CN111318267A - Block copolymer embedded nano zero-valent iron material, preparation method and application thereof - Google Patents
Block copolymer embedded nano zero-valent iron material, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a block copolymer embedded nano zero-valent iron material, a preparation method and application thereof. The preparation method comprises the following steps: dissolving the amphiphilic block copolymer and the nano zero-valent iron in an organic solvent, adding water, stirring, and then distilling under reduced pressure; adding a modified chitosan solution, and stirring for reaction in a nitrogen atmosphere; and finally, adding a cross-linking agent, and stirring for reaction in a nitrogen atmosphere to obtain the polyurethane foam material. Compared with the prior art, the amphiphilic block copolymer embedded nano zero-valent iron material is prepared by embedding nano zero-valent iron through the block copolymer in a self-assembly manner according to the hydrophobic effect, so that the stability and the dispersibility of the embedded nano zero-valent iron material in underground water are improved, and the efficient adsorption and degradation of CAHs are finally realized.
Description
Technical Field
The invention relates to a block copolymer embedded nano zero-valent iron material, a preparation method and application thereof.
Background
CAHs are Volatile Organic Compounds (VOCs), and most CAHs have higher density than water, lower solubility and strong fat solubility. Most of the CAHs have acute or chronic toxicity, can cause liver, kidney and heart malformation and cancerogenesis after long-term contact, and are widely applied to chemical industry, leather industry and dry cleaning industry.
The zero-valent iron reduction technology has become an important technology for removing chlorinated aliphatic hydrocarbon pollution of soil and underground water in recent years. The subject group carries out related research aiming at the pollution plume distribution, migration and transformation rule, natural attenuation rule and repairing material of CAHs in ground groundwater, and sends a plurality of high-level papers. However, in the process of removing chlorinated aliphatic hydrocarbon in underground water by using the repairing material in practical application, some problems which are difficult to overcome are encountered, for example, zero-valent iron and carbon-based composite material thereof react in underground water too fast and react with other substances in underground water without contacting with target CAHs.
The aerogel, as a nano porous material, has a continuous three-dimensional nano porous network structure formed by nano particles, and has the characteristics of low density, high porosity, high specific surface area, large pore volume and the like. The unique structural characteristics enable the aerogel to have good performances in the aspects of adsorption separation, water treatment and the like, and have wide application prospects in the field of environmental protection.
One of the block copolymer and the gel material is a high molecular polymer prepared by connecting two or more polymer segments with different properties. The block polymer with a specific structure has different properties from a mixture of a simple linear polymer, a plurality of random copolymers and homopolymers, and can be used as an interface modifier. In recent years, the self-assembly of a block copolymer and inorganic nanoparticles to form an organic/inorganic composite functional material has been widely used in many fields. Such as drug sustained release, chemical engineering, and the like.
According to the invention, the nano zero-valent iron is embedded by the block copolymer in a self-assembly manner according to the hydrophobic effect, so that the block copolymer embedded nano zero-valent iron material is prepared, the stability and the dispersibility of the embedded nano zero-valent iron material in underground water are improved, and the high-efficiency adsorption and degradation of CAHs are finally realized.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is that the zero-valent iron material reacts too quickly in repairing the polluted groundwater and reacts with other substances in the groundwater without contacting with the target CAHs.
The amphiphilic block copolymer embedded nano material has the advantages of controllable permeability, good water solubility and biocompatibility and the like, and has good application prospect in the field of controllable drug release. But the application in the aspect of environmental pollution control is still blank. Theoretically, the amphipathy of the block copolymer enables the composite core-shell material to be stably dispersed in water, and can adsorb hydrophobic pollutants, such as chlorinated aliphatic hydrocarbon and the like, by utilizing the hydrophobic characteristic. The nano material in the core is used for targeted removal of the fat-soluble pollutants, so that the anti-oxidation capability of the nano material in the core can be improved, and the fat-soluble pollutants can be efficiently removed.
In order to realize the purpose, the invention provides a preparation method of a block copolymer embedded nano zero-valent iron material, which comprises the following steps: dissolving the block copolymer and the nano zero-valent iron in an organic solvent, adding water, stirring, carrying out reduced pressure distillation, and carrying out magnet separation to obtain the nano-iron-based catalyst.
The invention also provides a preparation method of the block copolymer embedded nano zero-valent iron material, which comprises the following steps:
dissolving the block copolymer and the nano zero-valent iron in an organic solvent, adding water, stirring, and then distilling under reduced pressure;
then adding chitosan, and stirring and reacting under the nitrogen atmosphere;
and finally, adding a cross-linking agent, and stirring for reaction in a nitrogen atmosphere to obtain the polyurethane foam material.
The invention also provides a preparation method of the block copolymer embedded nano zero-valent iron material, which comprises the following steps:
dissolving the block copolymer and the nano zero-valent iron in an organic solvent, adding water, stirring, and then distilling under reduced pressure;
adding chitosan, stirring and reacting for 1-3 hours at 25-35 ℃ under the nitrogen atmosphere;
and finally adding a cross-linking agent, stirring and reacting for 1-3 hours at 35-50 ℃ in a nitrogen atmosphere to obtain the modified polyurethane.
Preferably, the chitosan solution is prepared by dissolving chitosan in dilute acid; more specifically, the chitosan solution provided by the invention is prepared by mixing chitosan according to the mass ratio of (1-3): 100 is added into 2-3 wt% acetic acid aqueous solution to prepare the product.
