CN113144920A - Preparation method of graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film - Google Patents

Preparation method of graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film Download PDF

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CN113144920A
CN113144920A CN202110100725.8A CN202110100725A CN113144920A CN 113144920 A CN113144920 A CN 113144920A CN 202110100725 A CN202110100725 A CN 202110100725A CN 113144920 A CN113144920 A CN 113144920A
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李中辉
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Hangzhou Tianlai New Material Co ltd
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Abstract

The invention relates to the technical field of heavy metal wastewater treatment, and discloses a graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption membrane, wherein an acrylonitrile monomer is subjected to nitroxide radical in-situ polymerization on the surface of the graphene oxide through an active tert-butyl peroxide group and 2,2,6, 6-tetramethylpiperidine oxide, and is grafted in a polyacrylonitrile substrate, oxygen-containing functional groups rich in the graphene oxide are electronegative in water and have good electrostatic adsorption performance, and meanwhile, the graphene oxide can form a complex with Cu (II) ions through coordination bond action to endow the polyacrylonitrile adsorption membrane with good adsorption effect, and the graphene oxide has good dispersibility in the polyacrylonitrile monomer and very high interface bonding degree in a chemical grafting mode, so that the stress generated in the stretching process is better eliminated, and the mechanical property of the polyacrylonitrile membrane is improved, overcomes the mechanical property defect caused by the electrostatic spinning technology.

