CN113831761A - Amino acid modified nano particle, preparation method and application thereof, and anti-fouling ultrafiltration membrane - Google Patents

Amino acid modified nano particle, preparation method and application thereof, and anti-fouling ultrafiltration membrane Download PDF

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CN113831761A
CN113831761A CN202111293966.5A CN202111293966A CN113831761A CN 113831761 A CN113831761 A CN 113831761A CN 202111293966 A CN202111293966 A CN 202111293966A CN 113831761 A CN113831761 A CN 113831761A
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amino acid
nanoparticle
nanoparticles
modified
membrane
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CN113831761B (en
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于有海
王�琦
陈春海
代凤娜
姚佳楠
钱广涛
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Donghua University
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Abstract

The invention provides amino acid modified nanoparticles, a preparation method and application thereof, and an anti-fouling ultrafiltration membrane, and relates to the technical field of ultrafiltration membrane materials. The amino acid modified nanoparticle provided by the invention comprises a nanoparticle, an amino acid and a grafting unit for grafting the nanoparticle and the amino acid, wherein the grafting unit is a silane coupling agent. In the invention, the amino acid has the advantages of organic compatibility and strong hydrophilicity, and the amino acid is grafted on the surface of the nano particle by means of the amphiphilic property of the silane coupling agent, so that the hydrophilic surface modification of the nano particle is realized, and on one hand, the interaction among the particles is reduced by coating the surface of the nano particle, and the agglomeration effect is weakened; on the other hand, the amino acid is grafted on the surface of the nano particle, so that the hydrophilicity of the material and the compatibility stability with the organic membrane matrix are enhanced.

Description

Amino acid modified nano particle, preparation method and application thereof, and anti-fouling ultrafiltration membrane
Technical Field
The invention relates to the technical field of ultrafiltration membrane materials, in particular to amino acid modified nanoparticles, a preparation method and application thereof, and an anti-fouling ultrafiltration membrane.
Background
Ultrafiltration (UF) is a low-pressure-driven membrane separation technique with separation precision between Microfiltration (MF) and Nanofiltration (NF), and has low driving pressure (0.1-0.6 MPa) and high permeation flux (100-500 L.m.-2·h-1·bar-1) And the molecular weight cut-off (1000-200000 Da) and the like, and is widely applied to the fields of wastewater treatment, medicine and health, municipal drinking water purification and the like.
However, in the practical application process, the traditional membrane-making material is easy to adsorb hydrophobic substances in the solution to be treated in the separation operation due to its strong hydrophobic property, so that the pores of the separation membrane are blocked, and the membrane is polluted to reduce the separation performance of the membrane. The membrane cleaning process aiming at membrane pollution greatly shortens the service life of the membrane on one hand; and the maintenance cost of the separation membrane is greatly increased. The polymer membrane is subjected to hydrophilic modification, so that the pollution resistance of the separation membrane can be effectively improved, and in the separation process, the hydrophilic membrane surface is easy to interact with water molecules to form a hydration layer on the membrane surface, so that the adsorption effect of hydrophobic pollutants on the membrane surface is effectively blocked, and the membrane pollution is reduced.
Blending modification is the simplest and most convenient and rapid hydrophilic modification means of the membrane. With the development of nanotechnology, more and more nanomaterials with excellent surface properties are beginning to receive wide attention from film researchers. The high specific surface energy of the nano particles leads to obvious agglomeration among nanometers, thereby limiting the exhibition of the performance advantage of the material on the nano scale.
Disclosure of Invention
The invention aims to provide amino acid modified nanoparticles, a preparation method and application thereof, and an anti-fouling ultrafiltration membrane.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an amino acid modified nanoparticle, which comprises a nanoparticle, an amino acid and a grafting unit for grafting the nanoparticle and the amino acid, wherein the grafting unit is a silane coupling agent.
Preferably, the nanoparticles comprise silicon dioxide, titanium dioxide, graphene oxide, aluminum oxide, zinc oxide or ferroferric oxide.
Preferably, the silane coupling agent includes vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, N-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, diethylaminomethyltriethoxysilane, N- (beta-methoxyethyl) -gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, and mixtures thereof, Anilinemethyltriethoxysilane or dichloromethyltriethoxysilane.
Preferably, the amino acid is an alpha-amino acid.
Preferably, the grafting amount of the amino acid is 5-15 wt% based on the total mass of the amino acid modified nanoparticles being 100%.
The invention provides a preparation method of amino acid modified nanoparticles, which comprises the following steps:
mixing the nano particles, a silane coupling agent and an ethanol water solution to obtain a nano particle dispersion liquid;
and mixing the nanoparticle dispersion liquid with an amino acid aqueous solution, and carrying out a grafting reaction to obtain the amino acid modified nanoparticles.
Preferably, the mass ratio of the silane coupling agent to the nanoparticles is 0.3-1.2: 1.
preferably, the mass ratio of the amino acid to the nanoparticles is 0.5-1: 1.
the invention provides application of the amino acid modified nanoparticles in the technical scheme or the amino acid modified nanoparticles prepared by the preparation method in the technical scheme in an anti-fouling ultrafiltration membrane.
