CN108325389B - Azlactone-based polyamide membrane and preparation method thereof - Google Patents

Azlactone-based polyamide membrane and preparation method thereof Download PDF

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CN108325389B
CN108325389B CN201810082215.0A CN201810082215A CN108325389B CN 108325389 B CN108325389 B CN 108325389B CN 201810082215 A CN201810082215 A CN 201810082215A CN 108325389 B CN108325389 B CN 108325389B
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azlactone
membrane
solution
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mass fraction
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CN108325389A (en
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牛青山
远冰冰
孙红红
李鹏飞
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China University of Petroleum East China
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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
    • B01D71/56—Polyamides, e.g. polyester-amides
    • 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
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/16—Membrane materials having positively charged functional groups
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Abstract

The invention discloses a novel azlactone-based polyamide membrane and a preparation method thereof, and belongs to the technical field of nanofiltration membranes (loose reverse osmosis membranes). The azlactone-based polyamide membrane is formed by interfacial polymerization of an azlactone group-containing monomer and a primary aliphatic amine monomer. The azlactone-based polyamide membrane is electrically neutral or electropositive in surface structure, has a smooth membrane surface, and has excellent retention effect on divalent and multivalent cations and good anti-pollution performance, and the CUT-OFF of the azlactone-based polyamide membrane is 600 Dalton. The method can be widely applied to material separation processes such as water softening, dye/salt separation, concentration and separation of amino acid polypeptide molecules with different molecular weights, and the like, and can also be applied to the water treatment fields such as seawater desalination, brackish water pretreatment, and the like.

Description

Azlactone-based polyamide membrane and preparation method thereof
Technical Field
The invention relates to the technical field of nanofiltration membranes (loose reverse osmosis membranes), in particular to a novel azlactone-based polyamide membrane. The present invention can be widely used for Ca2+、Mg2+Water softening process for removing divalent cations, which is mainly used for household water purifier, seawater desalination and brackish waterThe pretreatment field can also be used for removing COD in the wastewater, such as dye molecules, phenol molecules and the like, and separating dye/salt, and can also be used for the separation and concentration process of materials in the pharmaceutical and food industries.
Background
Compared with the traditional separation technologies such as distillation, rectification and the like, the membrane separation technology is a novel alternative separation technology, has the advantages of low energy consumption, small occupied area and the like, and is widely applied to industrial production and daily life. In the membrane separation technology, the separation membrane material is the key to realize separation and concentration. Commonly used membrane types are classified by pore size: microfiltration, ultrafiltration, nanofiltration, reverse osmosis, and the like; the preparation method comprises the following steps: phase inversion method, interfacial polymerization method, vapor deposition method, layer-by-layer assembly method, etc.
At present, commercial nanofiltration membranes and reverse osmosis membranes are prepared by a classical interfacial polymerization method or a phase inversion method. The nanofiltration membrane is divided into two types, one type of nanofiltration membrane has the characteristic of cutting according to different molecular weights of trapped substances, so that the separation of substances with different sizes can be realized, and the concentration of different substances can be realized while materials are separated; another type of nanofiltration membrane (actually a loose reverse osmosis membrane) has excellent divalent salts such as Ca2+、Mg2+The rejection rate is 70-90% of NaCl, and the nanofiltration membrane can be widely applied to the fields of water softening, wastewater and sewage treatment and recovery, seawater desalination, brackish water pretreatment and the like. Therefore, in general, the nanofiltration membrane can be used for separating and concentrating salt and materials in water; the other type of nanofiltration membrane can be used for advanced treatment of water, namely a water softening process, removal of COD in water and the like.
Among the important applications of nanofiltration membranes (loose reverse osmosis membranes) is water softening, i.e. the removal of high concentrations of Ca in water2+And Mg2+And scale formation reduction, which is important in water supply in life and industrial production, and pretreatment for desalting brackish water and seawater. In phase with conventional water-softening processes, e.g. ion-exchange or lime-soda processesCompared with the nanofiltration membrane process, the method has the advantages of low energy consumption, convenience and little environmental pollution.
