CN114832652A - Functional polymer nanofiltration membrane material and preparation method thereof - Google Patents
Functional polymer nanofiltration membrane material and preparation method thereof Download PDFInfo
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- CN114832652A CN114832652A CN202210444432.6A CN202210444432A CN114832652A CN 114832652 A CN114832652 A CN 114832652A CN 202210444432 A CN202210444432 A CN 202210444432A CN 114832652 A CN114832652 A CN 114832652A
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- polymer
- nanofiltration membrane
- membrane
- membrane material
- functional
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- 239000012528 membrane Substances 0.000 title claims abstract description 142
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 42
- 229920001002 functional polymer Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 43
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- 239000000843 powder Substances 0.000 claims abstract description 40
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- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- MUKJDVAYJDKPAG-UHFFFAOYSA-N 2,3-dibromopropyl prop-2-enoate Chemical compound BrCC(Br)COC(=O)C=C MUKJDVAYJDKPAG-UHFFFAOYSA-N 0.000 claims description 3
- CMPIGRYBIGUGTH-UHFFFAOYSA-N 2-bromoprop-2-enenitrile Chemical compound BrC(=C)C#N CMPIGRYBIGUGTH-UHFFFAOYSA-N 0.000 claims description 3
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 claims description 3
- RUROFEVDCUGKHD-UHFFFAOYSA-N 3-bromoprop-1-enylbenzene Chemical compound BrCC=CC1=CC=CC=C1 RUROFEVDCUGKHD-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
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- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 claims description 3
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- 125000005843 halogen group Chemical group 0.000 claims description 3
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- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 3
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Images
Classifications
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- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
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Abstract
The invention relates to a functional polymer nanofiltration membrane material and a preparation method thereof, wherein the method comprises the following steps: fully stirring and mixing the polymer powder, the vinyl monomer, the dispersing agent and the solvent, and performing high-energy ray irradiation treatment under a protective atmosphere to induce the vinyl monomer to perform graft polymerization reaction on the polymer powder; after washing and vacuum drying, dissolving the obtained modified powder in an organic solvent added with a pore-forming agent, and fully dissolving and degassing to obtain a membrane casting solution; obtaining a polymer composite membrane with a porous supporting layer or a polymer symmetrical membrane without a substrate by a flat plate blade coating or extrusion spinning-phase inversion method; and carrying out functionalization reaction treatment on the obtained polymer membrane and a functional modifier to obtain the functional polymer nanofiltration membrane material. Compared with the prior art, the technical route of the invention has the advantages of mature process, simple and convenient operation, controllable process, large process variability, low production cost and application prospect of mass production of the multifunctional polymer nanofiltration membrane.
Description
Technical Field
The invention relates to the technical field of nanofiltration membrane materials, in particular to a functional polymer nanofiltration membrane material and a preparation method thereof.
Background
Nanofiltration is a new membrane separation technology between reverse osmosis and ultrafiltration, and can trap particles or solutes with a particle size of several nanometers in a solvent. The nanofiltration membrane is mostly a charged nanoporous membrane, which can not only screen materials in size, but also show different Donnan potentials for ions with different charges and different valences. The pore diameter and surface charge characteristics of the nanofiltration membrane determine the unique performance of the nanofiltration membrane, the separation mechanism is the coexistence of screening and dissolution diffusion, and simultaneously, the nanofiltration membrane has a charge rejection effect, can effectively remove divalent and multivalent ions, various substances with the molecular weight more than 200, and can partially remove monovalent ions and substances with the molecular weight less than 200. The separation performance of the nanofiltration membrane is obviously superior to that of ultrafiltration and microfiltration, compared with the reverse osmosis membrane, the nanofiltration membrane has the advantages of partial removal of monovalent ions, low process osmotic pressure, low operating pressure, energy saving and the like, water is produced under the same water quality and environment, and the pressure required by the nanofiltration membrane is less than that required by the reverse osmosis membrane. Therefore, nanofiltration is well applied in the purification of drinking water and industrial water, purification of wastewater, concentration and separation of valuable components in industrial fluids, and the like.