The invention also provides an anti-fouling ultrafiltration membrane, which comprises a polymer membrane matrix and amino acid modified nano particles dispersed in the polymer membrane matrix; the amino acid modified nanoparticles are the amino acid modified nanoparticles in the technical scheme or the amino acid modified nanoparticles prepared by the preparation method in the technical scheme.
The invention provides an amino acid modified nanoparticle, which comprises a nanoparticle, an amino acid and a grafting unit for grafting the nanoparticle and the amino acid, wherein the grafting unit is a silane coupling agent. In the invention, the amino acid has the advantages of organic compatibility and strong hydrophilicity, and the amino acid is grafted on the surface of the nano particle by virtue of the amphiphilic property of the silane coupling agent, so that the hydrophilic surface modification of the nano particle is realized, on one hand, the amino acid is used for coating the surface of the nano particle, the interaction among particles is reduced, and the agglomeration effect is weakened, thereby being more beneficial to the dispersion in a polymer film matrix; on the other hand, the amino acid is grafted on the surface of the nano particles to enhance the hydrophilicity of the material, and when the amino acid modified nano particles are used for an anti-fouling ultrafiltration membrane, the compatibility and stability of the amino acid modified nano particles and a polymer membrane matrix are enhanced.
The amino acid modified nano particles provided by the invention are used as modified fillers to prepare the anti-fouling ultrafiltration membrane, so that the permeability, the selectivity and the anti-fouling performance of the anti-fouling ultrafiltration membrane are improved.
Drawings
FIG. 1 is a schematic diagram of amino acid-modified nanoparticles provided by the present invention;
FIG. 2 is a schematic diagram of modification of silica nanoparticles with lysine according to example 1;
FIG. 3 is a comparison graph of the infrared spectra of example 1 before and after lysine modification of silica nanoparticles;
FIG. 4 is a schematic view of the interaction between the amino acid-modified silica nanoparticles and the poly (arylene ether nitrile) polymer molecular chains in examples 1-3;
FIG. 5 is a comparison of the ultrafiltration cycle experiments of comparative example 1 and example 1;
FIG. 6 shows PEN/K-SiO prepared in example 12And the cross section of the/PVP-k 30 blended ultrafiltration membrane is subjected to scanning electron microscopy.
Detailed Description
The invention provides an amino acid modified nanoparticle, which comprises a nanoparticle, an amino acid and a grafting unit for grafting the nanoparticle and the amino acid, wherein the grafting unit is a silane coupling agent.
In the invention, the amino acid modified nanoparticles are subjected to surface hydrophilic modification on the nanoparticles through a covalent bond by using a silane coupling agent and amino acid. In a specific embodiment of the invention, the amino acid-modified nanoparticle is shown in fig. 1.
In the present invention, the nanoparticles preferably comprise silicon dioxide (SiO)2) Titanium dioxide (TiO)2) Graphene Oxide (GO) and aluminum oxide (Al)2O3) Zinc oxide (ZnO) or ferroferric oxide (Fe)3O4). In the invention, the particle diameter of the nano particles is preferably 10-500 nm, and more preferably 10-100 nm. In the invention, the nano particles have active hydroxyl groups, and amino acid can be grafted on the surfaces of the nano particles by using a silane coupling agent.
The amino acid modified nanoparticles provided by the invention comprise amino acid grafted on the surface of the nanoparticles. In the present invention, the amino acid is preferably an α -amino acid, and more preferably includes glycine, serine, threonine, cysteine, tyrosine, lysine, arginine, histidine, aspartic acid or glutamic acid. Compared with other kinds of amino acid, the alpha-amino acid adopted by the invention can improve the activity of the grafting reaction.
In the present invention, the grafting amount of the amino acid is preferably 5 to 15 wt%, and more preferably 10 to 15 wt%, based on 100% by mass of the total amino acid-modified nanoparticles.
In the present invention, the amino acid is grafted on the nanoparticle surface by a silane coupling agent. In the present invention, the silane coupling agent preferably includes vinyltriethoxysilane (A-151), vinyltrimethoxysilane (A-171), vinyltris (β -methoxyethoxy) silane (A-172), γ -aminopropyltrimethoxysilane (KH-540), γ -aminopropyltriethoxysilane (KH-550), 3-aminopropyltrimethoxysilane (KH-551), 3-glycidoxypropyltrimethoxysilane (KH-560), γ -methacryloxypropyltrimethoxysilane (KH-570), γ -mercaptopropyltriethoxysilane (KH-580), N- β -aminoethyl- γ -aminopropylmethyldimethoxysilane (KH-602), N- (β -aminoethyl) - γ -aminopropyltriethoxysilane (KH-791), N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (KH-792), gamma-aminopropylmethyldiethoxysilane (KH-902), diethylaminomethyltriethoxysilane (ND-22), anilinomethyltriethoxysilane (ND-42) or dichloromethyltriethoxysilane (ND-43). In the present invention, the silane coupling agent is preferably contained in an amount of 10 to 30% by mass, more preferably 20 to 25% by mass, based on 100% by mass of the total amino acid-modified nanoparticles.