The chitosan has poor solubility, is easily dissolved in dilute acid and is sticky, and the dissolved chitosan is in a gel state and has strong adsorption capacity.
The invention also provides a preparation method of the block copolymer embedded nano zero-valent iron material, which comprises the following steps:
dissolving the block copolymer and the nano zero-valent iron in an organic solvent, adding water, stirring, and then distilling under reduced pressure;
adding a modified chitosan solution, stirring and reacting for 1-3 hours at 25-35 ℃ under a nitrogen atmosphere;
and finally adding a cross-linking agent, stirring and reacting for 1-3 hours at 35-50 ℃ in a nitrogen atmosphere to obtain the modified polyurethane.
Preferably, the organic solvent is one of tetrahydrofuran and dichloromethane.
Preferably, the cross-linking agent is one of glutaraldehyde, glyoxal and genipin.
Preferably, the mass ratio of the block copolymer to the nano zero-valent iron is 1: (1-3).
Preferably, the preparation method of the modified chitosan solution comprises the following steps: dissolving 1-3 g of chitosan in 10mL of methanol, adding 15-20 mL of 20-50 wt% NaOH aqueous solution under stirring at 100-300 rpm and 10-30 ℃, then dropwise adding 15-20 mL of modifier at the speed of 5-10 mL/h, heating to 45-55 ℃, reacting for 2-14 h, filtering, washing obtained filter residue with water, ethanol and methanol in sequence, finally dehydrating with acetone, and drying at the temperature of 45-55 ℃ for 0.5-2.0 h to obtain modified chitosan; and dissolving the modified chitosan in water to prepare a 1-3 wt% modified chitosan aqueous solution.
Preferably, the modifier is ethanol solution containing 10-30 wt% of carbon disulfide and 10-30 wt% of cysteine.
Block copolymers are high molecular weight polymers prepared by linking together two or more polymer segments of different properties. The block polymer with a specific structure has different properties from a simple linear polymer, a plurality of random copolymers, a mixture of homopolymers, can be used as an interface modifier, and the like. In recent years, organic/inorganic composite functional materials formed by self-assembly of block copolymers and inorganic nanoparticles are widely used in various fields, such as drug sustained release, chemical engineering, and the like.
Amphiphilic block copolymers, which refer to macromolecular polymers having both hydrophilic and hydrophobic block ends, generally retain the incompatibility of the different blocks in solution. For example, in aqueous solution the hydrophobic segments drive the aggregation of the polymer chains, forcing the hydrophobic segments to form internally and the hydrophilic segments to form shell-stabilized micelles in solvated form. Micelles can only form above a certain concentration, the Critical Micelle Concentration (CMC). Below the critical micelle concentration, the individual polymers are dissolved in solution in the form of molecular chains, and the relative length of the blocks, the nature of the block copolymer and the relative molecular mass all affect the size of the CMC. In general, the relative molecular mass of the soluble segment remains constant, and the greater the relative molecular mass of the insoluble segment, the lower the CMC. The insoluble block in the block copolymer is covalently linked to the soluble block, and when the insoluble block is aggregated, the soluble block organizes the generation of precipitate, thereby micellizing to replace the precipitation process. In addition, the morphology of the micellar aggregates varies from case to case. Taking the self-assembly of polyacrylic acid-styrene in aqueous solution to obtain micelles as an example, according to the difference of the addition amount of water, spherical, rod-like, vesicle and other double-layer structures, hexagonal volume structures and large composite micelles can appear. The preparation conditions are controlled, and the balance of three forces (the extension degree of a nucleation block, the repulsion between shells and the interfacial energy) contributed by the free energy of the system is changed, so that the morphology of the micelle aggregate is influenced.
The amphiphilic block copolymer embedded nano material has the advantages of controllable permeability, good water solubility and biocompatibility and the like, and has good application prospect in the field of controllable drug release. But the application in the aspect of environmental pollution control is still blank. Theoretically, the amphipathy of the block copolymer enables the composite core-shell material to be stably dispersed in water, and can adsorb hydrophobic pollutants, such as chlorinated aliphatic hydrocarbon and the like, by utilizing the hydrophobic characteristic. The nano material in the core is used for targeted removal of the fat-soluble pollutants, so that the anti-oxidation capability of the nano material in the core can be improved, and the fat-soluble pollutants can be efficiently removed.
Preferably, the block copolymer is one of an amphiphilic block copolymer polyacrylic acid-styrene (PS-b-PAA), an amphiphilic block copolymer polyethylene glycol-poly (tert-butyl acrylate), and an amphiphilic block copolymer polyacrylic acid-b-poly (methyl acrylate).