The conventional commercial nanofiltration membrane is mostly prepared by oil-phase trimesoyl chloride (TMC) monomers, water-phase piperazine monomers (PIP) and m-phenylenediamine Monomers (MPD) through classical interfacial polymerization, and the surface of the prepared membrane presents certain negative charges due to carboxyl formed by hydrolysis of acyl chloride groups in the oil-phase monomers. Therefore, according to the separation mechanism (sieving effect and charging effect) of the nanofiltration membrane, the commercially prepared nanofiltration membrane, especially the trimesoyl chloride (TMC) -piperazine (PIP) base membrane, has lower divalent cation rejection rate, such as Ca2+、Mg2+. There are two strategies currently being investigated for nanofiltration membranes, one is to design the monomers at the molecular level to provide a suitable pore size and distribution of the nanofiltration membrane to reject all divalent cations, and the other is to manipulate the surface charge of the selection layer to be positive to reject divalent metal cations by the south-of-the-road effect. The key to solve the separation problem is to prepare a novel water-oil two-phase monomer with a specific structure, change the dissolution-diffusion mechanism of interfacial polymerization and form the prepared membrane into a specific structure with pertinence.
Most of the current commercialized nanofiltration membranes are prepared by performing interfacial polymerization on an acyl chloride monomer and an amine monomer on a porous support layer, such as DOW NF series, GE DK and DL series, wherein the acyl chloride monomer used for the preparation is trimesoyl chloride, and the amine monomer is piperazine, so that the prepared membrane has high electronegativity, low retention rate of divalent metal cations in a solution, and simultaneously contains Ca2+Of the polyamide membrane, which is poor in contamination resistance, thus making the polyamide membrane prepared present Ca for water softening applications2+、Mg2+The retention rate is low. On the other hand, although the commercial interfacial polymerization monomer pairs are composed of trimesoyl chloride and m-phenylenediamine, the polyamide membranes prepared by the method are controlled by the dissolving-diffusing mechanism of the m-phenylenediamine, and have large surface roughness and poor pollution resistance.
Disclosure of Invention
The invention aims to provide a novel azlactone-based polyamide membrane to solve the problem of the existing nanofiltration membrane (loose reverse osmosis membrane) membraneHigh surface electronegativity resulting in Ca2+And Mg2+The retention rate of divalent metal cations is low, and the surface roughness of the membrane is large, so that the pollution resistance is poor.
The invention designs a nanofiltration membrane (loose reverse osmosis membrane) by combining the defects of high electronegativity and large membrane surface roughness of the existing nanofiltration membrane, and has the characteristics of certain electropositivity and low roughness on the membrane surface.
Although many excellent acyl chloride monomers are developed, the monomers often have high divalent anion rejection rate and low divalent cation rejection rate when used for a nanofiltration membrane (loose reverse osmosis membrane) prepared by interfacial polymerization, so that excellent Ca cannot be embodied when used for trapping mixed solution containing multiple anions and cations2+、Mg2+The removal rate is caused by the fact that the acyl chloride monomer is easy to hydrolyze to form carboxylic acid groups with strong electronegativity. Based on the method, the nanofiltration membrane with neutral or electropositive surface electricity after the reaction with amine is developed to realize Ca2+With Mg2+Efficient interception is performed; meanwhile, when the novel azlactone-based monomer reacts with an amine monomer, the dissolution-diffusion mechanism is different from that of the traditional TMC-MPD during interface reaction, so that the generated nanofiltration membrane has reduced surface roughness and excellent stain resistance.
Therefore, the technical solution of the present invention for solving the above technical problems is as follows:
a method of making an azlactone-based polyamide membrane, comprising:
a primary aliphatic amine solution is coated or soaked on a porous supporting base film, and then the porous supporting base film with the surface containing the primary aliphatic amine solution and an azlactone-based monomer solution containing an azlactone-based monomer or an azlactone-based polymer monomer are subjected to interfacial polymerization to obtain the azlactone-based polyamide film.
The invention prepares azlactone polyamide film by interfacial polymerization of azlactone monomer or polymer thereof and primary aliphatic amine monomer, wherein the film contains the following two structures:
Figure BDA0001561340600000031
and
Figure BDA0001561340600000032
in contrast to the above-mentioned results,
Figure BDA0001561340600000033
has a large pKa, and thus its structure has a weak ability to ionize acids, and the surface can be electrically neutral or electropositive after reaction with amines. According to the separation principle of nanofiltration membrane charge repulsion, the nanofiltration membrane containing the structure has excellent Ca2+With Mg2+The retention rate.
In the preparation of the azlactone-based polyamide film of the invention, layer-by-layer assembly or vapor deposition may be employed in addition to interfacial polymerization.