Description

Preparation method of graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film
Technical Field
The invention relates to the technical field of heavy metal wastewater treatment, in particular to a preparation method of a graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film.
Background
Along with the rapid development of society, the pollution problem of the environment is increasingly serious nowadays, the ecological environment is seriously damaged, heavy metal water pollution is caused, as one kind of environmental pollution, the pollution to organisms is very serious, a small amount of heavy metal enters a water body, and the heavy metal content in the organisms at the upper end of a food chain is too high to cause poisoning and even death through the enrichment of the organisms in the water body, so that the heavy metal emission and the water pollution treatment are particularly important, and the ecological environment and the biological diversity are protected.
Polyacrylonitrile, as a polymer material with friendly price, strong hydrophilicity and good chemical stability, can adapt to complex water body environment, is a very good adsorption film material substrate, although the polyacrylonitrile does not have adsorption performance per se and has relatively poor mechanical property, after an adsorbent is added, heavy metal ions can be effectively adsorbed, graphene oxide is a very good adsorbent because the surface of the graphene oxide has rich oxygen-containing functional groups, a large amount of heavy metal ions such as Cu ions can be adsorbed in water body through electrostatic adsorption, and the polyacrylonitrile film has good adsorption effect because of the very good mechanical property, but the polyacrylonitrile film has a physical blending mode and has an undesirable influence on the mechanical property because of the agglomeration phenomenon in the substrate.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method of a graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film, and solves the problem of poor mechanical property caused by the agglomeration of graphene oxide in a polyacrylonitrile matrix.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film comprises the following steps:
(1) adding graphene oxide and chloropropyl triethoxysilane into an ethanol solution, performing ultrasonic dispersion, stirring, heating, reacting, filtering, washing, and vacuum drying to obtain functionalized modified graphene;
(2) functionalized modified graphene oxide, tert-butyl hydroperoxide and NaHCO3Adding the mixture into a1, 4-dioxane solvent, carrying out constant-temperature reaction, filtering, washing and vacuum drying to obtain tert-butyl graphene peroxide;
(3) adding acrylonitrile and tert-butyl graphene peroxide into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, adding 2,2,6, 6-tetramethylpiperidine oxide, performing heating and stirring reaction, standing for defoaming, placing the obtained spinning solution into an electrostatic spinning machine, and performing electrostatic spinning on a receiving plate under the spinning voltage of 18-20KV to obtain the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption membrane.
Preferably, the functionalized modified graphene oxide, tert-butyl hydroperoxide and NaHCO in the step (2)3The mass ratio of (A) to (B) is 100:30-50: 0.5-1.
Preferably, the constant-temperature reaction atmosphere in the step (2) is a nitrogen atmosphere, the reaction temperature is 25-35 ℃, and the reaction time is 10-20 h.
Preferably, in the step (3), the mass ratio of the acrylonitrile to the tert-butyl graphene peroxide to the 2,2,6, 6-tetramethylpiperidine oxide is 100:0.5-5: 0.15-0.5.
Preferably, the heating and stirring reaction atmosphere in the step (3) is a nitrogen atmosphere, the reaction temperature is 50-70 ℃, and the reaction time is 24-48 h.
Preferably, the electrostatic spinning machine in step (3) comprises a top frame plate, a liquid storage tank is fixedly connected to the upper portion of the top frame plate, a liquid storage tank pipe is fixedly connected to the liquid storage tank, a liquid outlet valve is arranged on the liquid storage tank pipe, a piston is fixedly connected to the lower portion of the top frame plate, a piston barrel column is movably connected to the piston, the top frame plate is movably connected to a spinning machine box through an electric telescopic rod, a digital display controller is fixedly connected to the spinning machine box, a positive high-voltage electrostatic output device is fixedly connected to the spinning machine box and movably connected with a spinning needle through an electric wire, and a receiving plate is arranged in the spinning machine box.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
according to the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film, chloropropyl triethoxysilane is introduced to the surface of graphene oxide, then the introduced chlorine atom and tert-butyl hydroperoxide are subjected to substitution reaction to obtain tert-butyl hydroperoxide graphene, an active tert-butyl hydroperoxide group and 2,2,6, 6-tetramethylpiperidine oxide are used for enabling an acrylonitrile monomer to carry out nitroxide radical in-situ polymerization on the surface of the graphene oxide, the graphene oxide with rich oxygen-containing functional groups on the surface is grafted to a polyacrylonitrile substrate, the rich oxygen-containing functional groups of the graphene oxide are electronegative in water and have very good electrostatic adsorption performance, meanwhile, the graphene oxide can form a complex with Cu (II) ions through coordination bond action, meanwhile, cyano groups contained on the surface of the polybenzonitrile are subjected to hydrolysis reaction in a solution, and the film material is made to have electronegativity, under the combined action of the graphene oxide and the polyacrylonitrile membrane, the polyacrylonitrile adsorption membrane has a good adsorption effect.
According to the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film, graphene oxide is connected through covalent bonds and chemically grafted in a polyacrylonitrile substrate, so that the graphene oxide has good dispersibility in a polyacrylonitrile monomer, the graphene oxide and the polyacrylonitrile substrate have very high interface bonding degree, stress generated in a stretching process can be better eliminated by the graphene, the mechanical property of the polyacrylonitrile film is improved, the defect of poor mechanical property caused by an electrostatic spinning technology is overcome, more complex water environment is responded, a better structure is still kept after the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film is used in the complex water, and the recycling performance of the material is improved.
Drawings
FIG. 1 is a schematic cross-sectional view of a thermostatic drying oven;