The preparation method of the amphiphilic block copolymer polyacrylic acid-styrene (PS-b-PAA) comprises the following steps:
preparation of S1 Tert-butyl polyacrylate (PtBA):
adding 3.5-4.5 g of cuprous bromide (CuBr), 4-5 mL of methyl 2-Bromopropionate (BMP), 6.5-7.5 mL of Pentamethyldiethylenetriamine (PMDETA) and 75-90 mL of tert-butyl acrylate (tBA) into 80-120 mL of toluene under the conditions of drying and no oxygen, carrying out freeze-thaw circulation, carrying out stirring reaction at 55-65 ℃ under a nitrogen atmosphere for 290-350 min, purifying, removing impurities, and carrying out reduced pressure distillation to obtain tert-butyl polyacrylate (PtBA);
preparation of S2 polystyrene-Polytert-butyl acrylate (PS-b-PtBA):
under the conditions of drying and no oxygen, adding 3.5-4.5 g of cuprous bromide (CuBr), 50-60 g of poly (tert-butyl acrylate) (PtBA) prepared in the step S1, 10-14 g of Pentamethyldiethylenetriamine (PMDETA) and 300-350 mL of styrene into 80-120 mL of toluene, carrying out freeze-thaw cycle, stirring and reacting at 65-75 ℃ for 310-370 min under a nitrogen atmosphere, purifying and removing impurities, adding the purified and removed impurities into a methanol solution to obtain a precipitate, and carrying out vacuum drying on the precipitate to obtain the polystyrene-poly (tert-butyl acrylate);
s3, dissolving 0.3-0.6 g of polystyrene-tert-butyl polyacrylate prepared in the step S2 in 30-40 mL of dichloromethane, adding 1.0-1.5 mL of trifluoroacetic acid, stirring and mixing for 44-52 h, adding cold methanol to obtain white precipitate, and drying the white precipitate in vacuum to obtain the amphiphilic block copolymer polyacrylic acid-styrene.
Preferably, the preparation method of the nano zero-valent iron (NZVI) comprises the following steps:
(1) mixing Cetyl Trimethyl Ammonium Bromide (CTAB), n-butanol and isooctane, and ultrasonically oscillating; then FeSO is added4Aqueous solution is ultrasonically oscillated to prepare FeSO4Micro-emulsion; the hexadecyl trimethyl ammonium bromide and FeSO4The molar ratio of (0.035-0.045): 0.0015; the n-butanol, the isooctane and the FeSO4The volume mol ratio of (6-10): (20-25): 0.0015 mL/mL/mol; the FeSO4The molar concentration of the aqueous solution is 0.10-0.20 mol/L;
(2) mixing Cetyl Trimethyl Ammonium Bromide (CTAB), n-butanol and isooctane, and ultrasonically oscillating; then adding KBH4Aqueous solution and ultrasonic oscillation to prepare KBH4Micro-emulsion; the hexadecyl trimethyl ammonium bromide and KBH4The molar ratio of (0.035-0.045): 0.0075; the KBH4The molar concentration of the aqueous solution is 0.70-0.80 mol/L; the FeSO in the step (1)4And the KBH in the step (2)4The molar ratio of (1) to (4-6);
(3) reacting KBH4The microemulsion is dripped into FeSO4And (3) stirring and reacting the microemulsion for 40-80 min at the temperature of 20-35 ℃ in a nitrogen atmosphere, separating the solid by using a magnet, and washing, vacuum freeze-drying to obtain the nano zero-valent iron (NZVI).
The amphiphilic block copolymer polyethylene glycol-poly (tert-butyl acrylate) can be prepared by the prior art, for example, the amphiphilic block copolymer polyethylene glycol-poly (tert-butyl acrylate) is synthesized by an ATRP method, and the method specifically refers to the ATRP method for synthesizing amphiphilic polyethylene glycol-poly (tert-butyl acrylate) block copolymer, the Palai silk and the like, the report of high efficiency chemical engineering, volume 25, No. 5 of 10 months in 2011.
The amphiphilic block copolymer polyacrylic acid-b-polymethyl acrylate can be prepared by adopting the prior art, and is specifically referred to ' an amphiphilic block copolymer prepared by an RAFT method and application thereof in emulsion polymerization ', a Master academic paper of northwest university, Chenyuman, 2014 '.
The invention also discloses a block copolymer embedded nano zero-valent iron material which is prepared by the preparation method of the block copolymer embedded nano zero-valent iron material.
The invention also discloses application of the block copolymer embedded nano zero-valent iron material in repairing chlorinated aliphatic hydrocarbon polluted underground water.
The specific application comprises the following steps:
and (2) adding the block copolymer embedded nano zero-valent iron material into underground water polluted by chlorinated aliphatic hydrocarbon according to the mass-volume ratio (0.6-1) g/L, and oscillating and mixing uniformly.
The invention has the beneficial effects that:
the problems existing in the prior art are as follows: the zero-valent iron material reacts with other substances in the underground water in the process of repairing polluted underground water, and a large part of the zero-valent iron material is consumed without timely contacting with target CAHs, so that the degradation effect of the nano zero-valent iron material on the CAHs is weakened. According to the invention, the block copolymer is used for embedding the zero-valent nano-iron material, the amphipathy of the prepared block copolymer enables the composite core-shell material to be stably dispersed in water, the hydrophobic characteristic can be used for adsorbing hydrophobic pollutants CAHs, the internal nano-zero-valent iron material is used for carrying out targeted removal on the fat-soluble pollutants CAHs, the anti-oxidation capability of the internal nano-zero-valent iron material can be improved, and the fat-soluble pollutants CAHs can be efficiently removed.
The self-assembly of the block copolymer macromolecule and the nano zero-valent iron material has poor self-assembly effect based on electrostatic action; according to the invention, the amphiphilic block copolymer and the nano zero-valent iron material are adopted, chitosan is matched with a cross-linking agent to realize the efficient coating of block copolymer macromolecules on the nano zero-valent iron material, the stability of the nano zero-valent iron material embedded by the block copolymer is effectively improved, and the adsorption degradation effect of the nano zero-valent iron material embedded by the block copolymer on fat-soluble pollutants CAHs is further realized.