Further, in a preferred embodiment of the present invention, the preparation method further includes: washing the prepared azlactone-based polyamide membrane with an organic solvent for 15-60s, removing the organic solvent, and performing heat treatment at 50-90 ℃ for 60s-10 min; wherein the organic solvent is one or more of n-hexane, cyclohexane, n-heptane, n-octane and iso-Par series; prior to the heat treatment, the azlactone-based polyamide film was immersed in a primary aliphatic amine solution having a concentration of 10 to 2000 mM.
The present invention washes the prepared azlactone-based polyamide film with an organic solvent to remove excess unreacted azlactone-based monomer from the surface to control the extent of reaction and thereby reduce the roughness of the newly formed film surface. Washing with organic solvent for 15-60s, removing organic solvent, and heat treating at 50-90 deg.C for 60s-10min to completely crosslink unreacted azlactone group with amine monomer. The aim of soaking the newly prepared azlactone-based polyamide membrane in a primary aliphatic amine solution before heat treatment is to further improve the electropositivity of the membrane surface and increase the hydrophilicity of the membrane surface, thereby improving the water flux of the azlactone-based polyamide membrane and the resistance to divalent metal cations such as Ca2+、Mg2+Is trapped byAnd (4) rate.
Further, in preferred embodiments of the present invention, the primary fatty amine is one or more combinations of D-glucosamine, hyperbranched polyethyleneimine, tris (2-aminoethyl) amine, diethylenetriamine, triethylenetetramine, ethylenediamine, and m-xylylenediamine.
Further, in a preferred embodiment of the present invention, the concentration of the above-mentioned primary aliphatic amine solution is 0.01 to 2% by weight, and the concentration of the azlactone-based monomer solution is 0.01 to 0.5% by weight.
Further, in a preferred embodiment of the present invention, the primary aliphatic amine solution comprises a primary aliphatic amine and an aqueous phase additive, wherein the mass fraction of the primary aliphatic amine is 0.01-2wt%, and the addition amount of the aqueous phase additive is 1-50wt% of the primary aliphatic amine.
Further, in a preferred embodiment of the present invention, the above azlactone-based monomer solution includes an azlactone-based monomer, an oil-phase solvent, and an oil-phase additive; wherein, the mass fraction of azlactone-based monomer is 0.01-0.5wt%, the mass fraction of oil phase solvent is 99.5-99.99wt%, and the mass fraction of oil phase additive is 0-1.99 wt%.
Further, in a preferred embodiment of the present invention, the aqueous phase additive is nanoparticles, organic phenol having a distorted spatial structure, a hydrophilic additive or a surfactant; the oil phase additive is a cosolvent or a phase transfer catalyst; wherein: the nano particles are sheet graphene, slender single-walled or multi-walled carbon nanotubes or organic spheres; organic phenols with distorted spatial structure, or porous molecules in cage or wheel shape, such as cyclodextrin, cucurbituril; the hydrophilic additive is quaternary ammonium salt, alcohol amine or camphor sulfonic acid; the cosolvent is acetone, toluene, benzene, polyalcohol, organic phosphide or dimethylformamide.
Further, in a preferred embodiment of the present invention, the above azlactone-based monomer solution includes an azlactone-based monomer and an oil-phase solvent; wherein the mass fraction of azlactone-based monomer is 0.01-0.5wt%, and the mass fraction of oil phase solvent is 99.5-99.99 wt%.
Further, in a preferred embodiment of the present invention, the above azlactone-based monomer solution includes an azlactone-based polymer monomer and an oil-phase solvent, the mass fraction of the azlactone-based polymer being 0.01 to 0.05 wt%, and the mass fraction of the oil-phase solvent being 99.95 to 99.99 wt%.
Further, in preferred embodiments of the present invention, the azlactone-based polymer or monomer is of the formula:
(1) poly (2-vinyl-4, 4-dimethylazlactone) (PVDMA):
Figure BDA0001561340600000051
wherein R is
Figure BDA0001561340600000052
n is 0, 1,2,3, or Ph.