In a specific embodiment of the present invention, when the nanoparticle is silicon dioxide, the amino acid is lysine, arginine or histidine, and the silane coupling agent is KH-560; when the nano particles are titanium dioxide, the amino acid is lysine, and the silane coupling agent is KH-570; when the nano particles are graphene oxide, the amino acid is aspartic acid, and the silane coupling agent is KH-540; when the nano particles are aluminum oxide, the amino acid is glutamic acid, and the silane coupling agent is A-171; when the nano particles are zinc oxide, the amino acid is serine, and the silane coupling agent is A-151.
The invention also provides a preparation method of the amino acid modified nano particle in the technical scheme, which comprises the following steps:
mixing the nano particles, a silane coupling agent and an ethanol water solution to obtain a nano particle dispersion liquid;
and mixing the nanoparticle dispersion liquid with an amino acid aqueous solution, and carrying out a grafting reaction to obtain the amino acid modified nanoparticles.
The method mixes the nano particles, the silane coupling agent and the ethanol water solution to obtain the nano particle dispersion liquid. In the present invention, the volume concentration of ethanol in the ethanol aqueous solution is preferably 20%. In the invention, the mass ratio of the silane coupling agent to the nanoparticles is preferably 0.3-1.2: 1, more preferably 0.8 to 1.0: 1. In the invention, the dosage ratio of the nanoparticles to the ethanol aqueous solution is preferably 0.5-4 g:1dL, more preferably 2.5 to 3g:1 dL.
In the present invention, the mixing of the nanoparticles, the silane coupling agent, and the aqueous ethanol solution preferably includes: dispersing the nano particles in an ethanol water solution, adding a silane coupling agent, adjusting the pH value of the system to be acidic, heating and stirring. In the present invention, the method of dispersion preferably includes mechanical stirring, ultrasonic vibration or cell pulverization. In the invention, the pH value of the system is preferably adjusted by adopting a hydrochloric acid solution; the concentration of the hydrochloric acid solution is preferably 1 mol/L. In the invention, the pH value of the system is preferably 3-6.5, and more preferably 4.5-5.3. In the invention, the heating and stirring temperature is preferably 30-80 ℃, and more preferably 60-65 ℃; the heating and stirring time is preferably 4-12 hours, and more preferably 4-6 hours; the rotation speed of the heating and stirring is preferably 300 rpm. The invention adjusts the pH value of the mixed system to be acidic, and can promote the hydrolysis of the siloxane end group of the silane coupling agent to generate active hydroxyl functional groups.
After the nano particle dispersion liquid is obtained, the nano particle dispersion liquid and an amino acid aqueous solution are mixed for grafting reaction to obtain the amino acid modified nano particles. In the invention, the mass ratio of the amino acid to the nanoparticles is preferably 0.5-1: 1, more preferably 0.6 to 0.8: 1. In the invention, the mass concentration of the amino acid in the amino acid aqueous solution is preferably 5-20%, and more preferably 10-15%.
In the invention, the temperature of the grafting reaction is preferably 30-80 ℃, and more preferably 60-65 ℃; the time of the grafting reaction is preferably 2-24 hours, more preferably 3-12 hours, and further preferably 4-8 hours.
In the grafting reaction process, a silane coupling agent is hydrolyzed under an acidic condition to generate an active hydroxyl functional group; then dehydrating and condensing with the hydroxyl on the surface of the nano particle to realize the grafting (also called coating) of the silane coupling agent on the surface of the nano particle; and the epoxy end of the silane coupling agent and the active carboxyl on the amino acid molecular chain generate ring-opening reaction, so that the amino acid is grafted to the surface of the nano particle through the silane coupling agent.
According to the invention, preferably, after the grafting reaction, the obtained grafting reaction system is subjected to solid-liquid separation, and the obtained solid material is washed and dried in sequence to obtain the amino acid modified nanoparticles. In the present invention, the method of solid-liquid separation is preferably centrifugation. In the invention, the reagent used for washing is preferably ethanol, the invention has no special requirement on the washing times, and the washing is carried out until the product is neutral. In the present invention, the temperature of the drying is preferably 80 ℃, and the time of the drying is preferably 8 hours. In the present invention, the drying is preferably performed in a vacuum oven.
The invention provides application of the amino acid modified nanoparticles in the technical scheme or the amino acid modified nanoparticles prepared by the preparation method in the technical scheme in an anti-fouling ultrafiltration membrane, and particularly preferably the amino acid modified nanoparticles are used as a modified filler to prepare the anti-fouling ultrafiltration membrane. In the invention, the mass content of the amino acid modified nanoparticles in the anti-fouling ultrafiltration membrane is preferably 1-8%, and more preferably 5-7%.