Detailed Description
Example 1
The preparation method of the nanometer zero-valent iron (NZVI) comprises the following steps:
under the condition of room temperature, 16g of Cetyl Trimethyl Ammonium Bromide (CTAB), 8mL of n-butanol and 23mL of isooctane are placed in a beaker, then ultrasonic oscillation is carried out for 3 minutes in an ultrasonic cleaner until the particle size of the ball block CTAB becomes small and uniform under the action of ultrasonic waves, the ball block CTAB is suspended and dispersed in the solution, and then 10mL of 0.15mol/L FeSO is added4The water solution is continued to be subjected to ultrasonic treatment until CTAB in the beaker is completely dissolved to form transparent and slightly viscous FeSO4Micro-emulsion;
under the condition of room temperature, 16g of Cetyl Trimethyl Ammonium Bromide (CTAB), 8mL of n-butanol and 23mL of isooctane are placed in a beaker, then ultrasonic oscillation is carried out for 3 minutes in an ultrasonic cleaner until the particle size of the ball block CTAB becomes small and uniform under the action of ultrasonic waves, the ball block CTAB is suspended and dispersed in the solution, and then 10mL of 0.75mol/L KBH is added4The water solution is continued to be subjected to ultrasonic treatment until CTAB in the beaker is completely dissolved to form transparent and slightly viscous KBH4Micro-emulsion;
FeSO (ferric oxide) is added4Adding the microemulsion into a three-neck flask, and adding KBH4And pouring the microemulsion into a constant-pressure funnel, introducing nitrogen, mechanically stirring for 60 minutes at 25 ℃, placing a rubidium magnet at the bottom of the three-neck flask, and washing with absolute ethyl alcohol and deionized water for multiple times until unreacted reagents adsorbed on the surface of the prepared nano zero-valent iron are removed. And finally, putting the obtained nano zero-valent iron into a vacuum drying oven for drying, and storing until the nano zero-valent iron is used in subsequent experiments.
Example 2
An amphiphilic block copolymer polyacrylic acid-styrene (PS-b-PAA), a preparation method thereof, comprising the following steps:
preparation of S1 Tert-butyl polyacrylate (PtBA):
firstly, adding (4.17g, 0.029mol) cuprous bromide into a schlenk bottle, opening a vacuum pump to exhaust air, and simultaneously heating the outer wall of the schlenk bottle by using a flame gun to remove water and remove oxygen for the whole glass device. Then adding (4.67mL, 0.042mol) methyl 2-Bromopropionate (BMP), (6.83mL, 0.033mol) Pentamethyldiethylenetriamine (PMDETA), (81mL, 0.558mol) tert-butyl acrylate (tBA) and 100mL toluene into a closed schlenk bottle, reacting for 3 times in an oil bath kettle at 60 ℃ after introducing nitrogen, continuously introducing nitrogen in the reaction process, continuously stirring by a magnetic stirrer, removing copper-containing impurities from the obtained tert-butyl polyacrylate through a neutral alumina chromatographic column to purify the polymer tert-butyl polyacrylate, and then carrying out reduced pressure distillation in a rotary evaporator to obtain transparent purified tert-butyl polyacrylate; GPC detection results show that the number average molecular weight of the poly (tert-butyl acrylate) is 1984;
preparation of S2 polystyrene-Polytert-butyl acrylate (PS-b-PtBA):
firstly, adding (4.17g, 0.029mol) cuprous bromide into a schlenk bottle, opening a vacuum pump to exhaust air, and simultaneously heating the outer wall of the schlenk bottle by using a flame gun to remove water and remove oxygen for the whole glass device. Then (57.67g, 0.029mol) poly (tert-butyl acrylate), (12.14mL, 0.058mol) Pentamethyldiethylenetriamine (PMDETA), (333mL, 2.907mol) styrene, 100mL toluene were put into Schlenk bottle, and after 3 times of nitrogen gas introduction, freeze-thaw cycle, nitrogen gas introduction again, and reaction was carried out in 70 ℃ oil bath for 340 minutes. After the reaction was completed, the schlenk bottle was transferred to liquid nitrogen to terminate the reaction. Removing impurities by a neutral alumina chromatographic column, pouring into cold methanol with the volume more than 10 times that of the polystyrene-poly (tert-butyl acrylate) to obtain polystyrene-poly (tert-butyl acrylate) precipitate, and finally drying in a vacuum drying oven to obtain the polystyrene-poly (tert-butyl acrylate); GPC detection results show that the polystyrene-poly (tert-butyl acrylate) has the number average molecular weight of 10931;
s3, dissolving 0.5g of polystyrene-poly (tert-butyl acrylate) prepared in the step S2 in 35mL of dichloromethane, adding 1.3mL of trifluoroacetic acid, stirring and mixing for 48h, adding cold methanol to obtain a white precipitate, and drying the white precipitate in vacuum to obtain the amphiphilic block copolymer polyacrylic acid-styrene.
Example 3
A preparation method of a block copolymer embedded nano zero-valent iron material comprises the following steps:
50mg of amphiphilic block copolymer acrylic acid-styrene and 125mg of nano zero-valent iron material are dissolved in 20mL of tetrahydrofuran (nitrogen is blown for deoxidation), then 100mL of deoxidized deionized water is rapidly added, and stirring is carried out for 30 minutes; and transferring the suspension into a round-bottom flask for reduced pressure distillation, removing residual tetrahydrofuran in the suspension, carrying out magnetic separation to obtain a solid, and carrying out vacuum reduced pressure freeze drying to obtain the amphiphilic block copolymer embedded nano zero-valent iron material.