fig. 2 is a schematic cross-sectional view of the electric telescopic rod.
1-a top frame plate; 2-a liquid storage tank; 3-a liquid storage tank pipe; 4-a liquid outlet valve; 5-a piston; 6-piston barrel column; 7-an electric telescopic rod; 8-spinning machine box; 9-a digital display controller; 10-positive electrode high-voltage electrostatic output device; 11-an electrical wire; 12-a spinning needle head; 13-receiving the plate.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film comprises the following steps:
(1) adding graphene oxide and chloropropyl triethoxysilane into an ethanol solution, performing ultrasonic dispersion, stirring, heating, reacting, filtering, washing, and vacuum drying to obtain functionalized modified graphene;
(2) functionalized modified graphene oxide, tert-butyl hydroperoxide and NaHCO3Adding the mixture into a1, 4-dioxane solvent, wherein the mass ratio of the three is 100:30-50:0.5-1, stirring and reacting for 10-20h at the reaction temperature of 25-35 ℃ in a nitrogen atmosphere, filtering, washing and drying in vacuum to obtain tert-butyl graphene peroxide;
(3) adding acrylonitrile and tert-butyl graphene peroxide into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, adding 2,2,6, 6-tetramethylpiperidine oxide, wherein the mass ratio of the acrylonitrile to the tert-butyl graphene peroxide is 100:0.5-5:0.15-0.5, stirring and reacting for 24-48h at 50-70 ℃ in the nitrogen atmosphere, standing and defoaming, and placing the obtained spinning solution into an electrostatic spinning machine, wherein the electrostatic spinning machine comprises a top frame plate, a liquid storage tank is fixedly connected above the top frame plate, a liquid storage tank pipe is fixedly connected with the liquid storage tank, a liquid outlet valve is arranged on the liquid storage tank pipe, a piston is fixedly connected below the top frame plate, a piston barrel column is movably connected with the piston, the top frame plate is movably connected with a spinning machine box through an electric telescopic rod, a digital display controller is fixedly connected with the spinning machine box, and a positive high-pressure electrostatic output device is fixedly connected with the spinning machine box, and the positive high-voltage electrostatic output device is movably connected with the spinning needle through a wire, a receiving plate is arranged in the spinning machine box, and electrostatic spinning is carried out on the receiving plate under the spinning voltage of 18-20KV, so that the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film is obtained.
Example 1
(1) Adding graphene oxide and chloropropyl triethoxysilane into an ethanol solution, performing ultrasonic dispersion, stirring, heating, reacting, filtering, washing, and vacuum drying to obtain functionalized modified graphene;
(2) functionalized modified graphene oxide, tert-butyl hydroperoxide and NaHCO3Adding the mixture into a1, 4-dioxane solvent, wherein the mass ratio of the three is 100:30:0.5, stirring and reacting for 10 hours at the reaction temperature of 25 ℃ in a nitrogen atmosphere, filtering, washing and drying in vacuum to obtain tert-butyl graphene peroxide;
(3) adding acrylonitrile and tert-butyl graphene peroxide into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, adding 2,2,6, 6-tetramethylpiperidine oxide, wherein the mass ratio of the acrylonitrile to the tert-butyl graphene peroxide is 100:0.5:0.15, stirring and reacting at 50 ℃ for 24 hours under the nitrogen atmosphere, standing and defoaming, placing the obtained spinning solution into an electrostatic spinning machine, wherein the electrostatic spinning machine comprises a top frame plate, a liquid storage tank is fixedly connected above the top frame plate, the liquid storage tank is fixedly connected with a liquid storage tank pipe, the liquid storage tank pipe is provided with a liquid outlet valve, a piston is fixedly connected below the top frame plate, the piston is movably connected with a piston barrel column, the top frame plate is movably connected with a spinning machine box through an electric telescopic rod, the spinning machine box is fixedly connected with a digital display controller, the spinning machine box is fixedly connected with a positive high-voltage electrostatic output device, and the positive high-voltage electrostatic output device is movably connected with a spinning needle through an electric wire, and arranging a receiving plate in the spinning case, and performing electrostatic spinning on the receiving plate under the spinning voltage of 18KV to obtain the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film.
Example 2
(1) Adding graphene oxide and chloropropyl triethoxysilane into an ethanol solution, performing ultrasonic dispersion, stirring, heating, reacting, filtering, washing, and vacuum drying to obtain functionalized modified graphene;
(2) functionalized modified graphene oxide, tert-butyl hydroperoxide and NaHCO3Adding the mixture into a1, 4-dioxane solvent, wherein the mass ratio of the three is 100:40:0.8, stirring and reacting for 15 hours at the reaction temperature of 30 ℃ in a nitrogen atmosphere, filtering, washing and drying in vacuum to obtain tert-butyl graphene peroxide;
(3) adding acrylonitrile and tert-butyl graphene peroxide into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, adding 2,2,6, 6-tetramethylpiperidine oxide, wherein the mass ratio of the acrylonitrile to the tert-butyl graphene peroxide to the N, N-dimethylformamide solvent is 100:3:0.3, stirring and reacting for 36h at 60 ℃ in the nitrogen atmosphere, standing and defoaming, and then putting the obtained spinning solution into an electrostatic spinning machine, wherein the electrostatic spinning machine comprises a top frame plate, a liquid storage tank is fixedly connected above the top frame plate, the liquid storage tank is fixedly connected with a liquid storage tank pipe, the liquid storage tank pipe is provided with a liquid outlet valve, a piston is fixedly connected below the top frame plate, the piston is movably connected with a piston barrel column, the top frame plate is movably connected with a spinning machine box through an electric telescopic rod, the spinning machine box is fixedly connected with a digital display controller, the spinning machine box is fixedly connected with a positive high-voltage electrostatic output device, and the positive high-voltage electrostatic output device is movably connected with a spinning needle through an electric wire, and arranging a receiving plate in the spinning case, and performing electrostatic spinning on the receiving plate under the spinning voltage of 19KV to obtain the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film.
Example 3
(1) Adding graphene oxide and chloropropyl triethoxysilane into an ethanol solution, performing ultrasonic dispersion, stirring, heating, reacting, filtering, washing, and vacuum drying to obtain functionalized modified graphene;