The invention also provides an anti-fouling ultrafiltration membrane, which comprises a polymer membrane matrix and amino acid modified nano particles dispersed in the polymer membrane matrix; the amino acid modified nanoparticles are the amino acid modified nanoparticles in the technical scheme or the amino acid modified nanoparticles prepared by the preparation method in the technical scheme. In the invention, the mass content of the amino acid modified nanoparticles in the anti-fouling ultrafiltration membrane is preferably 1-8%, and more preferably 5-7%. In the present invention, the polymer film substrate preferably includes a polysulfone film, a polyethersulfone film, a polybiphenyl sulfone film, a polyarylethernitrile film, or a polyvinylidene fluoride film.
In the invention, the thickness of the antifouling ultrafiltration membrane is preferably 50-300 μm, and more preferably 100-200 μm.
The invention also provides a preparation method of the anti-fouling ultrafiltration membrane, which comprises the following steps:
dispersing the amino acid modified nano particles in an organic solvent to obtain a homogeneous suspension; the amino acid modified nanoparticles are the amino acid modified nanoparticles in the technical scheme or the amino acid modified nanoparticles prepared by the preparation method in the technical scheme;
mixing the homogeneous suspension, a polymer and an additive to obtain a membrane casting solution;
and forming a film by using the membrane casting solution to obtain the anti-fouling ultrafiltration membrane.
The invention disperses the amino acid modified nano particles in the organic solvent to obtain homogeneous suspension. In the present invention, the organic solvent preferably includes N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone or sulfolane.
In the present invention, the method of dispersion preferably includes mechanical stirring, ultrasonic vibration or cell pulverization.
In the invention, the mass concentration of the amino acid modified nanoparticles in the homogeneous suspension is preferably 1-8%, and more preferably 5-7%.
After obtaining the homogeneous suspension, the invention mixes the homogeneous suspension with the polymer and the additive to obtain the casting solution. In the present invention, the polymer preferably includes polysulfone, polyethersulfone, polybiphenyl sulfone, polyarylethernitrile or polyvinylidene fluoride. In the present invention, the number average molecular weight of the polymer is preferably 5 to 20 ten thousand Da, and more preferably 10 to 15 ten thousand Da. In the invention, the mass ratio of the polymer to the amino acid modified nanoparticles is preferably 0.92-1: 1, and more preferably 0.95-0.98: 1.
In the present invention, the additive preferably includes polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, potassium chloride or ammonium chloride. In the invention, the mass ratio of the additive to the polymer is preferably 0-0.05: 1, more preferably 0.02 to 0.04: 1. In the present invention, the additive can increase the permeability of the flat sheet membrane.
According to the invention, preferably, after the homogeneous suspension, the polymer and the additive are mixed, the obtained mixed system is sequentially defoamed and kept stand to obtain the membrane casting solution. In the present invention, the defoaming method is preferably vacuum defoaming. In the present invention, the temperature of the standing is preferably room temperature, and the time is preferably 30 min.
After the membrane casting solution is obtained, the invention forms a membrane from the membrane casting solution to obtain the anti-fouling ultrafiltration membrane. In the present invention, the film formation of the casting solution preferably includes: and coating the membrane casting solution on a substrate material, and removing the organic solvent and the additive to obtain the anti-fouling ultrafiltration membrane. In the present invention, the environmental conditions of the coating preferably include: room temperature; the relative humidity of the air is 30-70%. In the present invention, the coating method is preferably knife coating. In the present invention, the substrate material preferably includes a glass plate, a metal plate, or a porous nonwoven fabric.
In the present invention, it is preferable that after the coating is completed, aeration is performed to form a liquid film on the surface of the substrate material. In the present invention, the time for aeration is preferably 30 to 120 seconds, and more preferably 60 to 100 seconds.
In the present invention, the method for removing the organic solvent and the additive preferably includes: and immersing the liquid film into a deionized water coagulating bath for phase separation, and completely replacing the organic solvent and the additive in the liquid film by repeatedly changing water for many times.
In the invention, a liquid membrane is formed through the aeration process, and the antifouling ultrafiltration membrane is obtained through phase separation and thorough curing and forming.
The amino acid modified nano particles provided by the invention can effectively reduce the agglomeration phenomenon among the nano particles, and meanwhile, the amino acid grafted on the surfaces of the nano particles further increases the hydrophilicity of the nano material and the compatibility between the nano material and an organic film matrix. According to the invention, the amino acid modified nanoparticles are doped into the polymer ultrafiltration membrane matrix through physical blending, so that hydrophilic modification on the membrane surface is realized, and the prepared anti-fouling ultrafiltration membrane has high permeability, high selectivity and excellent anti-fouling performance.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of lysine modified silica particles and poly (arylene ether nitrile) (PEN) blended ultrafiltration membrane:
1.0g of SiO2Adding the nanoparticles into 50mL of ethanol aqueous solution (20 percent, V/V), and dispersing for 30min by ultrasonic oscillation to obtain uniformly dispersed suspension; then, 0 was added to the suspension.3g of silane coupling agent (KH-560) and a little hydrochloric acid to adjust the pH of the system to 6.5; the magnetic stirring system is kept under 60 ℃ for reaction for 6 h; dropwise adding 5mL of lysine aqueous solution (10 percent, g/g) into the reaction system, and continuously keeping the reaction for 3 hours; centrifuging to obtain modified SiO2Centrifuging and washing the nano particles with ethanol for multiple times to neutrality, and drying in a vacuum oven at 80 deg.C for 8h to obtain lysine modified nano particles (K-SiO)2)，K-SiO2As a white powder.