The preparation method of the amphiphilic block copolymer polyacrylic acid-styrene is the same as that of example 2.
The preparation method of the nano zero-valent iron material is the same as that of the embodiment 1.
Example 4
A preparation method of a block copolymer embedded nano zero-valent iron material comprises the following steps:
50mg of amphiphilic block copolymer polyacrylic acid-styrene and 125mg of nano zero-valent iron material are dissolved in 20mL of tetrahydrofuran (nitrogen is blown for deoxidation), then 100mL of deoxidized deionized water is rapidly added, and stirring is carried out for 30 minutes; transferring the suspension into a round-bottom flask for reduced pressure distillation, and removing residual tetrahydrofuran in the suspension; and transferring the suspension into a dry three-neck flask, adding 2mL of acetic acid aqueous solution of chitosan, introducing nitrogen, mechanically stirring for 2 hours at the temperature of 30 ℃, subsequently adding 1mL of 2.5 wt% glutaraldehyde aqueous solution, mechanically stirring for 2 hours at the temperature of 40 ℃, and performing vacuum decompression freeze drying to obtain the amphiphilic block copolymer embedded nano zero-valent iron material.
The preparation method of the amphiphilic block copolymer polyacrylic acid-styrene is the same as that of example 2.
The preparation method of the nano zero-valent iron material is the same as that of the embodiment 1.
The acetic acid aqueous solution of chitosan is prepared by adding 0.2g of chitosan into 10mL of 2.5 wt% acetic acid and magnetically stirring for 2 hours until the chitosan is completely dissolved.
Example 5
In substantial agreement with example 4, the only difference is that: in the preparation method of the block copolymer embedded nano zero-valent iron material, the mass ratio of the amphiphilic block copolymer polyacrylic acid-styrene to the nano zero-valent iron material is 1:1, and the mass ratio is 50mg and 50mg respectively.
Example 6
In substantial agreement with example 4, the only difference is that: in the preparation method of the block copolymer embedded nano zero-valent iron material, the mass ratio of the amphiphilic block copolymer polyacrylic acid-styrene to the nano zero-valent iron material is 1:2, and the mass ratio is 50mg and 100mg respectively.
Example 7
In substantial agreement with example 4, the only difference is that: in the preparation method of the block copolymer embedded nano zero-valent iron material, the mass ratio of the amphiphilic block copolymer polyacrylic acid-styrene to the nano zero-valent iron material is 1:3, and the mass ratio is 50mg and 150mg respectively.
Example 8
A preparation method of a block copolymer embedded nano zero-valent iron material comprises the following steps:
50mg of amphiphilic block copolymer polyacrylic acid-styrene and 125mg of nano zero-valent iron material are dissolved in 20mL of tetrahydrofuran (nitrogen is blown for deoxidation), then 100mL of deoxidized deionized water is rapidly added, and stirring is carried out for 30 minutes; transferring the suspension into a round-bottom flask for reduced pressure distillation, and removing residual tetrahydrofuran in the suspension; and transferring the suspension into a dry three-neck flask, adding 2mL of modified chitosan solution, introducing nitrogen, mechanically stirring for 2 hours at 30 ℃, subsequently adding 1mL of 2.5 wt% glutaraldehyde aqueous solution, mechanically stirring for 2 hours at 40 ℃, and performing vacuum pressure reduction and freeze drying to obtain the amphiphilic block copolymer embedded nano zero-valent iron material.
The preparation method of the amphiphilic block copolymer polyacrylic acid-styrene is the same as that of example 2.
The preparation method of the nano zero-valent iron material is the same as that of the embodiment 1.
The preparation method of the modified chitosan solution comprises the following steps: dissolving 2g of chitosan in 10mL of methanol, adding 18mL of 40 wt% NaOH aqueous solution under stirring at 200rpm and 25 ℃, then dropwise adding 20mL of modifier at the speed of 10mL/h, heating to 50 ℃, reacting for 10h, filtering, washing obtained filter residue with water, ethanol and methanol in sequence, finally dehydrating with acetone, and drying at 50 ℃ for 1.0h to obtain modified chitosan; 0.2g of modified chitosan is dissolved in 10mL of water to obtain a modified chitosan aqueous solution.
The modifier is obtained by adding 10g of carbon disulfide into 10g of ethanol and uniformly mixing.
Example 9
A preparation method of a block copolymer embedded nano zero-valent iron material comprises the following steps:
50mg of amphiphilic block copolymer polyacrylic acid-styrene and 125mg of nano zero-valent iron material are dissolved in 20mL of tetrahydrofuran (nitrogen is blown for deoxidation), then 100mL of deoxidized deionized water is rapidly added, and stirring is carried out for 30 minutes; transferring the suspension into a round-bottom flask for reduced pressure distillation, and removing residual tetrahydrofuran in the suspension; and transferring the suspension into a dry three-neck flask, adding 2mL of modified chitosan solution, introducing nitrogen, mechanically stirring for 2 hours at 30 ℃, subsequently adding 1mL of 2.5 wt% glutaraldehyde aqueous solution, mechanically stirring for 2 hours at 40 ℃, and performing vacuum pressure reduction and freeze drying to obtain the amphiphilic block copolymer embedded nano zero-valent iron material.
The preparation method of the amphiphilic block copolymer polyacrylic acid-styrene is the same as that of example 2.