(2) 2-hydroxypropane-1, 2, 3-tris-4, 4-dimethylazlactone (CMDMA):
Figure BDA0001561340600000053
(3)1, 3, 5-cyclohexanetri4, 4-dimethylazlactone (HMDMA):
Figure BDA0001561340600000061
(4)1, 3, 5-benzenetris-4, 4-dimethylazlactone (TMDMA):
Figure BDA0001561340600000062
(5)1, 2,3, 4-cyclobutyltetra-4, 4-dimethylazlactone (BMDMA):
Figure BDA0001561340600000063
wherein A is alicyclic or aromatic, and is a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring or an eight-membered ring; r1、R2、R3、R4Is composed of
Figure BDA0001561340600000071
Or a combination of H and a nitrogen atom,
Figure BDA0001561340600000072
the number of (2) is 3-6, two
Figure BDA0001561340600000073
The groups are in ortho-position or meta-position.
Further, in a preferred embodiment of the present invention, the azlactone structure of the alicyclic or aromatic azlactone-containing structure is three or more
Figure BDA0001561340600000074
And are attached to cycloaliphatic or aromatic hydrocarbons, such as cyclobutane, benzene rings, cyclopentane or cyclohexane.
Preferably, the alicyclic or aromatic azlactone structure selected for use in the present invention is 1,3, 5-cyclohexanetri4, 4-dimethylazlactone, 1,2,3, 4-cyclobutyltetra-4, 4-dimethylazlactone, 1,2,4, 5-cyclohexanetetra-4, 4-dimethylazlactone, 1,2, 4-cyclopentetri4, 4-dimethylazlactone or 1,3, 5-benzenetri-4, 4-dimethylazlactone.
Further, in a preferred embodiment of the present invention, the azlactone-based monomer solution described above includes mixed acid chloride-based and azlactone-based monomer molecules. Wherein the structural formula of the doped acyl chloride monomer is as follows:
Figure BDA0001561340600000075
wherein A is alicyclic or aromatic, and is a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring or an eight-membered ring; r1、R2、R3、R4is-C (O) Cl or H, the number of-C (O) Cl groups being from 3 to 6 and the two-C (O) Cl groups being ortho-or meta-positioned.
Further, in the preferred embodiment of the present invention, the structures of the primary aliphatic amines are as follows:
(1) hyperbranched Polyethyleneimine (PEI):
Figure BDA0001561340600000081
(2) tris (2-aminoethylamine) (TAEA):
Figure BDA0001561340600000082
(2) m-Xylylenediamine (XMD):
Figure BDA0001561340600000083
(3) diethylenetriamine (EDA):
Figure BDA0001561340600000084
(4)1, 2-Ethylenediamine (EA)
Figure BDA0001561340600000085
(5) Tris (aminomethyl) amine (TAMA):
Figure BDA0001561340600000086
(4) triethylene Tetramine (TEEA):
Figure BDA0001561340600000087
further, in a preferred embodiment of the present invention, the supporting base membrane is an organic polymer ultrafiltration membrane, a hollow fiber ultrafiltration membrane, an inorganic ultrafiltration membrane material, or an organic and inorganic hybrid porous membrane; the organic polymer ultrafiltration membrane is polysulfone, polyethersulfone, polyacrylonitrile or polyimide; the inorganic ultrafiltration membrane material is porous alumina or porous ceramic.
The azlactone-based polyamide film prepared by the above-described preparation method.
The invention has the following beneficial effects:
according to the invention, the azlactone-based monomer solution or the mixed oil phase monomer solution and the primary aliphatic amine monomer solution are subjected to interfacial polymerization, so that the polyamide loose reverse osmosis membrane with a neutral or positively charged surface is prepared, and the rejection rate of divalent ions is increased.
Azlactone-based polyamide membrane prepared by the invention is CaCl2The retention rate can reach more than 97 percent, and the flux can reach 80-90kg m-2h-1MPa-1The water-softening agent has excellent water-softening performance, low surface roughness and excellent anti-pollution capacity. At a certain concentration of mixed salt solution, the invention prepares azlactone polyamide membrane pair Mg2+、Ca2+、SO4 2-The rejection rate of the salt can reach more than 98 percent, and the salt has extremely high rejection rate of divalent salt; the surface roughness of the film is below 10nm, and the azlactone-based polyamide film prepared by the method is suitable for water softening, water quality desalting and denitration; the brine is divided into quality, concentration, heavy metal separation, material separation, biological medicine and other fields.
Compared with the commercialized common acyl chloride-based monomer, the method can obviously reduce the negative charge on the surface of the membrane, so that the electrostatic repulsion of divalent and polyvalent metal cations is reduced when the divalent and polyvalent metal cations penetrate through the nanofiltration membrane, and the effect of divalent metal cations such as Ca is improved2+With Mg2+The retention rate of the water softening agent is high, and an obvious water softening effect is achieved.