The preparation method of the nanofiltration membrane mainly comprises an interfacial polymerization method, a surface charge method and a phase inversion method. The interfacial polymerization method is the most effective nanofiltration membrane preparation method at present, and is also the method for producing the most industrialized nanofiltration membrane varieties and the maximum yield. The general operation process is that the water solution with monomer or prepolymer dissolved is adsorbed by microporous base film, after the excessive casting film liquid is drained, the film is contacted with oil phase (such as cyclohexane) with another monomer or prepolymer dissolved for a certain time, so that the two reactants are diffused to the interface of two phases to generate polycondensation reaction, and a layer of compact polymer film is formed, thus obtaining the nanofiltration membrane. The interfacial polymerization monomer has high reactivity and high reaction speed, and simultaneously, because the reaction only occurs at a two-phase interface, the equivalent ratio of reactants does not need to be strictly controlled, the reaction degree is controlled by monomer diffusion and has self-inhibition property, an extremely thin film layer (50 nm) can be obtained, and the formed polymer film layer has less defects (desalinization, 2015,356: 226-254). However, the interfacial polymerization reaction speed is high, a plurality of factors influencing the reaction process increase the difficulty in controlling the interfacial polymerization process, the regulation and control on selecting a separation layer structure are reduced, the solvent consumption is high, the equipment utilization rate is low, and the production cost of the nanofiltration membrane is not easy to control. In addition, the nanofiltration membrane prepared by the interfacial polymerization method has great defects in the aspects of membrane pollution resistance, oxidation resistance, high-temperature stability, solvent resistance and the like, and the application range of the nanofiltration membrane is limited.
The surface charge method is an important method for preparing the nanofiltration membrane, and not only can improve the pollution resistance, acid and alkali resistance and pressure resistance of the membrane, but also can improve the selectivity of the membrane by charging. The main charging methods at present are: impregnation, polymerization, surface activation, grafting, crosslinking, coating, and the like. The method is often used together with other methods to improve the charging effect and increase the separation performance of the nanofiltration membrane.
The phase-inversion film-forming method is to make a homogeneous polymer solution with a certain composition undergo mass transfer exchange between a solvent and a non-solvent in the surrounding environment through a certain physical process, change the thermodynamic state of the solution, make the solution undergo phase separation from the homogeneous polymer solution, convert the solution into a three-dimensional macromolecular gel network structure, and finally solidify the solution to form a film. According to the physical method of changing thermodynamic state, it can be divided into: solvent evaporation phase inversion, thermal phase inversion, vapor deposition phase inversion, solution phase inversion, and the like. The solution phase transition method has simple preparation process and large process variability, can adjust the structure and performance of the membrane according to different application requirements, is a main method for preparing various separation membrane materials, and most membranes used for reverse osmosis, ultrafiltration, gas separation and the like are manufactured by the method, so the membrane is called a milestone in the development history of membrane preparation technology. However, the filter membrane material prepared by the phase inversion method also has the problems of poor pollution resistance and the like, and the separation performance of the filter membrane is usually obviously reduced by the subsequent functionalization treatment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a functional polymer nanofiltration membrane material and a preparation method thereof. The method is used for solving the problems that the existing polymer nanofiltration membrane has poor hydrophilicity, membrane pollution, short service life and the like, and the subsequent functional treatment has great influence on the membrane performance.