The preparation method of the nano zero-valent iron material is the same as that of the embodiment 1.
The preparation method of the modified chitosan solution comprises the following steps: dissolving 2g of chitosan in 10mL of methanol, adding 18mL of 40 wt% NaOH aqueous solution under stirring at 200rpm and 25 ℃, then dropwise adding 20mL of modifier at the speed of 10mL/h, heating to 50 ℃, reacting for 10h, filtering, washing obtained filter residue with water, ethanol and methanol in sequence, finally dehydrating with acetone, and drying at 50 ℃ for 1.0h to obtain modified chitosan; 0.2g of modified chitosan is dissolved in 10mL of water to obtain a modified chitosan aqueous solution.
The modifier is obtained by adding 10g of cysteine into 10g of ethanol and uniformly mixing.
Example 10
A preparation method of a block copolymer embedded nano zero-valent iron material comprises the following steps:
50mg of amphiphilic block copolymer polyacrylic acid-styrene and 125mg of nano zero-valent iron material are dissolved in 20mL of tetrahydrofuran (nitrogen is blown for deoxidation), then 100mL of deoxidized deionized water is rapidly added, and stirring is carried out for 30 minutes; transferring the suspension into a round-bottom flask for reduced pressure distillation, and removing residual tetrahydrofuran in the suspension; and transferring the suspension into a dry three-neck flask, adding 2mL of modified chitosan solution, introducing nitrogen, mechanically stirring for 2 hours at 30 ℃, subsequently adding 1mL of 2.5 wt% glutaraldehyde aqueous solution, mechanically stirring for 2 hours at 40 ℃, and performing vacuum pressure reduction and freeze drying to obtain the amphiphilic block copolymer embedded nano zero-valent iron material.
The preparation method of the amphiphilic block copolymer polyacrylic acid-styrene is the same as that of example 2.
The preparation method of the nano zero-valent iron material is the same as that of the embodiment 1.
The preparation method of the modified chitosan solution comprises the following steps: dissolving 2g of chitosan in 10mL of methanol, adding 18mL of 40 wt% NaOH aqueous solution under stirring at 200rpm and 25 ℃, then dropwise adding 20mL of modifier at the speed of 10mL/h, heating to 50 ℃, reacting for 10h, filtering, washing obtained filter residue with water, ethanol and methanol in sequence, finally dehydrating with acetone, and drying at 50 ℃ for 1.0h to obtain modified chitosan; 0.2g of modified chitosan is dissolved in 10mL of water to obtain a modified chitosan aqueous solution.
The modifier is obtained by adding 5g of carbon disulfide and 5g of cysteine into 10g of ethanol and uniformly mixing.
Example 11
A preparation method of a block copolymer embedded nano zero-valent iron material comprises the following steps:
50mg of amphiphilic block copolymer polyethylene glycol-poly (tert-butyl acrylate) and 125mg of nano zero-valent iron material are dissolved in 20mL of tetrahydrofuran (blown by nitrogen for deoxidation), then 100mL of deoxidized deionized water is rapidly added, and stirring is carried out for 30 minutes; transferring the suspension into a round-bottom flask for reduced pressure distillation, and removing residual tetrahydrofuran in the suspension; and transferring the suspension into a dry three-neck flask, adding 2mL of modified chitosan solution, introducing nitrogen, mechanically stirring for 2 hours at 30 ℃, subsequently adding 1mL of 2.5 wt% glutaraldehyde aqueous solution, mechanically stirring for 2 hours at 40 ℃, and performing vacuum pressure reduction and freeze drying to obtain the amphiphilic block copolymer embedded nano zero-valent iron material.
The amphiphilic block copolymer polyethylene glycol-poly (tert-butyl acrylate) is prepared by referring to a method disclosed in 'ATRP method for synthesizing amphiphilic polyethylene glycol-poly (tert-butyl acrylate) block copolymer, creazan and the like, high-efficiency chemical engineering report, 2011, 10, 25, 5 th volume'.
The preparation method of the nano zero-valent iron material is the same as that of the embodiment 1.
The preparation method of the modified chitosan solution comprises the following steps: dissolving 2g of chitosan in 10mL of methanol, adding 18mL of 40 wt% NaOH aqueous solution under stirring at 200rpm and 25 ℃, then dropwise adding 20mL of modifier at the speed of 10mL/h, heating to 50 ℃, reacting for 10h, filtering, washing obtained filter residue with water, ethanol and methanol in sequence, finally dehydrating with acetone, and drying at 50 ℃ for 1.0h to obtain modified chitosan; 0.2g of modified chitosan is dissolved in 10mL of water to obtain a modified chitosan aqueous solution.
The modifier is obtained by adding 5g of carbon disulfide and 5g of cysteine into 10g of ethanol and uniformly mixing.
Example 12
A preparation method of a block copolymer embedded nano zero-valent iron material comprises the following steps:
50mg of amphiphilic block copolymer polyacrylic acid-b-polymethyl acrylate and 125mg of nano zero-valent iron material are dissolved in 20mL of tetrahydrofuran (blown by nitrogen for deoxidation), then 100mL of deoxidized deionized water is rapidly added, and the mixture is stirred for 30 minutes; transferring the suspension into a round-bottom flask for reduced pressure distillation, and removing residual tetrahydrofuran in the suspension; and transferring the suspension into a dry three-neck flask, adding 2mL of modified chitosan solution, introducing nitrogen, mechanically stirring for 2 hours at 30 ℃, subsequently adding 1mL of 2.5 wt% glutaraldehyde aqueous solution, mechanically stirring for 2 hours at 40 ℃, and performing vacuum pressure reduction and freeze drying to obtain the amphiphilic block copolymer embedded nano zero-valent iron material.