0.25g of the K-SiO2Adding into 18.75g N, N-dimethylacetamide, and ultrasonically oscillating for 30min to obtain homogeneous suspension; 4g of poly (arylene ether nitrile) (PEN, Mn 1.13X 10)5Da) and 2g of polyvinylpyrrolidone (PVP-k30), and mechanically stirring until all the components are completely dissolved to obtain a homogeneous membrane casting solution; defoaming, standing, uniformly coating the casting solution on a clean glass plate by a 100-micron film scraper, and aerating for 30 s; immersing the film into deionized water coagulation bath at room temperature to carry out phase separation, and finally curing to form a film; the solid membrane is continuously soaked in deionized water for 48h, and water is changed for many times to replace residual solvent and additive components in the polymer membrane, so that the anti-fouling ultrafiltration membrane (PEN/K-SiO)2/PVP-k30) film thickness 100. + -. 5 μm.
Example 2
Preparing an arginine modified silicon dioxide particle and poly (arylene ether nitrile) (PEN) blending ultrafiltration membrane:
1.0g of SiO2Adding the nanoparticles into 50mL of ethanol aqueous solution (20 percent, V/V), and dispersing for 30min by ultrasonic oscillation to obtain uniformly dispersed suspension; then, adding 0.3g of silane coupling agent (KH-560) and a little hydrochloric acid into the suspension to adjust the pH of the system to 6.3; the magnetic stirring system is kept under 60 ℃ for reaction for 6 h; dropwise adding 5mL of arginine aqueous solution (10 percent, g/g) into the reaction system, and continuously keeping the reaction for 12 hours; centrifuging to obtain modified SiO2Centrifuging and washing the nano particles with ethanol for multiple times until the nano particles are neutral, and drying the nano particles in a vacuum oven at the temperature of 80 ℃ for 8 hours to obtain arginine modified nano particles (R-SiO)2)，R-SiO2As a white powder.
0.25g of the R-SiO2Adding into 18.75g N, N-dimethyl acetamideCarrying out ultrasonic oscillation for 30min to obtain a homogeneous suspension; 4g of poly (arylene ether nitrile) (PEN, Mn 1.13X 10)5Da) and 2g of polyvinylpyrrolidone (PVP-k30), and mechanically stirring until all the components are completely dissolved to obtain a homogeneous membrane casting solution; defoaming, standing, uniformly coating the casting solution on a clean glass plate by a 100-micron film scraper, and aerating for 30 s; immersing the film into deionized water coagulation bath at room temperature to carry out phase separation, and finally curing to form a film; the solid membrane is continuously soaked in deionized water for 48h, and water is changed for many times to replace residual solvent and additive components in the polymer membrane, so that the anti-fouling ultrafiltration membrane (PEN/R-SiO)2/PVP-k30) film thickness 100. + -. 5 μm.
Example 3
Preparation of histidine-modified silica particles and poly (arylene ether nitrile) (PEN) blended ultrafiltration membrane:
1.0g of SiO2Adding the nanoparticles into 50mL of ethanol aqueous solution (20 percent, V/V), and dispersing for 30min by ultrasonic oscillation to obtain uniformly dispersed suspension; then, adding 0.3g of silane coupling agent (KH-560) and a little hydrochloric acid into the suspension to adjust the pH of the system to 4.5; the magnetic stirring system is kept under 60 ℃ for reaction for 6 h; 5mL of histidine aqueous solution (10 percent, g/g) is dropwise added into the reaction system, and the reaction is continuously kept for 8 hours; centrifuging to obtain modified SiO2Centrifuging and washing the nanoparticles with ethanol for multiple times to neutrality, and drying in a vacuum oven at 80 deg.C for 8 hr to obtain histidine modified nanoparticles (H-SiO)2)，H-SiO2As a white powder.
0.25g of the H-SiO2Adding into 18.75g N, N-dimethylacetamide, and ultrasonically oscillating for 30min to obtain homogeneous suspension; 4g of poly (arylene ether nitrile) (PEN, Mn 1.13X 10)5Da) and 2g of polyvinylpyrrolidone (PVP-k30), and mechanically stirring until all the components are completely dissolved to obtain a homogeneous membrane casting solution; defoaming, standing, uniformly coating the casting solution on a clean glass plate by a 100-micron film scraper, and aerating for 30 s; immersing the film into deionized water coagulation bath at room temperature to carry out phase separation, and finally curing to form a film; continuously soaking the solid film in deionized water for 48h, and replacing residual solvent and additive components in the polymer film by changing water for many times to obtain the final productTo antifouling ultrafiltration membranes (PEN/H-SiO)2/PVP-k30) film thickness 100. + -. 5 μm.