The purpose of the invention can be realized by the following technical scheme:
according to the technical scheme for preparing the functional polymer nanofiltration membrane material by combining the polymer powder grafting modification and the phase conversion film forming technology, the polymer powder is grafted and modified in advance, the polymer porous membrane is prepared by a phase conversion method, and finally, the functions of hydrophilicity, chargeability, antibacterial property, pollution resistance, oxidation resistance and the like are endowed to the obtained polymer nanofiltration membrane through charge functionalization treatment. The technical route has the advantages of mature process, simple and convenient operation, controllable process, large process variability and low production cost, and has the application prospect of producing the multifunctional polymer nanofiltration membrane in batch, and the method specifically comprises the following steps:
a method for preparing a functional polymer nanofiltration membrane material comprises the following steps:
fully stirring and mixing the polymer powder, the vinyl monomer, the dispersing agent and the solvent, and performing high-energy ray irradiation treatment under a protective atmosphere to induce the vinyl monomer to perform graft polymerization reaction on the polymer powder;
after washing and vacuum drying, dissolving the obtained modified powder in an organic solvent added with a pore-forming agent, and fully dissolving and degassing to obtain a membrane casting solution;
obtaining a polymer composite membrane with a porous supporting layer or a polymer symmetrical membrane without a substrate by a flat plate blade coating or extrusion spinning-phase inversion method;
and carrying out functional reaction treatment on the obtained polymer membrane and a functional modifier to obtain the functional polymer nanofiltration membrane material.
Further, the vinyl monomer is an organic compound containing carboxyl, nitrile, hydroxyl or amino; the dispersant is a nonionic dispersant; the protective atmosphere condition is vacuum sealing, nitrogen or inert atmosphere protection.
Further, the polymer powder comprises cellulose and derivatives thereof, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyvinylidene fluoride and copolymers thereof, polyurethane, polyether sulfone, polysulfone, polyarylsulfone, polyvinyl alcohol, polyvinyl acetals, polyester, polycarbonate, polysulfonamide, polyether ketone or polyether ether ketone;
the vinyl monomer comprises acrylonitrile, methacrylonitrile, chloroacrylonitrile, bromoacrylonitrile, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylic acid, vinyl acetate, 2-aminoethyl methacrylate, glycidyl methacrylate, 2, 3-dibromopropyl acrylate, chloromethyl styrene or bromomethyl styrene;
the dispersing agent comprises methanol, ethanol, ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trihydroxymethyl propane, glycerol, acetone or tween series emulsifying agents;
the solvent comprises methanol, ethanol, glycol, acetone, ethyl acetate, tetrahydrofuran, chloroform or water.
Further, the pore-forming agent comprises polyvinylpyrrolidone, polyethylene glycol, lithium chloride, zinc chloride or calcium carbonate; the organic solvent for preparing the casting solution comprises dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide or tetramethyl sulfoxide.
Further, the functional modifier comprises organic amine compounds such as methylamine, ethylamine, methylethylamine, diethylamine, ethylenediamine, propylamine, isopropylamine, diethylenetriamine and triethylenetetramine, inorganic alkali compounds such as ammonia water, sodium hydroxide and potassium hydroxide, amino acid compounds such as glycine and alanine, polyethyleneimine, polyvinylamine, polyvinyl alcohol, polyethylene glycol, taurine, propane sultone, butane sultone or hydroxylamine hydrochloride.
Further, the high-energy rays are electron beams or gamma rays; the irradiation condition is normal temperature, normal pressure and static treatment, the dosage rate is 50-50000Gy/h, and the absorbed dosage is 1-500 kGy.
Furthermore, in the grafting reaction system, the mass percent of the dispersing agent is 0.1-50%, the mass percent of the vinyl monomer is 0.1-45%, and the mass percent of the polymer powder is 1-40%.
Furthermore, the mass percent of the modified powder in the membrane casting solution is 5-45%, and the mass percent of the pore-forming agent is 0.5-20%.
Further, the functionalization reaction is a general organic reaction of a reactive group with respect to a cyano group, a halo group, a hydroxyl group, an ester group or a carboxyl group on the graft chain, including amination, hydrolysis, esterification, oxime amination and ring-opening reaction.
A functional polymer nanofiltration membrane material prepared by the method.
Compared with the prior art, the invention has the following advantages:
(1) the invention starts from modification of polymer powder, and then the pore size and distribution of the filter membrane prepared by phase inversion are not reduced due to grafting modification, and the graft chains are distributed on the surface of the filter membrane and in the interior of the membrane pores, and the three-dimensional functionalized filter membrane material can be obtained by subsequent functionalization reaction;
(2) the invention can obtain nanofiltration membrane materials with different functions through the functionalization reaction of the grafting chain; thirdly, the method is simple and controllable, is easy to operate, and is more suitable for continuous production compared with an interface polymerization method;
(3) the invention solves the problems that the polymer nanofiltration membrane prepared by the prior art has poor hydrophilicity, membrane pollution, short service life and the like, and the subsequent functionalization treatment has great influence on the membrane performance.