The amphiphilic block copolymer polyacrylic acid-b-polymethyl acrylate is prepared by a method disclosed in the second chapter of the ' RAFT method for preparing the amphiphilic block copolymer and the application thereof in emulsion polymerization ', Chenyuman, the Master theory of academic parlance, northwest university, 2014 '.
The preparation method of the nano zero-valent iron material is the same as that of the embodiment 1.
The preparation method of the modified chitosan solution comprises the following steps: dissolving 2g of chitosan in 10mL of methanol, adding 18mL of 40 wt% NaOH aqueous solution under stirring at 200rpm and 25 ℃, then dropwise adding 20mL of modifier at the speed of 10mL/h, heating to 50 ℃, reacting for 10h, filtering, washing obtained filter residue with water, ethanol and methanol in sequence, finally dehydrating with acetone, and drying at 50 ℃ for 1.0h to obtain modified chitosan; 0.2g of modified chitosan is dissolved in 10mL of water to obtain a modified chitosan aqueous solution.
The modifier is obtained by adding 5g of carbon disulfide and 5g of cysteine into 10g of ethanol and uniformly mixing.
Example 13
A method for remedying chlorinated aliphatic hydrocarbon pollution in underground water comprises the following specific steps:
0.1g of the block copolymer embedded nano zero-valent iron material prepared in the embodiment 3-12 is put into 50 mL of 100mg/L TCE aqueous solution, then the solution is put into a constant temperature shaking table with the shaking speed of 180rpm and the temperature of 25 ℃ for reaction, 1mL of sample is taken by a disposable needle tube after 240min, the sample is filtered by a 0.22 mu m filter membrane and then placed into a sample feeding bottle, then the sample feeding GC analysis is carried out, and the TCE degradation rate is calculated according to the TCE concentration change, which is specifically shown in Table 1. The dissolved oxygen amount of the 100mg/L TCE aqueous solution was 7.3mg/L, and the initial pH was 7.
Trichloroethylene (TCE), as an efficient industrial solvent and cleaning agent, has long been used in the chemical, mechanical, electronic, leather and dry cleaning industries. TCEs, due to their improper use or disposal, permeate into soil and groundwater and migrate and transform in the environment as groundwater flows, causing a wide range of site soil and groundwater contamination.
Gas chromatography method parameters
TABLE 1 TCE degradation rate
| Rate of degradation | |
| Example 3 | 76.3％ |
| Example 4 | 86.3％ |
| Example 5 | 68.2％ |
| Example 6 | 80.7％ |
| Example 7 | 78.1％ |
| Example 8 | 90.7％ |
| Example 9 | 92.8％ |
| Example 10 | 95.2％ |
| Example 11 | 94.7％ |
| Example 12 | 94.3％ |
As can be seen from Table 1, the block copolymer embedded nano zero-valent iron material prepared in example 4 has a significantly better effect on the degradation of TCE than the block copolymer embedded nano zero-valent iron material prepared in example 3. The reasons for this are: embodiment 4 has adopted amphiphilic block copolymer and nanometer zero-valent iron material to realize block copolymer macromolecule to nanometer zero-valent iron material's high-efficient cladding through chitosan and cooperation cross-linking agent, compares the amphiphilic block copolymer that embodiment 3 adopted and nanometer zero-valent iron material electrostatic interaction's self-assembly effect better, and the nano zero-valent iron material's that the block copolymer embedding that prepares cladding effect is better, and stability is better, has finally promoted the degradation effect to TCE.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. A preparation method of a block copolymer embedded nano zero-valent iron material is characterized by comprising the following steps: dissolving the block copolymer and the nano zero-valent iron in an organic solvent, adding water, stirring, carrying out reduced pressure distillation, and carrying out magnet separation to obtain the nano-iron-based catalyst.
2. A preparation method of a block copolymer embedded nano zero-valent iron material is characterized by comprising the following steps:
dissolving the block copolymer and the nano zero-valent iron in an organic solvent, adding water, stirring, and then distilling under reduced pressure;
then adding a chitosan solution, and stirring and reacting under the nitrogen atmosphere;
and finally, adding a cross-linking agent, and stirring for reaction in a nitrogen atmosphere to obtain the polyurethane foam material.
3. A preparation method of a block copolymer embedded nano zero-valent iron material is characterized by comprising the following steps:
dissolving the block copolymer and the nano zero-valent iron in an organic solvent, adding water, stirring, and then distilling under reduced pressure;
then adding a chitosan solution, stirring and reacting for 1-3 hours at 25-35 ℃ under a nitrogen atmosphere;
and finally adding a cross-linking agent, stirring and reacting for 1-3 hours at 35-50 ℃ in a nitrogen atmosphere to obtain the modified polyurethane.
4. A preparation method of a block copolymer embedded nano zero-valent iron material is characterized by comprising the following steps:
dissolving the block copolymer and the nano zero-valent iron in an organic solvent, adding water, stirring, and then distilling under reduced pressure;
adding a modified chitosan solution, stirring and reacting for 1-3 hours at 25-35 ℃ under a nitrogen atmosphere;
and finally adding a cross-linking agent, stirring and reacting for 1-3 hours at 35-50 ℃ in a nitrogen atmosphere to obtain the modified polyurethane.
