added, and dopamine hydrochloride was added to a pH of 9.0;
(4) 0.01g of NH2-GNPs are dissolved in Tris-HCl buffer solution, 1g of D-PAN is added, the mixture reacts for 3 hours in a constant-temperature magnetic stirrer at the temperature of 100 ℃, absolute ethyl alcohol and distilled water are repeatedly used for cleaning after the reaction is finished, the mixture is placed in a 60 ℃ oven for drying for 12 hours in the reaction process, and the aminated graphene modified polyacrylonitrile active fiber is prepared, and is marked as NH2-GNPs/D-PAN; the Tris-HCl buffer may be prepared by dissolving 0.6057g of Tris in 100mL of water and titrating the solution to pH 8.5 with 1mol of HCl solution.
The tensile strength of the product obtained by detection is 754Mpa, and the elastic modulus is 7595 Mpa.
Application example 4
150g of SK-70A bitumen are weighed out and dried in an oven at 135 ℃ for 2h to remove excess water, and the NH obtained in example 1 is dried2-GNPs/D-PAN are mixed into the asphalt, the temperature is kept constant at 150 ℃, the fiber is dispersed for 2 hours under a high-speed shearing machine of 350rpm, and the fiber is evenly dividedDispersing in asphalt to obtain NH2-GNPs/D-PAN modified bitumen; NH (NH)2The content of-GNPs/D-PAN accounts for 1 percent of the total mass of the asphalt.
Application example 5
150g of SK-70A bitumen are weighed out and dried in an oven at 135 ℃ for 2h to remove excess water, and the NH obtained in example 2 is dried2-GNPs/D-PAN is mixed into the asphalt, the temperature is kept constant at 165 ℃, the fiber is dispersed for 2 hours under a high-speed shearing machine with the speed of 400rpm, so that the fiber is uniformly dispersed in the asphalt, and NH is obtained2-GNPs/D-PAN modified bitumen; NH (NH)2The content of-GNPs/D-PAN accounts for 2 percent of the total mass of the asphalt.
Application example 6
150g of SK-70A bitumen are weighed out and dried in an oven at 135 ℃ for 2h to remove excess water, and the NH obtained in example 3 is dried2-GNPs/D-PAN is mixed into the asphalt, the temperature is kept constant at 200 ℃, the fiber is dispersed for 2 hours under a high-speed shearing machine with 450rpm, so that the fiber is uniformly dispersed in the asphalt, and NH is obtained2-GNPs/D-PAN modified bitumen; NH (NH)2The content of-GNPs/D-PAN accounts for 3 percent of the total mass of the asphalt.
Comparative example 1
Weighing 150g of SK-70A asphalt, drying in a 135 ℃ oven for 2h to remove excess moisture, doping Polyacrylonitrile (PAN) fiber into the asphalt, keeping the temperature constant at 150 ℃, dispersing the fiber for 2h under a 350rpm high-speed shearing machine, and uniformly dispersing the fiber in the asphalt to obtain PAN modified asphalt; the PAN content accounts for 1 percent of the total mass of the asphalt.
Comparative example 2
Weighing 150g of SK-70A asphalt, drying in a 135 ℃ oven for 2h to remove redundant moisture, doping Polyacrylonitrile (PAN) fiber into the asphalt, keeping the temperature at 165 ℃ constant, dispersing the fiber for 2h under a 400rpm high-speed shearing machine, and uniformly dispersing the fiber in the asphalt to obtain PAN modified asphalt; the PAN content accounts for 2 percent of the total mass of the asphalt.
Comparative example 3
Weighing 150g of SK-70A asphalt, drying in a 135 ℃ oven for 2h to remove redundant moisture, doping Polyacrylonitrile (PAN) fiber into the asphalt, keeping the temperature constant at 200 ℃, dispersing the fiber for 2h under a 450rpm high-speed shearing machine, and uniformly dispersing the fiber in the asphalt to obtain PAN modified asphalt; the PAN content accounts for 3 percent of the total mass of the asphalt.