Drawings
FIG. 1 shows the contents of carbon, nitrogen and oxygen in the powder after graft modification of the polymer in example 4;
FIG. 2 is a graph of the IR spectra of the nanofiltration membrane before and after the polymer graft modification and after the functionalization in example 6;
fig. 3 shows the contact angles of the surface of the nanofiltration membrane after the polymer graft modification and before and after the functionalization in example 6.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
A functional polymer nanofiltration membrane material and a preparation method thereof comprise the following steps
Fully stirring and mixing the polymer powder, the vinyl monomer, the dispersant and the solvent according to a certain proportion, and inducing the vinyl monomer to perform graft polymerization reaction on the polymer powder by irradiation treatment with high-energy rays under a certain atmosphere condition; the high energy radiation is electron beam (from experimental or production type electron accelerators) or gamma radiation (from cobalt or cesium sources); the irradiation condition is normal temperature, normal pressure and static treatment, the dosage rate is 50-50000Gy/h, and the absorbed dosage is 1-500 kGy.
In the grafting reaction system, the mass percent of the dispersant is 0.1-50%, the mass percent of the monomer is 0.1-45%, and the mass percent of the polymer powder is 1-40%.
After washing and vacuum drying, the obtained modified powder is dissolved in an organic solvent added with a pore-forming agent, and a membrane casting solution is obtained after full dissolution and degassing, wherein the mass percent of the modified polymer in the membrane casting solution is 5-45%, and the mass percent of the pore-forming agent is 0.5-20%.
Obtaining a polymer composite membrane with a porous supporting layer or a polymer symmetrical membrane without a substrate by a flat plate blade coating or extrusion spinning-phase inversion method;
the obtained polymer membrane is reacted with a functional modifier to obtain the polymer nanofiltration membrane material with different functions. The functionalization reaction is a conventional organic reaction aiming at reactive groups such as cyano, halo, hydroxyl, ester or carboxyl on the grafted chain, and comprises amination, hydrolysis, esterification, oxime amination, ring opening and the like.
Wherein the polymer powder is raw material powder commonly used for preparing polymer membrane materials in a laboratory or an industrial production line; the vinyl monomer is an organic compound containing carboxyl, nitrile, hydroxyl or amido; the dispersant is a nonionic dispersant; the pore-forming agent is an organic or inorganic pore-forming agent commonly used in laboratories or industrial production lines; the functional modifier is an organic or inorganic substance with special functional groups; the certain atmosphere condition is vacuum sealing, nitrogen or inert atmosphere protection.
More specifically, the polymer powder is a powder of a commercially available common film-forming polymer, and the material thereof includes cellulose and derivatives thereof, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyvinylidene fluoride and copolymers thereof, polyurethane, polyether sulfone, polysulfone, polyarylsulfone, polyvinyl alcohol, polyvinyl acetals, polyester, polycarbonate, polysulfone amide, polyether ketone, polyether ether ketone, and the like.
The dispersant is selected from methanol, ethanol, ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trihydroxymethyl propane, glycerin, acetone, Tween series emulsifier, etc.
The pore-forming agent is selected from polyvinylpyrrolidone, polyethylene glycol, lithium chloride, zinc chloride, calcium carbonate, etc.
The vinyl monomer is selected from acrylonitrile, methacrylonitrile, chloroacrylonitrile, bromoacrylonitrile, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylic acid, vinyl acetate, 2-aminoethyl methacrylate, glycidyl methacrylate, 2, 3-dibromopropyl acrylate, chloromethylstyrene, bromomethylstyrene, and the like.
The grafting reaction solvent is selected from common solvents such as methanol, ethanol, ethylene glycol, acetone, ethyl acetate, tetrahydrofuran, chloroform, water and the like.