In addition, after the proper amine monomer is selected, the polyamide nanofiltration membrane prepared from the azlactone structure-containing monomer and the proper amine monomer has excellent divalent salt rejection rate, wherein the rejection rate of sodium sulfate, magnesium sulfate and calcium chloride can reach more than 98%, and the rejection rate of sodium chloride is 15-30%, so that the polyamide nanofiltration membrane has excellent monovalent and divalent selectivity and excellent water softening performance, and can be used in the fields of material separation, pretreatment of brackish water and seawater desalination, dye/salt separation and the like.
Detailed Description
The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The method for producing an azlactone-based polyamide film of this example included the steps of:
(1) soaking a polyethersulfone ultrafiltration membrane in polyethyleneimine (Mw 70,000) containing 2wt% for 4min, and then gas purging for 3min to remove excess aqueous amine solution;
(2) and (2) soaking the polyether sulfone ultrafiltration membrane with the polyethyleneimine solution prepared in the step (1) in a solution containing 0.1 wt% of 1,3, 5-trimesic tri-4, 4-dimethyl azlactone benzene/cyclohexane, wherein the interfacial polymerization time is 120s, and then treating the prepared polyamide nanofiltration membrane at 60 ℃ for 15min to obtain the azlactone-based polyamide membrane.
Table 1 shows the salt rejection performance of azlactone-based polyamide membranes prepared by interfacial polymerization of 1,3, 5-trime-4, 4-dimethylazlactone and polyethyleneimine according to examples of the present invention; and (3) testing conditions are as follows: the cross-flow test shows that the single salt solution is 2000ppm, 25 ℃, 1MPa and the flow rate is 7 LPM.
TABLE 1
Figure BDA0001561340600000101
Example 2
The method for producing an azlactone-based polyamide film of this example included the steps of:
(1) soaking a polyether sulfone ultrafiltration basement membrane in an aqueous solution containing 1.5 wt% of tris (2-aminoethyl) amine for 4min, and then, purging with gas for 3min to remove redundant aqueous phase solution;
(2) and (2) soaking the polyether sulfone ultrafiltration membrane with the tris (2-aminoethyl) amine solution prepared in the step (1) in a 1,3, 5-sym-benzenetris-4, 4-dimethyl azlactone benzene/cyclohexane solution with the interfacial polymerization time of 60s, and then treating the prepared polyamide nanofiltration membrane at 60 ℃ for 15min to obtain the azlactone-based polyamide membrane.
Table 2 shows the salt rejection performance of a polyamide nanofiltration membrane prepared by interfacial polymerization of 1,3, 5-benzenetris-4, 4-dimethylazlactone and tris (2-aminoethyl) amine; and (3) testing conditions are as follows: the cross-flow test shows that the single salt solution is 2000ppm, 25 ℃, 1MPa and the flow rate is 7 LPM.
TABLE 2
Figure BDA0001561340600000111
Example 3
Unlike examples 1 and 2, this example, in which monomers having an azlactone structure were incorporated into an acid chloride monomer oil phase solution and then reacted with an amine, produced an azlactone-based polyamide film, comprising the steps of:
(1) soaking a polysulfone ultrafiltration basement membrane in 1 wt% piperazine water solution for 2min, and then blowing gas for 2min to remove redundant aqueous phase solution;
(2) soaking the polysulfone ultrafiltration membrane of the piperazine water solution prepared in the step (1) in a solution containing 0.025 wt% of 1,3, 5-trimesoyl tri-4, 4-dimethyl azlactone and 0.15 wt% of 1,3, 5-trimesoyl chloride benzene/cyclohexane, wherein the mass fraction of the 1,3, 5-trimesoyl tri-4, 4-dimethyl azlactone is 0.025 wt%, the mass fraction of the 1,3, 5-trimesoyl chloride is 0.15 wt%, the mass fraction of the solvent benzene is 2wt%, and the mass fraction of the solvent cyclohexane is 97.825 wt%; the interfacial polymerization time is 15s, and then the prepared polyamide nanofiltration membrane is treated for 4min at 60 ℃ to obtain the azlactone-based polyamide membrane.