DSR testing
Examples 4-6, comparative examples 1-3 were subjected to the DSR test by pouring asphalt into the center of a 25mm diameter plaque so that the asphalt covered substantially the entire plaque, and then loading the plaque back into the rheometer. The test plate is moved to extrude asphalt between the two test plates, the test piece trimmer is heated, the redundant asphalt on the periphery is corrected, and then the gap is adjusted to be a test gap of 1 mm. When the temperature is balanced, the equipment automatically performs the test at the frequency of 10rad/s and the selected stress target value, and the recording and the calculation are completed by a data acquisition system.
DSR test results
2.1 FIG. 1 is a graph comparing the storage modulus of tests using the product of example 4 and comparative example 1. From FIG. 1, it can be seen that the complex shear modulus G of the two modified asphalts*At the same temperature, NH from example 4 was used2Complex shear modulus G of-GNPs/D-PAN modified asphalt*Both greater than the complex shear modulus G of the PAN-modified asphalt of comparative example 1*Proves that the fiber NH modified by the aminated graphene and the polydopamine2GNPs/D-PAN, when added to bitumen, stiffens the bitumen and thus increases its resistance to deformation.
2.2 FIG. 2 is a graph comparing the storage modulus of tests using the products of example 5 and comparative example 2. As can be seen from FIG. 2, the energy storage G' of the two modified asphalts is NH at the same temperature2The storage modulus G' of the-GNPs/D-PAN modified asphalt is larger than that of the PAN modified asphalt, indicating NH2The elastic performance of the-GNPs/D-PAN modified asphalt is enhanced.
2.3 FIG. 3 is a graph comparing the storage modulus of tests using the products of example 6 and comparative example 3. As can be seen from FIG. 3, NH was observed at the same temperature for both modified asphalts2The loss modulus G 'of the GNPs/D-PAN modified asphalt is all greater than the loss modulus G' of the PAN modified asphalt, indicating NH2The viscosity performance of the-GNPs/D-PAN modified asphalt is enhanced.
As can be seen from FIGS. 1 to 3, NH2-GNPs/D-PAN modified fibersComplex shear modulus of dimension G*The storage modulus G 'and loss modulus G' are all greater than PAN modified asphalt. This indicates that while the tack is improved, the elasticity is also improved somewhat. Proved that the viscoelastic property and the anti-deformation capability of the asphalt can be effectively improved after the fiber modified by the aminated graphene and the polydopamine is added into the asphalt.
Example 7
A preparation method of an aminated graphene modified polyacrylonitrile active fiber specifically comprises the following steps:
(1) adding graphene oxide into an aqueous solution, adding ethylenediamine, heating to 80 ℃ at a constant temperature, reacting for 15 hours under magnetic stirring, performing vacuum filtration after the reaction is finished to obtain a product, namely aminated graphene, drying the aminated graphene for later use, and marking the product as NH2-GNPs; the mass ratio of the graphene oxide to the ethylenediamine to the water is 0.5:0.5:400 in sequence;
(2) putting polyacrylonitrile fiber into a lotion toluene solution for ultrasonic treatment, washing away the lotion with deionized water, and drying to obtain pretreated fiber for later use;
(3) placing the pretreated fiber in a dopamine solution for reaction for 12 hours at room temperature, taking out after the reaction is finished, cleaning with absolute ethyl alcohol, and drying to obtain the dopamine-modified polyacrylonitrile fiber, wherein the label is D-PAN; the preparation method of the dopamine solution comprises the following steps: adding dopamine hydrochloride into 0.01mol/L trihydroxymethyl aminomethane aqueous solution until the pH value of the solution is 8;
(4) reacting NH2dissolving-GNPs in Tris-HCl buffer solution, adding D-PAN, heating to 100 ℃ at constant temperature, reacting for 3h under magnetic stirring, repeatedly cleaning with absolute ethyl alcohol after reaction, and drying to obtain the aminated graphene modified polyacrylonitrile active fiber marked as NH2-GNPs/D-PAN; wherein, the NH2The mass ratio of-GNPs, Tris-HCl buffer solution and D-PAN is 0.01:100: 1.