Dissolving the modified powder, and preparing the casting solution from an organic solvent selected from dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethyl sulfoxide and the like.
The functional modifier is selected from organic amine compounds such as methylamine, ethylamine, methylethylamine, diethylamine, ethylenediamine, propylamine, isopropylamine, diethylenetriamine and triethylenetetramine, inorganic alkali compounds such as ammonia water, sodium hydroxide and potassium hydroxide, amino acid compounds such as glycine and alanine, polyethyleneimine, polyvinylamine, polyvinyl alcohol, polyethylene glycol, taurine, propane sultone, butane sultone and hydroxylamine hydrochloride.
The pure water flux of the functional nanofiltration membrane is tested by adopting a cross-flow device, before the test, the pressure is adjusted to 3bar, the pre-pressing is carried out for 20 minutes, then the pressure is adjusted to 2bar, and the effective surface area of the membrane is 0.002826m 2 Recording the volume of pure water passing through the membrane over a specified time; a0.1 g/L dye solution was prepared for the retention test, and the same procedure was carried out for each example.
Example 1
Fully stirring and mixing 10g of polysulfone, 5g of acrylonitrile, 50g of ethylene glycol and 50g of water, and performing gamma ray irradiation treatment under the conditions of normal temperature, normal pressure and static treatment in a nitrogen atmosphere, wherein the dose rate is 2000Gy/h, and the absorbed dose is 50 kGy; after washing and drying, adding 10g of the obtained modified polysulfone powder into 30ml of dimethylformamide containing 1g of polyvinylpyrrolidone, fully dissolving and degassing to obtain a membrane casting solution, and carrying out blade coating on a flat plate to obtain a polysulfone composite membrane; and soaking the obtained composite membrane in 20 wt% diethylenetriamine solution at 80 ℃ for 12h, and then cleaning the composite membrane with a large amount of pure water to obtain the functional polysulfone nanofiltration membrane material.
Example 2
Fully stirring and mixing 10g of polysulfone, 10g of acrylonitrile, 50g of ethylene glycol and 50g of water, and performing gamma ray irradiation treatment under the conditions of normal temperature, normal pressure and static treatment in a nitrogen atmosphere, wherein the dose rate is 2000Gy/h, and the absorption dose is 50 kGy; after washing and drying, adding 10g of the obtained modified polysulfone powder into 30ml of dimethylformamide containing 1g of polyvinylpyrrolidone, fully dissolving and degassing to obtain a membrane casting solution, and carrying out blade coating on a flat plate to obtain a polysulfone composite membrane; and (3) soaking the obtained composite membrane in a diethylenetriamine solution with the concentration of 20 wt% and the temperature of 80 ℃ for 12h, and then cleaning the composite membrane by using a large amount of pure water to obtain the functionalized polysulfone nanofiltration membrane material.
Example 3
Fully stirring and mixing 10g of polysulfone, 20g of acrylonitrile, 50g of ethylene glycol and 50g of water, and performing gamma ray irradiation treatment under the conditions of normal temperature, normal pressure and static treatment in a nitrogen atmosphere, wherein the dose rate is 2000Gy/h, and the absorbed dose is 50 kGy; after washing and drying, adding 10g of the obtained modified polysulfone powder into 30ml of dimethylformamide containing 1g of polyvinylpyrrolidone, fully dissolving and degassing to obtain a membrane casting solution, and carrying out blade coating on a flat plate to obtain a polysulfone composite membrane; and soaking the obtained composite membrane in 20 wt% diethylenetriamine solution at 80 ℃ for 12h, and then cleaning the composite membrane with a large amount of pure water to obtain the functional polysulfone nanofiltration membrane material.