(2) functionalized modified graphene oxide, tert-butyl hydroperoxide and NaHCO3Adding the mixture into a1, 4-dioxane solvent, wherein the mass ratio of the three is 100:50:0.1, stirring and reacting for 20 hours at 35 ℃ in a nitrogen atmosphere, filtering, washing and drying in vacuum to obtain tert-butyl graphene peroxide;
(3) adding acrylonitrile and tert-butyl graphene peroxide into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, adding 2,2,6, 6-tetramethylpiperidine oxide, wherein the mass ratio of the acrylonitrile to the tert-butyl graphene peroxide is 100:5:0.5, stirring and reacting for 48 hours at 70 ℃ in a nitrogen atmosphere, standing and defoaming, and then putting the obtained spinning solution into an electrostatic spinning machine, wherein the electrostatic spinning machine comprises a top frame plate, a liquid storage tank is fixedly connected above the top frame plate, the liquid storage tank is fixedly connected with a liquid storage tank pipe, the liquid storage tank pipe is provided with a liquid outlet valve, a piston is fixedly connected below the top frame plate, the piston is movably connected with a piston barrel column, the top frame plate is movably connected with a spinning machine box through an electric telescopic rod, the spinning machine box is fixedly connected with a digital display controller, the spinning machine box is fixedly connected with a positive high-voltage electrostatic output device, and the positive high-voltage electrostatic output device is movably connected with a spinning needle through an electric wire, and arranging a receiving plate in the spinning case, and performing electrostatic spinning on the receiving plate under the spinning voltage of 20KV to obtain the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film.
Comparative example 1
(1) Adding graphene oxide and chloropropyl triethoxysilane into an ethanol solution, performing ultrasonic dispersion, stirring, heating, reacting, filtering, washing, and vacuum drying to obtain functionalized modified graphene;
(2) functionalized modified graphene oxide, tert-butyl hydroperoxide and NaHCO3Adding the mixture into a1, 4-dioxane solvent, wherein the mass ratio of the three is 100:15:0.1, stirring and reacting for 10 hours at the reaction temperature of 25 ℃ in a nitrogen atmosphere, filtering, washing and drying in vacuum to obtain tert-butyl graphene peroxide;
(3) adding acrylonitrile and tert-butyl graphene peroxide into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, adding 2,2,6, 6-tetramethylpiperidine oxide, wherein the mass ratio of the acrylonitrile to the tert-butyl graphene peroxide is 100:0.1:0.05, stirring and reacting at 50 ℃ for 24 hours under the nitrogen atmosphere, standing and defoaming, placing the obtained spinning solution into an electrostatic spinning machine, wherein the electrostatic spinning machine comprises a top frame plate, a liquid storage tank is fixedly connected above the top frame plate, the liquid storage tank is fixedly connected with a liquid storage tank pipe, the liquid storage tank pipe is provided with a liquid outlet valve, a piston is fixedly connected below the top frame plate, the piston is movably connected with a piston barrel column, the top frame plate is movably connected with a spinning machine box through an electric telescopic rod, the spinning machine box is fixedly connected with a digital display controller, the spinning machine box is fixedly connected with a positive high-voltage electrostatic output device, and the positive high-voltage electrostatic output device is movably connected with a spinning needle through an electric wire, and arranging a receiving plate in the spinning case, and performing electrostatic spinning on the receiving plate under the spinning voltage of 18KV to obtain the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film.
Comparative example 2
(1) Adding graphene oxide and chloropropyl triethoxysilane into an ethanol solution, performing ultrasonic dispersion, stirring, heating, reacting, filtering, washing, and vacuum drying to obtain functionalized modified graphene;
(2) functionalized modified graphene oxide, tert-butyl hydroperoxide and NaHCO3Adding the mixture into a1, 4-dioxane solvent, wherein the mass ratio of the three is 100:90:5, stirring and reacting for 20 hours at 35 ℃ in a nitrogen atmosphere, filtering, washing and drying in vacuum to obtain tert-butyl graphene peroxide;
(3) adding acrylonitrile and tert-butyl graphene peroxide into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, adding 2,2,6, 6-tetramethylpiperidine oxide, wherein the mass ratio of the acrylonitrile to the tert-butyl graphene peroxide to the N, N-dimethylformamide solvent is 100:30:5, stirring and reacting for 48h at 70 ℃ in the nitrogen atmosphere, standing and defoaming, and then placing the obtained spinning solution into an electrostatic spinning machine, wherein the electrostatic spinning machine comprises a top frame plate, a liquid storage tank is fixedly connected above the top frame plate, the liquid storage tank is fixedly connected with a liquid storage tank pipe, the liquid storage tank pipe is provided with a liquid outlet valve, a piston is fixedly connected below the top frame plate, the piston is movably connected with a piston barrel column, the top frame plate is movably connected with a spinning machine box through an electric telescopic rod, the spinning machine box is fixedly connected with a digital display controller, the spinning machine box is fixedly connected with a positive high-voltage electrostatic output device, and the positive high-voltage electrostatic output device is movably connected with a spinning needle through an electric wire, and arranging a receiving plate in the spinning case, and performing electrostatic spinning on the receiving plate under the spinning voltage of 20KV to obtain the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film.
100mg of polyacrylonitrile adsorption films of examples and comparative examples are respectively added into 100ml of Cu (II) ion solution with the concentration of 100mg/L, the pH value is adjusted to 5, the solution is stirred and adsorbed at constant temperature for 12h, the concentration of copper ions is measured by using an HG96 atomic absorption spectrophotometer, and the maximum adsorption capacity is calculated, wherein the test standard is GB/T38224.2-2019.
Item Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2
Maximum adsorption capacity (mg/g) 65.7 92.6 71.8 46.8 43.3
The polyacrylonitrile absorption films of the examples and the comparative examples are tested for the tensile strength of the material by using an SHK-A101 electronic universal tester, and the test standard is GB/T7689.5-2013.
Item Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2
Tensile strength (Mpa) 7.49 9.83 5.94 3.40 2.87