Example 8
A preparation method of an aminated graphene modified polyacrylonitrile active fiber specifically comprises the following steps:
(1) adding graphene oxide into an aqueous solution, adding ethylenediamine, heating to 90 ℃ at a constant temperature, reacting for 24 hours under magnetic stirring, performing vacuum filtration after the reaction is finished to obtain a product, namely aminated graphene, drying the aminated graphene for later use, and marking the product as NH2-GNPs; the mass ratio of the graphene oxide to the ethylenediamine to the water is 1.0:1.5:600 in sequence;
(2) putting polyacrylonitrile fiber into a lotion toluene solution for ultrasonic treatment, washing away the lotion with deionized water, and drying to obtain pretreated fiber for later use;
(3) placing the pretreated fiber in a dopamine solution for reacting for 18h at room temperature, taking out after the reaction is finished, cleaning with absolute ethyl alcohol, and drying to obtain the dopamine-modified polyacrylonitrile fiber marked as D-PAN; the preparation method of the dopamine solution comprises the following steps: adding dopamine hydrochloride into a 0.05mol/L trihydroxymethylaminomethane aqueous solution until the pH value of the solution is 9;
(4) reacting NH2dissolving-GNPs in Tris-HCl buffer solution, adding D-PAN, heating to 90 ℃ at constant temperature, reacting for 2h under magnetic stirring, repeatedly cleaning with absolute ethyl alcohol after reaction, and drying to obtain the aminated graphene modified polyacrylonitrile active fiber marked as NH2-GNPs/D-PAN; wherein, the NH2The mass ratio of-GNPs, Tris-HCl buffer solution and D-PAN is 0.02:200: 1.5.
Example 9
A preparation method of an aminated graphene modified polyacrylonitrile active fiber specifically comprises the following steps:
(1) adding graphene oxide into an aqueous solution, adding hexamethylenediamine into the aqueous solution, heating the aqueous solution to 85 ℃ at a constant temperature, reacting the mixture for 10 hours under magnetic stirring, performing vacuum filtration after the reaction is finished to obtain a product, namely aminated graphene, drying the aminated graphene for later use, and marking the product as NH2-GNPs; the mass ratio of the graphene oxide to the hexamethylene diamine to the water is 0.5:1.5:600 in sequence;
(2) putting polyacrylonitrile fiber into a lotion toluene solution for ultrasonic treatment, washing away the lotion with deionized water, and drying to obtain pretreated fiber for later use;
(3) placing the pretreated fiber in a dopamine solution for reaction for 20 hours at room temperature, taking out after the reaction is finished, cleaning with absolute ethyl alcohol, and drying to obtain the dopamine-modified polyacrylonitrile fiber, wherein the label is D-PAN; the preparation method of the dopamine solution comprises the following steps: adding dopamine hydrochloride into 0.03mol/L trihydroxymethylaminomethane aqueous solution until the pH value of the solution is 8.5;
(4) reacting NH2dissolving-GNPs in Tris-HCl buffer solution, adding D-PAN, heating to 80 ℃ at constant temperature, reacting for 1h under magnetic stirring, repeatedly cleaning with absolute ethyl alcohol after reaction is finished, and drying to obtain the aminated graphene modified polyacrylonitrile active fiber marked as NH2-GNPs/D-PAN; wherein, the NH2The mass ratio of-GNPs, Tris-HCl buffer solution and D-PAN is 0.015:150: 1.2.