The polysulfone nanofiltration membranes obtained in each example were passed through a cross-flow device to obtain pure water flux and retention to bismarck brown R as shown in table 1:
TABLE 1
| Flux L/(m) 2 .h) | Retention (%) | |
| Example 1 | 106.5 | 91.1 |
| Example 2 | 50.7 | 94.5 |
| Example 3 | 28.1 | 98.0 |
As can be seen from Table 1, with the increase of the monomer content in the grafting system, the pure water flux of the obtained membrane material gradually decreases, and the retention rate of the dye gradually increases. The reason is that the monomer concentration is increased, so that the powder grafting rate is improved, after film formation, more grafting chains are arranged on the surface of the film, and after functionalization treatment, more hydrated grafting chains are gathered on the surface, so that the pore diameter of the film is reduced, and the pore distribution of the film is uniform.
Example 4
Fully stirring and mixing 10g of polyether sulfone, 5g of acrylonitrile, 50g of methanol and 50g of water, and performing gamma ray irradiation treatment under the conditions of normal temperature, normal pressure and static treatment in a nitrogen atmosphere, wherein the dose rate is 2000Gy/h, and the absorption dose is 25 kGy; after washing and drying, adding 10g of the obtained modified polyether sulfone powder into 30ml of dimethylformamide containing 1g of polyvinylpyrrolidone, fully dissolving and degassing to obtain a membrane casting solution, and carrying out blade coating on a flat plate to obtain a polyether sulfone composite membrane; and soaking the obtained composite membrane in 20 wt% diethylenetriamine solution at 80 ℃ for 12h, and then cleaning the composite membrane with a large amount of pure water to obtain the functional polyether sulfone nanofiltration membrane material. The content of carbon, nitrogen and oxygen elements in the powder after the polyether sulfone graft modification is shown in figure 1, and N appears at 401.0eV 1s Thereby deducing the success of the polyether sulfone graft modification.
Example 5
Fully stirring and mixing 10g of polyether sulfone, 5g of acrylonitrile, 50g of methanol and 50g of water, and performing gamma ray irradiation treatment under the conditions of normal temperature, normal pressure and static treatment in a nitrogen atmosphere, wherein the dose rate is 2000Gy/h, and the absorption dose is 50 kGy; after washing and drying, adding 10g of the obtained modified polyether sulfone powder into 30ml of N, N' -dimethylformamide containing 1g of polyvinylpyrrolidone, fully dissolving and degassing to obtain a membrane casting solution, and carrying out plate blade coating-phase conversion to obtain a polyether sulfone composite membrane; and soaking the obtained composite membrane in 20 wt% diethylenetriamine solution at 80 ℃ for 12h, and then cleaning the composite membrane with a large amount of pure water to obtain the functional polyether sulfone nanofiltration membrane material.
Example 6
Fully stirring and mixing 10g of polyether sulfone, 10g of acrylonitrile, 50g of methanol and 50g of water, and performing gamma ray irradiation treatment under the conditions of normal temperature, normal pressure and static treatment in a nitrogen atmosphere, wherein the dose rate is 1000Gy/h, and the absorption dose is 50 kGy; after washing and drying, adding 10g of the obtained modified polyether sulfone powder into 30ml of N, N' -dimethylformamide containing 1g of polyvinylpyrrolidone, fully dissolving and degassing to obtain a membrane casting solution, and carrying out blade coating on a flat plate to obtain a polyether sulfone composite membrane; and soaking the obtained composite membrane in 20 wt% diethylenetriamine solution at 80 ℃ for 12h, and then cleaning the composite membrane with a large amount of pure water to obtain the functional polyether sulfone nanofiltration membrane material.