Table 3 shows salt rejection performance of azlactone-based polyamide membranes prepared by interfacial polymerization of 1,3, 5-trimesoyl chloride monomer solution with piperazine, with 1,3, 5-trimesoyl chloride monomer solution incorporated into 1,3, 5-dimethyl azlactone; and (3) testing conditions are as follows: the cross-flow test shows that the single salt solution is 2000ppm, 25 ℃, 1MPa and the flow rate is 7 LPM.
TABLE 3
Figure BDA0001561340600000112
Comparative example 1
This comparative example is compared to example 3.
The preparation method of the polyamide nanofiltration membrane by using the acyl chloride oil phase monomer solution not doped with azlactone structure monomer and the amine monomer water phase solution comprises the following specific steps:
(1) firstly, soaking a polyether sulfone ultrafiltration basement membrane in 1.5 wt% piperazine aqueous phase solution, taking out after 2min, and blowing the surface of the ultrafiltration membrane with gas to remove redundant piperazine aqueous solution on the membrane surface; the piperazine water solution consists of piperazine and an aqueous phase solvent, wherein the aqueous phase solvent is water, the mass fraction of the piperazine is 1.5 wt%, and the mass fraction of the aqueous phase solvent is 98.5 wt%;
(2) soaking the 1,3, 5-trimesoyl chloride solution on the ultrafiltration basement membrane with the piperazine solution on the surface prepared in the step (1), and taking out after 10 seconds; wherein the oil phase solvent is n-hexane, the mass fraction of the 1,3, 5-trimesoyl chloride is 0.15 wt%, and the mass fraction of the n-hexane is 99.85 wt%;
(3) and (4) washing the polyamide nanofiltration membrane prepared in the step (3) by using normal hexane for 15s, and similarly, carrying out heat treatment at 60 ℃ for 2min to obtain a full-alicyclic polyamide nanofiltration membrane product.
Table 4 shows the salt rejection performance of the polyamide nanofiltration membrane prepared by interfacial polymerization of 1,3, 5-trimesoyl chloride monomer solution and piperazine; and (3) testing conditions are as follows: the cross-flow test shows that the single salt solution is 2000ppm, 25 ℃, 1MPa and the flow rate is 7 LPM.
TABLE 4
Figure BDA0001561340600000121
Example 4
An azlactone-based polyamide membrane of this example was prepared in substantially the same manner as in example 3 by incorporating an acid chloride monomer into a monomer having an azlactone structure to form an oil phase solution and then reacting the oil phase solution with an amine, and differs from example 3 in that tris (2-aminoethyl) amine was used as the aqueous phase and comprises the steps of:
(1) soaking polysulfone ultrafiltration basement membrane in 1 wt% tris (2-aminoethyl) amine aqueous solution for 2min, and then purging with gas for 2min to remove excessive aqueous solution;
(2) soaking the polysulfone ultrafiltration membrane which is prepared in the step (1) and contains tris (2-aminoethyl) amine molecules on the surface in a solution containing 0.025 weight percent of 1,3, 5-benzenetris-4, 4-dimethylazlactone and 0.15 weight percent of 1,3, 5-benzenetricarbonylbenzene/cyclohexane, wherein the mass fraction of the 1,3, 5-benzenetricarbazine is 0.025 weight percent, the mass fraction of the 1,3, 5-benzenetricarbonyl chloride is 0.15 weight percent, the mass fraction of the solvent benzene is 2 weight percent, and the mass fraction of the solvent cyclohexane is 97.825 weight percent; the interfacial polymerization time is 15s, and then the prepared polyamide nanofiltration membrane is treated for 2min at 60 ℃ to obtain the azlactone-based polyamide membrane.
Table 5 shows salt rejection performance of azlactone-based polyamide membranes prepared by interfacial polymerization of 1,3, 5-trimesoyl chloride doped with 1,3, 5-trimesoyl tri-4, 4-dimethyl azlactone and a solution of tris (2-aminoethyl) amine; and (3) testing conditions are as follows: the cross-flow test shows that the single salt solution is 2000ppm, 25 ℃, 1MPa and the flow rate is 7 LPM.
TABLE 5
Figure BDA0001561340600000131
Comparative example 2
This comparative example is compared to example 4.