Example 4
Preparation of lysine modified titanium dioxide particles and poly (arylene ether nitrile) (PEN) blended ultrafiltration membrane:
1.0g of TiO2Adding the nanoparticles into 50mL of ethanol aqueous solution (20 percent, V/V), and dispersing for 1h by ultrasonic oscillation to obtain uniformly dispersed suspension; then, adding 0.3g of silane coupling agent (KH-570) and a little hydrochloric acid into the suspension to adjust the pH of the system to 5.5; the magnetic stirring system is kept to react for 4 hours at 80 ℃; dropwise adding 8mL of lysine aqueous solution (10 percent, g/g) into the reaction system, and continuously keeping the reaction for 2 hours; centrifuging to obtain modified TiO2Centrifuging and washing the nano particles with ethanol for multiple times until the nano particles are neutral, and drying the nano particles in a vacuum oven at the temperature of 80 ℃ for 8 hours to obtain lysine modified nano particles (K-TiO)2)，K-TiO2As a white powder.
0.25g of the K-TiO2Adding into 18.75g N, N-dimethylacetamide, and ultrasonically oscillating for 30min to obtain homogeneous suspension; 4g of poly (arylene ether nitrile) (PEN, Mn 1.13X 10)5Da) and 2g of polyvinylpyrrolidone (PVP-k30), and mechanically stirring until all the components are completely dissolved to obtain a homogeneous membrane casting solution; defoaming, standing, uniformly coating the casting solution on a clean glass plate by a 100-micron film scraper, and aerating for 30 s; immersing the film into deionized water coagulation bath at room temperature to carry out phase separation, and finally curing to form a film; continuously soaking the solid membrane in deionized water for 48h, and replacing residual solvent and additive components in the polymer membrane by changing water for many times to obtain anti-fouling ultrafiltration membrane (PEN/K-TiO)2/PVP-k30) film thickness 100. + -. 5 μm.
Example 5
Preparation of aspartic acid modified graphene oxide particles and Polysulfone (PSF) blended ultrafiltration membrane:
adding 0.8g of Graphene Oxide (GO) nanoparticles into 50mL of ethanol aqueous solution (20%, V/V), and dispersing for 30min by ultrasonic oscillation to obtain a uniformly dispersed suspension; then, adding 0.5g of silane coupling agent (KH-540) and a little hydrochloric acid into the suspension to adjust the pH of the system to 6.5; reacting for 4 hours at 65 ℃ by using a magnetic stirring holding system; dropwise adding 10mL of aspartic acid aqueous solution (10 percent, g/g) into the reaction system, and continuously keeping the reaction for 4 hours; centrifuging to obtain modified GO nano particles, centrifuging and washing the modified GO nano particles to be neutral by ethanol for multiple times, and drying the modified GO nano particles in a vacuum oven at the temperature of 80 ℃ for 8 hours to obtain aspartic acid modified nano particles (D-GO), wherein the D-GO is black powder.
Adding 0.25g of the D-GO into 18.75g of N, N-dimethylformamide, and carrying out ultrasonic oscillation for 30min to obtain a homogeneous suspension; 4g polysulfone (PSF, Mn 9.55X 10) were added4) And 2g of polyethylene glycol (PEG-6000), and mechanically stirring until all the components are completely dissolved to obtain a homogeneous membrane casting solution; defoaming, standing, uniformly coating the casting solution on a clean glass plate by a 100-micron film scraper, and aerating for 30 s; immersing the film into deionized water coagulation bath at room temperature to carry out phase separation, and finally curing to form a film; and continuously soaking the solid membrane in deionized water for 48h, and replacing residual solvent and additive components in the polymer membrane by changing water for many times to obtain the antifouling ultrafiltration membrane (PSF/D-GO/PEG-6000), wherein the membrane thickness is 100 +/-5 microns.
Example 6
Preparing a glutamic acid modified alumina particle and polyether sulfone (PES) blended ultrafiltration membrane:
adding 0.5g of aluminum oxide nano particles into 80mL of ethanol water solution (20 percent, V/V), and crushing and dispersing cells for 10min to obtain a uniformly dispersed suspension; then, 0.2g of a silane coupling agent (A-171) and a little hydrochloric acid were added to the suspension to adjust the pH of the system to 6.0; the magnetic stirring system is kept under 80 ℃ for reaction for 12 h; dropwise adding 25mL of glutamic acid aqueous solution (10 percent, g/g) into the reaction system, and continuously keeping the reaction for 24 hours; centrifuging to obtain modified aluminum oxide nanoparticles, centrifuging and washing with ethanol for multiple times to neutrality, and drying in a vacuum oven at 80 deg.C for 8 hr to obtain glutamic acid modified nanoparticles (E-Al)2O3)，E-Al2O3As a white powder.