The infrared spectra of the polyethersulfone nanofiltration membrane before and after grafting modification and functionalization are shown in figure 2, PES-g-AN is 2323cm -1 The absorption peak of tensile vibration appears at (C ≡ N), and when a new group (N-H) is introduced on the surface of PES-g-AN, the peak value is reduced, so that the success of functionalizing the polyether sulfone composite membrane can be obtained. The contact angle conditions of the polyethersulfone nanofiltration membrane surface before and after graft modification and after functionalization are shown in figure 3, acrylonitrile is a hydrophilic monomer, and after graft modification, the polyethersulfone is functionalized, and hydrophilic groups (-NH) are introduced 2 ) So that the contact angle is PES>PES-g-AN>PES-NH 2 。
The pure water flux and the methyl blue rejection rate of the polyethersulfone nanofiltration membrane obtained in each example are shown in table 2 after passing through a cross-flow device:
TABLE 2
| Water flux L/(m) 2 .h) | Retention (%) | |
| Example 4 | 128.6 | 91.6 |
| Example 5 | 97.7 | 93.3 |
| Example 6 | 85.9 | 95.2 |
As can be seen from Table 2, the larger the absorbed dose, the lower the pure water flux of the resulting filter membrane, and the higher the retention rate of the dye. This is because increasing the absorbed dose is advantageous in increasing the grafting ratio of the monomer. In addition, increasing the dosage rate is not beneficial to improving the grafting rate because the dosage rate is high, the self-polymerization of the monomer is more active, and the grafting polymerization is not beneficial, so that the pure water flux of a membrane material prepared from the modified powder at the high dosage rate is larger, and the interception rate is lower.
Example 7
Fully stirring and mixing 10g of polyether sulfone, 5g of vinyl acetate, 50g of ethanol and 50g of water, and performing gamma ray irradiation treatment under the conditions of normal temperature, normal pressure and static treatment in a nitrogen atmosphere, wherein the dose rate is 1000Gy/h, and the absorbed dose is 30 kGy; after washing and drying, adding 10g of the obtained modified polyether sulfone powder into 50ml of dimethylformamide containing 1.5g of polyvinylpyrrolidone, fully dissolving and degassing to obtain a membrane casting solution, and carrying out blade coating on a flat plate to obtain a polyether sulfone composite membrane; and soaking the obtained composite membrane in a sodium hydroxide solution with the concentration of 10 wt% and the temperature of 80 ℃ for 12h, and then cleaning the composite membrane by using a large amount of pure water to obtain the functionalized polyether sulfone nanofiltration membrane material.
Example 8
Fully stirring and mixing 10g of polyvinylidene fluoride, 5g of 2-aminoethyl methacrylate, 50g of methanol and 50g of water, and performing gamma ray irradiation treatment under the conditions of normal temperature, normal pressure and static treatment in a nitrogen atmosphere, wherein the dose rate is 1000Gy/h, and the absorption dose is 30 kGy; after washing and drying, adding 10g of modified polyether sulfone powder and 2g of polyethylene glycol into 33ml of N, N' -dimethylformamide, fully dissolving and degassing to obtain a membrane casting solution, and carrying out blade coating on a flat plate to obtain a polyvinylidene fluoride composite membrane; and soaking the obtained composite membrane in 5 wt% of 1, 3-propane sultone solution for 8 hours, and then cleaning with a large amount of pure water to obtain the functionalized polyvinylidene fluoride filter membrane material.
Example 9
Fully stirring and mixing 10g of polysulfone, 10g of chloromethylstyrene, 50g of methanol and 50g of water, and performing gamma ray irradiation treatment under the conditions of normal temperature, normal pressure and static treatment in a nitrogen atmosphere, wherein the dose rate is 2000Gy/h, and the absorbed dose is 50 kGy; after washing and drying, adding 10g of the obtained modified polysulfone powder and 2.5g of polyvinylpyrrolidone into 27.5ml of dimethylformamide, fully dissolving and degassing to obtain a membrane casting solution, and carrying out blade coating on a flat plate to obtain a polysulfone composite membrane; and soaking the obtained composite membrane in 20 wt% diethylenetriamine solution at 80 ℃ for 12h, and then cleaning the composite membrane with a large amount of pure water to obtain the functional polysulfone nanofiltration membrane material.