5. The method for preparing the block copolymer embedded nano zero-valent iron material according to any one of claims 1 to 4, wherein: the block copolymer is one of amphiphilic block copolymer polyacrylic acid-styrene, amphiphilic block copolymer polyethylene glycol-poly (tert-butyl acrylate), and amphiphilic block copolymer polyacrylic acid-b-polymethyl acrylate.
6. The method for preparing the block copolymer embedded nano zero-valent iron material according to claim 5, wherein the method for preparing the amphiphilic block copolymer polyacrylic acid-styrene comprises the following steps:
preparation of S1 Tert-butyl polyacrylate:
adding cuprous bromide, 2-bromomethyl propionate, pentamethyldiethylenetriamine and tert-butyl acrylate into toluene under the dry and oxygen-free conditions, performing freeze-thaw cycle, stirring and reacting at 55-65 ℃ for 290-350 min under the nitrogen atmosphere, purifying, removing impurities, and distilling under reduced pressure to obtain the tert-butyl acrylate;
preparation of S2 polystyrene-Polyt-butyl acrylate:
adding cuprous bromide, the tert-butyl polyacrylate prepared in the step S1, pentamethyldiethylenetriamine and styrene into toluene under the dry and oxygen-free conditions, performing freeze-thaw cycle, stirring and reacting for 310-370 min at 65-75 ℃ under a nitrogen atmosphere, purifying, removing impurities, adding into a methanol solution to obtain a precipitate, and performing vacuum drying on the precipitate to obtain the polystyrene-tert-butyl polyacrylate;
s3, dissolving the polystyrene-poly (tert-butyl acrylate) prepared in the step S2 in dichloromethane, adding trifluoroacetic acid, stirring and mixing for 44-52 hours, adding cold methanol to obtain white precipitate, and drying the white precipitate in vacuum to obtain the amphiphilic block copolymer polyacrylic acid-styrene.
7. The method for preparing the block copolymer embedded nano zero-valent iron material as claimed in any one of claims 1 to 4, wherein the method for preparing the nano zero-valent iron comprises the following steps:
(1) mixing cetyl trimethyl ammonium bromide, n-butanol and isooctane, and ultrasonically oscillating; then FeSO is added4Aqueous solution is ultrasonically oscillated to prepare FeSO4Micro-emulsion;
(2) mixing cetyl trimethyl ammonium bromide, n-butanol and isooctane, and ultrasonically oscillating; then adding KBH4Aqueous solution and ultrasonic oscillation to prepare KBH4Micro-emulsion;
(3) reacting KBH4The microemulsion is dripped into FeSO4And (3) stirring and reacting the microemulsion for 40-80 min at the temperature of 20-35 ℃ in a nitrogen atmosphere, separating solids by using a magnet, washing and drying in vacuum to obtain the nano zero-valent iron.
8. The method for preparing the block copolymer embedded nano zero-valent iron material according to any one of claims 2 to 4, wherein: the cross-linking agent is one of glutaraldehyde, glyoxal and genipin.
9. A block copolymer embedded nano zero-valent iron material is characterized in that: the block copolymer embedded nano zero-valent iron material is prepared by the preparation method of the block copolymer embedded nano zero-valent iron material as claimed in any one of claims 1 to 8.
10. Use of the block copolymer embedded nano zero valent iron material of claim 9 in remediation of chlorinated aliphatic hydrocarbon contaminated groundwater.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280069A (en) * | 2008-05-22 | 2008-10-08 | 复旦大学 | Preparation of cross linker for synthesizing amphipathic gel and application of the cross linker |
| CN105664884A (en) * | 2016-03-29 | 2016-06-15 | 中国地质大学（北京） | Magnetic adsorbent for removing heavy metal in water and method for preparing magnetic adsorbent |
| CN107445289A (en) * | 2017-08-22 | 2017-12-08 | 西安交通大学 | PVA/ chitosan sphere bio-carriers and preparation method thereof |
-
2020
- 2020-02-27 CN CN202010124021.XA patent/CN111318267A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280069A (en) * | 2008-05-22 | 2008-10-08 | 复旦大学 | Preparation of cross linker for synthesizing amphipathic gel and application of the cross linker |
| CN105664884A (en) * | 2016-03-29 | 2016-06-15 | 中国地质大学（北京） | Magnetic adsorbent for removing heavy metal in water and method for preparing magnetic adsorbent |
| CN107445289A (en) * | 2017-08-22 | 2017-12-08 | 西安交通大学 | PVA/ chitosan sphere bio-carriers and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| DONGYANG SHI等: "Highly reactive and stable nanoscale zero-valent iron prepared within vesicles and its high-performance removal of water pollutants", 《APPLIED CATALYSIS B-ENVIRONMENTAL》 * |
| 徐柳等: "壳聚糖包覆型纳米铁去除水中三氯乙烯实验研究", 《工业水处理》 * |
| 詹聪: "PAA-b-PS包埋纳米Fe/Ni双金属去除地下水中1,1,1-TCA和Cr(VI)", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113231104A (en) * | 2021-05-31 | 2021-08-10 | 华中科技大学 | Amino acid modified nano zero-valent iron material and preparation method thereof |
| CN113231104B (en) * | 2021-05-31 | 2022-06-14 | 华中科技大学 | Amino acid modified nano zero-valent iron material and preparation method thereof |
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