Claims (6)

1. The heavy metal adsorption film of the graphene oxide grafted polyacrylonitrile fiber is characterized in that: the preparation method of the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film comprises the following steps:
(1) adding graphene oxide and chloropropyl triethoxysilane into an ethanol solution, performing ultrasonic dispersion, stirring, heating, reacting, filtering, washing, and vacuum drying to obtain functionalized modified graphene;
(2) functionalized modified graphene oxide, tert-butyl hydroperoxide and NaHCO3Adding the mixture into a1, 4-dioxane solvent, carrying out constant-temperature reaction, filtering, washing and vacuum drying to obtain tert-butyl graphene peroxide;
(3) adding acrylonitrile and tert-butyl graphene peroxide into an N, N-dimethylformamide solvent, performing ultrasonic dispersion, adding 2,2,6, 6-tetramethylpiperidine oxide, performing heating and stirring reaction, standing for defoaming, placing the obtained spinning solution into an electrostatic spinning machine, and performing electrostatic spinning on a receiving plate under the spinning voltage of 18-20KV to obtain the graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption membrane.
2. The graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film according to claim 1, which is characterized in that: the functionalized modified graphene oxide, tert-butyl hydroperoxide and NaHCO in the step (2)3The mass ratio of (A) to (B) is 100:30-50: 0.5-1.
3. The graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film according to claim 1, which is characterized in that: the constant-temperature reaction atmosphere in the step (2) is a nitrogen atmosphere, the reaction temperature is 25-35 ℃, and the reaction time is 10-20 h.
4. The graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film according to claim 1, which is characterized in that: in the step (3), the mass ratio of the acrylonitrile to the tert-butyl graphene peroxide to the 2,2,6, 6-tetramethyl piperidine oxide is 100:0.5-5: 0.15-0.5.
5. The graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film according to claim 1, which is characterized in that: the heating and stirring reaction atmosphere in the step (3) is a nitrogen atmosphere, the reaction temperature is 50-70 ℃, and the reaction time is 24-48 h.
6. The graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film according to claim 1, which is characterized in that: the electrostatic spinning machine in the step (3) comprises a top frame plate, a liquid storage tank is fixedly connected to the upper portion of the top frame plate, a liquid storage tank pipe is fixedly connected to the liquid storage tank, a liquid outlet valve is arranged on the liquid storage tank pipe, a piston is fixedly connected to the lower portion of the top frame plate, a piston barrel column is movably connected to the piston, the top frame plate is movably connected with a spinning machine box through an electric telescopic rod, a digital display controller is fixedly connected with the spinning machine box, a positive high-voltage electrostatic output device is fixedly connected with the spinning machine box and is movably connected with a spinning needle through an electric wire, and a receiving plate is arranged in the spinning machine box.
CN202110100725.8A 2021-04-14 2021-04-14 Preparation method of graphene oxide grafted polyacrylonitrile fiber heavy metal adsorption film Withdrawn CN113144920A (en)

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Publication number Priority date Publication date Assignee Title
CN114797503A (en) * 2022-06-28 2022-07-29 南通纳爱斯环保科技有限公司 Graphene-quaternary ammonium salt modified polyacrylonitrile composite fiber filtering membrane and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114797503A (en) * 2022-06-28 2022-07-29 南通纳爱斯环保科技有限公司 Graphene-quaternary ammonium salt modified polyacrylonitrile composite fiber filtering membrane and preparation method thereof

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Application publication date: 20210723