The surface charge of the nanofiltration membrane obtained in each example measured by a solid surface zeta potentiometer is shown in table 3:
TABLE 3
| Surface charge mV | |
| Example 7 | -5.8 |
| Example 8 | -6.6 |
| Example 9 | 23.5 |
As can be seen from Table 3, filter membrane materials with different surface charge properties can be obtained by selecting different grafting monomers and functional modification reagents.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a functional polymer nanofiltration membrane material is characterized by comprising the following steps:
fully stirring and mixing the polymer powder, the vinyl monomer, the dispersing agent and the solvent, and performing high-energy ray irradiation treatment under a protective atmosphere to induce the vinyl monomer to perform graft polymerization reaction on the polymer powder;
after washing and vacuum drying, dissolving the obtained modified powder in an organic solvent added with a pore-forming agent, and fully dissolving and degassing to obtain a membrane casting solution;
obtaining a polymer composite membrane with a porous supporting layer or a polymer symmetrical membrane without a substrate by a flat blade coating or extrusion spinning-phase inversion method;
and carrying out functional reaction treatment on the obtained polymer membrane and a functional modifier to obtain the functional polymer nanofiltration membrane material.
2. The method for preparing a functional polymer nanofiltration membrane material according to claim 1, wherein the vinyl monomer is an organic compound containing carboxyl, nitrile, hydroxyl or amine groups; the dispersant is a nonionic dispersant; the protective atmosphere condition is vacuum sealing, nitrogen or inert atmosphere protection.
3. The method for preparing a functional polymer nanofiltration membrane material according to claim 1 or 2, wherein the polymer powder comprises cellulose and derivatives thereof, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyvinylidene fluoride and copolymers thereof, polyurethane, polyethersulfone, polysulfone, polyarylsulfone, polyvinyl alcohol, polyvinyl acetals, polyester, polycarbonate, polysulfonamides, polyetherketone or polyetheretherketone;
the vinyl monomer comprises acrylonitrile, methacrylonitrile, chloroacrylonitrile, bromoacrylonitrile, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylic acid, vinyl acetate, 2-aminoethyl methacrylate, glycidyl methacrylate, 2, 3-dibromopropyl acrylate, chloromethyl styrene or bromomethyl styrene;
the dispersing agent comprises methanol, ethanol, ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trihydroxymethyl propane, glycerol, acetone or tween series emulsifying agents;
the solvent comprises methanol, ethanol, glycol, acetone, ethyl acetate, tetrahydrofuran, chloroform or water.
4. The method for preparing a functional polymer nanofiltration membrane material according to claim 1, wherein the pore-forming agent comprises polyvinylpyrrolidone, polyethylene glycol, lithium chloride, zinc chloride or calcium carbonate; the organic solvent for preparing the casting solution comprises dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide or tetramethyl sulfoxide.
5. The method for preparing a functional polymer nanofiltration membrane material according to claim 1, wherein the functional modifier comprises organic amine compounds such as methylamine, ethylamine, methylethylamine, diethylamine, ethylenediamine, propylamine, isopropylamine, diethylenetriamine, triethylenetetramine, etc., inorganic alkali compounds such as ammonia water, sodium hydroxide, potassium hydroxide, etc., amino acid compounds such as glycine, alanine, etc., polyethyleneimine, polyvinylamine, polyvinyl alcohol, polyethylene glycol, taurine, propane sultone, butane sultone, or hydroxylamine hydrochloride.
6. The method for preparing a functional polymer nanofiltration membrane material according to claim 1, wherein the high energy radiation is electron beam or gamma radiation; the irradiation condition is normal temperature, normal pressure and static treatment, the dosage rate is 50-50000Gy/h, and the absorbed dosage is 1-500 kGy.
7. The method for preparing a functional polymer nanofiltration membrane material according to claim 1, wherein in the grafting reaction system, the mass percent of the dispersant is 0.1-50%, the mass percent of the vinyl monomer is 0.1-45%, and the mass percent of the polymer powder is 1-40%.
8. The method for preparing a functional polymer nanofiltration membrane material according to claim 1, wherein the mass percent of the modified powder in the membrane casting solution is 5-45%, and the mass percent of the pore-forming agent is 0.5-20%.
9. The method of claim 1, wherein the functionalization reaction is a conventional organic reaction with respect to a reactive group of a cyano group, a halo group, a hydroxyl group, an ester group or a carboxyl group on the graft chain, and includes amination, hydrolysis, esterification, oxime amination and ring opening reaction.
10. A functional polymer nanofiltration membrane material prepared according to any one of claims 1 to 9.
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