Example 10
A preparation method of an aminated graphene modified polyacrylonitrile active fiber specifically comprises the following steps:
(1) adding graphene oxide into an aqueous solution, adding hexamethylenediamine into the aqueous solution, heating the aqueous solution to 83 ℃ at a constant temperature, reacting the mixture for 18 hours under magnetic stirring, performing vacuum filtration after the reaction is finished to obtain a product, namely aminated graphene, drying the aminated graphene for later use, and marking the product as NH2-GNPs; the mass ratio of the graphene oxide to the hexamethylene diamine to the water is 1.0:0.5:400 in sequence;
(2) putting polyacrylonitrile fiber into acetone as a lotion for ultrasonic treatment, washing the lotion with deionized water, and drying to obtain pretreated fiber for later use;
(3) placing the pretreated fiber in a dopamine solution for reaction for 22h at room temperature, taking out after the reaction is finished, cleaning with absolute ethyl alcohol, and drying to obtain the dopamine-modified polyacrylonitrile fiber, wherein the label is D-PAN; the preparation method of the dopamine solution comprises the following steps: adding dopamine hydrochloride into 0.01mol/L trihydroxymethyl aminomethane aqueous solution until the pH value of the solution is 8;
(4) reacting NH2Dissolving GNPs in Tris-HCl buffer, adding D-PAN, and keeping the temperature constantHeating to 95 ℃, reacting for 2 hours under magnetic stirring, repeatedly cleaning with absolute ethyl alcohol after the reaction is finished, and drying to obtain the aminated graphene modified polyacrylonitrile active fiber marked as NH2-GNPs/D-PAN; wherein, the NH2The mass ratio of-GNPs, Tris-HCl buffer solution and D-PAN is 0.01:200: 1.5.
Example 11
A preparation method of an aminated graphene modified polyacrylonitrile active fiber specifically comprises the following steps:
(1) adding graphene oxide into an aqueous solution, adding hexamethylenediamine into the aqueous solution, heating the aqueous solution to 84 ℃ at a constant temperature, reacting the mixture for 18 hours under magnetic stirring, performing vacuum filtration after the reaction is finished to obtain a product, namely aminated graphene, drying the aminated graphene for later use, and marking the product as NH2-GNPs; the mass ratio of the graphene oxide to the hexamethylene diamine to the water is 0.8:1.0:500 in sequence;
(2) putting polyacrylonitrile fiber into acetone as a lotion for ultrasonic treatment, washing the lotion with deionized water, and drying to obtain pretreated fiber for later use;
(3) placing the pretreated fiber in a dopamine solution for reaction for 12 hours at room temperature, taking out after the reaction is finished, cleaning with absolute ethyl alcohol, and drying to obtain the dopamine-modified polyacrylonitrile fiber, wherein the label is D-PAN; the preparation method of the dopamine solution comprises the following steps: adding dopamine hydrochloride into 0.05mol/L trihydroxymethyl aminomethane water solution until the pH value of the solution is 8-9;
(4) reacting NH2dissolving-GNPs in Tris-HCl buffer solution, adding D-PAN, heating to 90 ℃ at constant temperature, reacting for 1h under magnetic stirring, repeatedly cleaning with absolute ethyl alcohol after reaction is finished, and drying to obtain the aminated graphene modified polyacrylonitrile active fiber marked as NH2-GNPs/D-PAN; wherein, the NH2The mass ratio of-GNPs, Tris-HCl buffer solution and D-PAN is 0.02:150: 1.1.
NH obtained in examples 7 to 112the-GNPs/D-PAN are respectively applied to the modified asphalt, and the detection result of the modified asphalt is similar to that of the examples 4-6. The product of the invention hasGood reproducibility.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive faculty, based on the technical solutions of the present invention.