0.25g of the E-Al2O3Adding into 18.75g N, N-dimethylformamide, and pulverizing cells for 10min to obtain homogeneous suspension; 4g of polyethersulfone (PES, Mn 1.04X 10)5) And 2g polyethylene glycol (PEG-10000), mechanicalStirring until all the components are completely dissolved to obtain a homogeneous casting solution; defoaming, standing, uniformly coating the casting solution on a clean glass plate by a 100-micron film scraper, and aerating for 30 s; immersing the film into deionized water coagulation bath at room temperature to carry out phase separation, and finally curing to form a film; continuously soaking the solid membrane in deionized water for 48h, and replacing residual solvent and additive components in the polymer membrane by changing water for several times to obtain antifouling ultrafiltration membrane (PES/E-Al)2O3PEG-10000) with a film thickness of 100 + -5 μm.
Example 7
Preparation of serine modified zinc oxide particles and polyvinylidene fluoride (PVDF) blended ultrafiltration membrane:
adding 0.5g of zinc oxide nanoparticles into 80mL of ethanol aqueous solution (20 percent, V/V), and crushing and dispersing cells for 10min to obtain uniformly dispersed suspension; then, adding 0.2g of silane coupling agent (A-151) and a little hydrochloric acid into the suspension to adjust the pH of the system to 5.3; the magnetic stirring system is kept under 80 ℃ for reaction for 12 h; dropwise adding 30mL of serine aqueous solution (10 percent, g/g) into the reaction system, and continuously keeping the reaction for 24 hours; centrifuging to obtain modified zinc oxide nanoparticles, centrifuging and washing with ethanol for multiple times to neutrality, and drying in a vacuum oven at 80 deg.C for 8 hr to obtain serine modified nanoparticles (S-ZnO), wherein S-ZnO is white powder.
Adding 0.25g of S-ZnO into 18.75g N-methyl pyrrolidone, and crushing cells for 10min to obtain a homogeneous suspension; 4g of polyvinylidene fluoride (PVDF, Mn 6.53X 10) were then added4) And 2g of polyethylene glycol (PEG-10000), and mechanically stirring until all the components are completely dissolved to obtain a homogeneous casting solution; defoaming, standing, uniformly coating the casting solution on a clean glass plate by a 125-micron film scraper, and aerating for 30 s; immersing the film into deionized water coagulation bath at room temperature to carry out phase separation, and finally curing to form a film; and continuously soaking the solid membrane in deionized water for 48h, and replacing residual solvent and additive components in the polymer membrane by changing water for many times to obtain the anti-fouling ultrafiltration membrane (PVDF/S-ZnO/PEG-10000), wherein the membrane thickness is 100 +/-5 mu m.
Comparative example 1
Preparing a poly (arylene ether nitrile) ultrafiltration membrane:
4g of polyarylene ether nitrile (PEN, Mn 1.13X 10)5) And 2g of N-methyl pyrrolidone (PVP-k30), dissolving in 18.75g of N, N-dimethylacetamide, stirring until all components are completely dissolved to obtain a homogeneous membrane casting solution, defoaming, standing, uniformly coating the membrane casting solution on a clean glass plate by a 100-micrometer membrane scraper, aerating for 30s, immersing the membrane casting solution in a deionized water coagulation bath at room temperature for phase separation, and finally curing to form a membrane; and continuously soaking the solid membrane in deionized water for 48h, and replacing residual solvent and additive components in the polymer membrane by changing water for many times to obtain the poly (arylene ether nitrile) ultrafiltration membrane (PEN/PVP-k30), wherein the membrane thickness is 100 +/-5 mu m.
Test example 1
The separation performance and flux recovery rate of the pure PEN ultrafiltration membrane in the comparative example 1 and the antifouling ultrafiltration membranes prepared in the examples 1 to 7 are shown in Table 1.
Table 1 shows the separation performance and flux recovery rate of the pure PEN ultrafiltration membrane prepared in comparative example 1 and the anti-fouling ultrafiltration membranes prepared in examples 1 to 7
Figure BDA0003335789410000121
In Table 1, PWF represents pure water flux, Jp represents permeate flux, R represents rejection, and FRR represents flux recovery.
As can be seen from Table 1, the blend-doped modified K-SiO film is comparable to the pure PEN matrix film2、R-SiO2、H-SiO2、K-TiO2The PEN blended film prepared by the filler has better permeability, and simultaneously retains good BSA (bovine serum albumin) interception efficiency; the flux recovery rate is obviously increased, which shows that the antifouling performance of the blend membrane is obviously improved. Although different modified fillers influence the selection and permeability of the separation membrane, the flux recovery rate of the blended membrane prepared by taking PSF, PES and PVDF as the membrane matrix is obviously higher than that of a pure PEN membrane. The amino acid modified nano particle is used as a modifier, so that the surface hydrophilicity of the polymer blend membrane can be well improved, and the anti-pollution performance of the separation membrane is improved.