The preparation method of the polyamide nanofiltration membrane by using the acyl chloride oil phase monomer solution not doped with azlactone structure monomer and the amine monomer water phase solution comprises the following specific steps:
(1) firstly, soaking a polyether sulfone ultrafiltration basement membrane in 1.5 wt% of tris (2-aminoethyl) amine aqueous solution, taking out after 2min, and blowing the surface of the ultrafiltration membrane with gas to remove the redundant tris (2-aminoethyl) amine aqueous solution on the membrane surface; the tris (2-aminoethyl) amine aqueous solution consists of tris (2-aminoethyl) amine and an aqueous phase solvent, wherein the aqueous phase solvent is water, the mass fraction of the tris (2-aminoethyl) amine is 1.5 wt%, and the mass fraction of the aqueous phase solvent is 98.5 wt%;
(2) soaking the 1,3, 5-trimesoyl chloride solution on the ultrafiltration basement membrane which is prepared in the step (1) and has the surface containing the tri (2-aminoethyl) amine solution, and taking out after 10 seconds; wherein the oil phase solvent is cyclohexane, the mass fraction of the 1,3, 5-trimesoyl chloride is 0.15 wt%, and the mass fraction of the oil phase solvent is 99.85 wt%;
(3) and (4) washing the polyamide nanofiltration membrane prepared in the step (3) by using normal hexane for 15s, and similarly, carrying out heat treatment at 60 ℃ for 2min to obtain a polyamide nanofiltration membrane product.
Table 6 shows the salt rejection performance of the polyamide nanofiltration membrane prepared by interfacial polymerization of a 1,3, 5-trimesoyl chloride monomer solution and a tris (2-aminoethyl) amine solution; and (3) testing conditions are as follows: the cross-flow test shows that the single salt solution is 2000ppm, 25 ℃, 1MPa and the flow rate is 7 LPM.
TABLE 6
Figure BDA0001561340600000141
Example 5
The azlactone-based polyamide membrane of this example, also prepared by incorporating an acid chloride monomer into an azlactone-structure-containing monomer to form an oil phase solution and then reacting with an amine, differs from example 4 in that an aqueous phase amine and an oil phase are used and comprises the following steps:
(1) soaking polysulfone ultrafiltration basement membrane in 1.5 wt% piperazine water solution for 2min, and then purging with gas for 2min to remove excessive water phase solution;
(2) soaking the polysulfone ultrafiltration membrane with piperazine molecules on the surface prepared in the step (1) in a solution containing 0.025 wt% of 1,3, 5-trimesic tri-4, 4-dimethyl azlactone and 0.15 wt% of 1,3, 5-cyclohexanetriyl chloride acetone/toluene/cyclohexane, wherein the mass fraction of the 1,3, 5-trimesic tri-4, 4-dimethyl azlactone is 0.025 wt%, the mass fraction of the 1,3, 5-cyclohexanetriyl chloride is 0.15 wt%, the mass fraction of solvent acetone is 1.5 wt%, the mass fraction of solvent toluene is 3.5 wt%, and the mass fraction of solvent cyclohexane is 94.825 wt%; the interfacial polymerization time is 60s, and then the prepared polyamide nanofiltration membrane is treated for 6min at 60 ℃ to obtain the azlactone-based polyamide membrane.
Table 7 shows the desalting performance of the azlactone-based polyamide membrane prepared in this example; and (3) testing conditions are as follows: the cross-flow test shows that the single salt solution is 2000ppm, 25 ℃, 1MPa and the flow rate is 7 LPM.
TABLE 7
Figure BDA0001561340600000151
Comparative example 3
This comparative example is compared to example 5.
The preparation method of the polyamide nanofiltration membrane by using the acyl chloride oil phase monomer solution not doped with azlactone structure monomer and the amine monomer water phase solution comprises the following specific steps:
(1) firstly, soaking a polyether sulfone ultrafiltration basement membrane in 1.5 wt% piperazine aqueous phase solution, taking out after 2min, and blowing the surface of the ultrafiltration membrane with gas to remove redundant piperazine aqueous solution on the membrane surface; the piperazine water solution consists of piperazine and an aqueous phase solvent, wherein the aqueous phase solvent is water, the mass fraction of the piperazine is 1.5 wt%, and the mass fraction of the aqueous phase solvent is 98.5 wt%;
(2) soaking the 1,3, 5-cyclohexanetricarboxylic chloride solution on the ultrafiltration basement membrane with the piperazine solution on the surface prepared in the step (1), and taking out after 60 seconds; wherein the oil phase solvent is acetone, toluene and cyclohexane, the mass fraction of the 1,3, 5-cyclohexanetriyl chloride is 0.15 wt%, and the mass fractions of the acetone, the toluene and the cyclohexane in the oil phase solvent are respectively 1.5 wt%, 3.5 wt% and 94.85 wt%;
(3) and (4) washing the polyamide nanofiltration membrane prepared in the step (3) by using normal hexane for 15s, and similarly, carrying out heat treatment at 60 ℃ for 6min to obtain a polyamide nanofiltration membrane product.