Claims (10)
1. The active fiber is characterized in that a polydopamine coating is adhered to the surface of a polyacrylonitrile fiber through the self-polymerization reaction of dopamine, and then the aminated graphene is grafted to the surface of the polyacrylonitrile fiber modified by the dopamine, and is marked as NH2GNPs/D-PAN, the tensile strength of the obtained product reaches more than 753Mpa, and the elastic modulus reaches more than 7593 Mpa.
2. The preparation method of the aminated graphene-modified polyacrylonitrile active fiber of claim 1, which is characterized by comprising the following steps:
(1) adding graphene oxide into an aqueous solution, adding ethylenediamine or hexamethylenediamine into the aqueous solution, reacting under constant temperature and stirring conditions, performing vacuum filtration after the reaction is finished to obtain a product, namely aminated graphene, drying the aminated graphene for later use, and marking the aminated graphene as NH2-GNPs；
(2) Putting polyacrylonitrile fiber into a lotion for ultrasonic treatment, washing the lotion with absolute ethyl alcohol or deionized water, and drying to obtain pretreated fiber for later use;
(3) placing the pretreated fiber in a dopamine solution for reaction at room temperature, taking out after the reaction is finished, cleaning with absolute ethyl alcohol, and drying to obtain the dopamine-modified polyacrylonitrile fiber marked as D-PAN;
(4) reacting NH2dissolving-GNPs in Tris-HCl buffer solution, adding D-PAN, reacting under constant temperature and stirring conditions, repeatedly washing with absolute ethyl alcohol after reaction is finished, and drying to obtain the aminated graphene modified polyacrylonitrile active fiber marked as NH2-GNPs/D-PAN。
3. The method for preparing the aminated graphene-modified polyacrylonitrile active fiber according to claim 2, wherein in the step (1), the mass ratio of the graphene oxide to the ethylenediamine to the water is 0.5-1.0:0.5-1.5: 400-; the mass ratio of the graphene oxide to the hexamethylene diamine to the water is 0.5-1.0:0.5-1.5:400-600 in sequence.
4. The preparation method of the aminated graphene-modified polyacrylonitrile active fiber according to claim 2, wherein in the step (2), the washing agent is acetone or toluene solution.
5. The preparation method of the aminated graphene-modified polyacrylonitrile active fiber according to claim 2, wherein in the step (3), the preparation method of the dopamine solution is as follows: adding dopamine hydrochloride into 0.01-0.05mol/L trihydroxymethyl aminomethane water solution until the pH value of the solution is 8-9; the reaction time is 12-24 h.
6. The preparation method of the aminated graphene-modified polyacrylonitrile active fiber according to claim 2, wherein the reaction is carried out under constant temperature and stirring conditions, and in the step (1), the reaction is carried out for 10-24h under magnetic stirring by heating to 80-90 ℃ at constant temperature; in the step (4), the reaction is carried out for 1 to 3 hours by heating to 80 to 100 ℃ at constant temperature and stirring by magnetic force.
7. The method for preparing the aminated graphene-modified polyacrylonitrile active fiber according to claim 2, wherein the NH is2The mass ratio of-GNPs, Tris-HCl buffer solution and D-PAN is 0.01-0.02:100-200: 1-1.5.
8. The application of the aminated graphene-modified polyacrylonitrile active fiber of claim 1, wherein dried NH2-GNPs/D-PAN are mixed into the asphalt to be uniformly dispersed in the asphalt, and the asphalt is obtainedTo NH2-GNPs/D-PAN modified bitumen.
9. The application of the aminated graphene-modified polyacrylonitrile active fiber according to claim 8, characterized in that NH is added2When the-GNPs/D-PAN is mixed into the asphalt, the temperature is kept constant at 150 ℃ and 200 ℃, and the fiber is dispersed at the rotating speed of 350rpm and 450rpm, so that the fiber is uniformly dispersed in the asphalt.
10. The application of the aminated graphene-modified polyacrylonitrile active fiber according to claim 8, characterized in that the dried NH2The content of-GNPs/D-PAN is 1-3% of the total mass of the asphalt.
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