Test example 2
FIG. 2 is a schematic diagram of modification of silica nanoparticles with lysine in example 1. As can be seen from FIG. 2, the silane coupling agent is acidified and hydrolyzed to generate active hydroxyl, the active hydroxyl and the hydroxyl on the surface of the nanoparticle are subjected to dehydration condensation, and simultaneously, the active epoxy end group on the silane coupling agent and the active amino group on the amino acid are subjected to ring-opening reaction.
FIG. 3 is a comparison of infrared spectra of lysine before and after modification of silica nanoparticles of example 1. SiO is clearly observed in both spectra in FIG. 32Located at 1106cm-1、970cm-1And 806cm-1Characteristic absorption peaks are respectively attributed to the asymmetric and symmetric stretching vibration of Si-O-Si and the bending vibration of Si-OH. And SiO after modification2Found in the FTIR spectrum of the nanoparticles at 2940cm-1、1508cm-1、1409cm-1Three new peaks are respectively corresponding to a methylene stretching vibration peak, an amino shearing vibration peak and an OH bond plane bending vibration peak on carboxyl.
FIG. 4 is a schematic diagram of the interaction between the amino acid-modified silica nanoparticles and the poly (arylene ether nitrile) polymer molecular chains in examples 1-3. As can be seen from fig. 4, there is a significant H bond interaction between the doped amino acid modified silica nanoparticles and the poly (arylene ether nitrile) polymer matrix.
FIG. 5 is a comparison of the ultrafiltration cycle experiments of comparative example 1 and example 1. As can be seen from FIG. 5, the poly (arylene ether nitrile) composite film doped with the amino acid modified silica nanoparticles has obvious antifouling durability.
FIG. 6 shows PEN/K-SiO prepared in example 12Cross-sectional Scanning Electron Microscope (SEM) of the/PVP-k 30 blended ultrafiltration membrane. As can be seen from FIG. 6, PEN/K-SiO2the/PVP-k 30 blended ultrafiltration membrane is a typical asymmetric membrane.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The amino acid modified nanoparticle is characterized by comprising a nanoparticle, an amino acid and a grafting unit for grafting the nanoparticle and the amino acid, wherein the grafting unit is a silane coupling agent.
2. The amino acid-modified nanoparticle of claim 1, wherein the nanoparticle comprises silica, titania, graphene oxide, alumina, zinc oxide, or ferroferric oxide.
3. The amino acid-modified nanoparticle according to claim 1, wherein the silane coupling agent comprises vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β -methoxyethoxy) silane, γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, γ -mercaptopropyltriethoxysilane, N- β -aminoethyl- γ -aminopropylmethyldimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltriethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, N- (β -methoxyethyl) - γ -aminopropyltriethoxysilane, N- (β -aminoethylmethyl) trimethoxysilane, N- (β -methoxyethyl) - γ -aminopropyltrimethoxysilane, N- (β -ethoxypropyl-trimethoxysilane, N-ethoxypropyl-trimethoxysilane, or N- (β -aminopropyltriethoxysilane, or N- (β -aminoethyl) - γ -aminopropyltriethoxysilane, Gamma-aminopropylmethyldiethoxysilane, diethylaminomethyltriethoxysilane, anilinomethyltriethoxysilane or dichloromethyltriethoxysilane.
4. The amino acid-modified nanoparticle according to claim 1, wherein the amino acid is an alpha-amino acid.
5. The amino acid-modified nanoparticle according to any one of claims 1 to 4, wherein the graft amount of the amino acid is 5 to 15 wt% based on 100% by mass of the total amino acid-modified nanoparticle.
6. A method for preparing amino acid modified nanoparticles according to any one of claims 1 to 5, comprising the steps of:
mixing the nano particles, a silane coupling agent and an ethanol water solution to obtain a nano particle dispersion liquid;
and mixing the nanoparticle dispersion liquid with an amino acid aqueous solution, and carrying out a grafting reaction to obtain the amino acid modified nanoparticles.
7. The preparation method according to claim 6, wherein the mass ratio of the silane coupling agent to the nanoparticles is 0.3-1.2: 1.
8. the preparation method according to claim 6 or 7, wherein the mass ratio of the amino acid to the nanoparticles is 0.5-1: 1.
9. use of the amino acid modified nanoparticles according to any one of claims 1 to 5 or the amino acid modified nanoparticles prepared by the preparation method according to any one of claims 6 to 8 in an anti-fouling ultrafiltration membrane.
10. An anti-fouling ultrafiltration membrane comprising a polymer membrane matrix and amino acid-modified nanoparticles dispersed in the polymer membrane matrix; the amino acid modified nanoparticles are amino acid modified nanoparticles as described in any one of claims 1 to 5 or amino acid modified nanoparticles prepared by the preparation method as described in any one of claims 6 to 8.
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