Table 8 shows the desalting performance of the polyamide nanofiltration membrane prepared in this comparative example; and (3) testing conditions are as follows: the cross-flow test shows that the single salt solution is 2000ppm, 25 ℃, 1MPa and the flow rate is 7 LPM.
TABLE 8
Figure BDA0001561340600000152
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. A method of making an azlactone-based polyamide membrane, comprising:
covering a primary aliphatic amine solution on a supporting base membrane in a coating or soaking mode, and then carrying out interfacial polymerization reaction on the supporting base membrane with the primary aliphatic amine solution on the surface and an azlactone-based monomer solution containing an azlactone-based monomer to obtain an azlactone-based polyamide membrane with calcium and magnesium ion interception function; washing the prepared azlactone-based polyamide membrane with an organic solvent for 15-60s, removing the organic solvent, and performing heat treatment at 50-90 ℃ for 60s-10 min; wherein the organic solvent is one or more of n-hexane, cyclohexane, n-heptane, n-octane and iso-Par series;
immersing the azlactone-based polyamide membrane in a primary aliphatic amine solution having a concentration of 10-2000mM before the heat treatment
Wherein the name and structural formula of the azlactone-based monomer are as follows:
2-hydroxypropane-1, 2, 3-tris-4, 4-dimethylazlactone:
Figure 978756DEST_PATH_IMAGE001
，
1,3, 5-cyclohexanetri4, 4-dimethylazlactone:
Figure 99159DEST_PATH_IMAGE002
，
1,3, 5-benzenetris-4, 4-dimethylazlactone:
Figure 954595DEST_PATH_IMAGE003
，
1,2,3, 4-cyclobutyltetra-4, 4-dimethylazlactone:
Figure DEST_PATH_IMAGE005
；
the supporting basement membrane is an organic polymer ultrafiltration membrane or an inorganic ultrafiltration membrane material or an organic and inorganic hybrid porous membrane;
the primary fatty amine solution comprises primary fatty amine and a water phase additive, wherein the mass fraction of the primary fatty amine is 0.01-2wt%, and the addition amount of the water phase additive is 1-50wt% of the primary fatty amine;
the azlactone-based monomer solution includes an azlactone-based monomer, an oil phase solvent, and an oil phase additive; wherein the mass fraction of the azlactone-based monomer is 0.01-0.5wt%, the mass fraction of the oil phase solvent is 99.5-99.99wt%, and the mass fraction of the oil phase additive is 0-1.99 wt%.
2. An azlactone-based polyamide film production method as defined in claim 1, wherein the primary aliphatic amine is one or more combinations of D-glucosamine, hyperbranched polyethyleneimine, tris (2-aminoethyl) amine, diethylenetriamine, triethylenetetramine, ethylenediamine, and m-xylylenediamine.
3. An azlactone-based polyamide film production method as defined in claim 1, wherein the concentration of the primary aliphatic amine solution is 0.01-2wt% and the concentration of the azlactone-based monomer solution is 0.01-0.5 wt%.
4. An azlactone-based polyamide film production method of claim 1, wherein the aqueous phase additive is a nanoparticle, an organic phenol having a distorted spatial structure, a hydrophilic additive, or a surfactant; the oil phase additive is a cosolvent or a phase transfer catalyst; wherein:
the nano particles are sheet graphene, elongated single-walled or multi-walled carbon nanotubes;
the organic phenol with the distorted space structure is a cage-shaped porous molecule;
the hydrophilic additive is quaternary ammonium salt, alcohol amine or camphor sulfonic acid;
the cosolvent is acetone, toluene, benzene, polyalcohol, organic phosphide or dimethylformamide.
5. An azlactone-based polyamide film production method of claim 1, wherein the azlactone-based monomer solution comprises an azlactone-based monomer and an oil-phase solvent; wherein the mass fraction of the azlactone-based monomer is 0.01-0.5wt%, and the mass fraction of the oil-phase solvent is 99.5-99.99 wt%.
6. An azlactone-based polyamide film produced by the production method of any one of claims 1 to 5.
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