CN113617233A - Preparation method of novel nano-structure composite membrane - Google Patents
Preparation method of novel nano-structure composite membrane Download PDFInfo
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- CN113617233A CN113617233A CN202010381437.XA CN202010381437A CN113617233A CN 113617233 A CN113617233 A CN 113617233A CN 202010381437 A CN202010381437 A CN 202010381437A CN 113617233 A CN113617233 A CN 113617233A
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- 239000012528 membrane Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008346 aqueous phase Substances 0.000 claims abstract description 17
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 229920000768 polyamine Polymers 0.000 claims abstract description 14
- 239000012071 phase Substances 0.000 claims abstract description 13
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 10
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 39
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 34
- 239000012074 organic phase Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 230000004907 flux Effects 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- 238000000108 ultra-filtration Methods 0.000 claims description 7
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 150000004885 piperazines Chemical class 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229940058302 antinematodal agent piperazine and derivative Drugs 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 claims description 2
- PVCOXMQIAVGPJN-UHFFFAOYSA-N piperazine-1,4-diamine Chemical compound NN1CCN(N)CC1 PVCOXMQIAVGPJN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 229940066771 systemic antihistamines piperazine derivative Drugs 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 11
- 239000013543 active substance Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 239000011780 sodium chloride Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000012466 permeate Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000003321 amplification Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
Classifications
-
- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of membranes, and relates to a preparation method of a novel nano-structure composite membrane. According to the preparation method of the novel nano-structure composite membrane provided by the invention, the sodium p-styrenesulfonate monomer is added into the aqueous phase solution of interfacial polymerization to serve as a reactive active agent, so that the degree and the speed of polymerization reaction can be effectively improved by the para-sulfonic acid group, and meanwhile, the hydrophilicity of the membrane can be remarkably enhanced. The thermal stability of the sodium p-styrenesulfonate monomer can also improve the thermal stability of a polymerized structure; during the polymerization reaction, the copolymer and polyamine in the water phase and trimesoyl chloride in the oil phase are subjected to copolycondensation reaction to generate a turing nano structure, and the turing nano structure is used as a separation layer to provide more excellent and stable molecular interception effect. The preparation method provided by the invention realizes a high-performance low-cost preparation process under the condition that raw materials and parameter variables are greatly reduced through simpler and more convenient operation steps, and greatly widens the application range of the composite membrane.
Description
Technical Field
The invention belongs to the technical field of membranes, and relates to a preparation method of a nano-structure composite membrane.
Background
The interfacial polymerization method is a very common composite membrane preparation process, not only can a polymer layer with good performance be prepared by means of simpler and more convenient process steps and excellent polymerization degree, but also can realize the improvement of one or more performance parameters of the original composite membrane by adding or changing monomers of a water phase and an oil phase in the interfacial polymerization process. The existing method for preparing the nano composite membrane by the interfacial polymerization method not only needs a complex aqueous phase solution system, even needs to carry out pretreatment on an aqueous phase or a base membrane, but also can not avoid the trade-off relationship between the retention rate and the membrane flux in terms of performance.
With the continuous development of membrane preparation technology in recent years, the discovery of a nano polymerization structure enables an interfacial polymerization method to have greater application potential, and the interception effect of the composite membrane is further enhanced, but the formation of the nano structure in the polymerization process still needs to involve the increase of various monomers and preparation steps, so that the difficulty of continuous production is greatly increased, and the hydrophilicity of the membrane is not effectively improved.
Therefore, a simple and efficient preparation method of the composite membrane is needed to further improve the retention effect, enhance the hydrophilicity, simplify the preparation process, reduce the monomers involved in the polymerization process and create a preparation process of the composite membrane with the nano structure, which can be developed towards industrialization.
Disclosure of Invention
The invention aims to provide a preparation method of a novel nano-structure composite membrane aiming at the defects in the prior art and the method.
For this reason, the above object of the present invention is achieved by the following technical solutions:
the method adopts three or more than three of piperazine, piperazine derivatives, non-piperazine polyamines and sodium p-styrenesulfonate as water phase mixtures, and carries out impregnation on a polymerization layer in a pressurized environment and polymerization in a negative pressure environment, and the method comprises the following specific operation steps:
1) the total mass fraction of piperazine and derivatives thereof in the water phase is 0.15-2%, the mass fraction of non-piperazine polyamine in the water phase is 0.01-1%, and the mass fraction of sodium p-styrene sulfonate is 0.5-5%, and the piperazine and the derivatives thereof are uniformly mixed by magnetic stirring or ultrasonic oscillation at the solution temperature of more than or equal to 25 ℃;
(2) preparing an organic phase monomer solution under the condition that the solution temperature is more than or equal to 25 ℃;
(3) the interfacial polymerization reaction, firstly washing the base film with deionized water and soaking in the deionized water for 24 hours, then taking out the base film, pouring the prepared aqueous phase monomer solution on the separation layer surface of the base film and soaking for 0.5-10 minutes under the conditions that the pressure is 0.1-0.4Mpa and the solution temperature is more than or equal to 25 ℃, removing the redundant aqueous phase solution on the surface by using an air knife or a rubber roller, then soaking the base film in the prepared organic phase monomer solution for 15-120 seconds, pouring out the organic phase solution, placing the soaked base film into a 50-100 ℃ oven to carry out heat treatment for 2-15 minutes under the pressure of-0.01-0.03 Mpa, washing with the deionized water after the heat treatment is finished, and soaking in the deionized water to obtain the novel nano-structure composite film.
While adopting the above technical scheme, the present invention can also adopt or combine the following further technical schemes:
preferably, in the step (1), the piperazine derivative is one of 1, 4-diaminopiperazine, 1, 4-bis (3-aminopropyl) piperazine, N-aminoethylpiperazine or 4-aminomethylpiperazine; the non-piperazine polyamine is one of ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, o-phenylenediamine, m-phenylenediamine or p-phenylenediamine.
Preferably, in the step (2), the organic phase monomer is 0.1-0.3% of trimesoyl chloride organic solution; the organic phase solvent is normal or isomeric alkane solvent.
Preferably, the bottom membrane in step (3) may be an ultrafiltration membrane prepared from one or more of polysulfone, polyethersulfone, sulfonated polyethersulfone, polyimide, polypropylene, polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, and polyetherketone.
Preferably, the ultrafiltration membrane has a molecular weight cut-off of 20000-50000 Da.
Preferably, under the condition of 25 ℃ and the operating pressure of 0.7MPa, the desalination rate of the nano-structure composite membrane to 2000mg/L magnesium sulfate is more than or equal to 99%, the desalination rate of sodium chloride is more than or equal to 45%, and the water flux is more than or equal to 40L/(m)2·h)。
The invention belongs to the technical field of membranes, and relates to a preparation method of a novel nano-structure composite membrane. According to the preparation method of the novel nano-structure composite membrane provided by the invention, the sodium p-styrenesulfonate monomer is added into the aqueous phase solution of interfacial polymerization to serve as a reactive active agent, so that the degree and the speed of polymerization reaction can be effectively improved by the para-sulfonic acid group, and meanwhile, the hydrophilicity of the membrane can be remarkably enhanced. The thermal stability of the sodium p-styrenesulfonate monomer can also improve the thermal stability of a polymerized structure; the preparation method provided by the invention realizes a high-performance low-cost preparation process under the condition that raw materials and parameter variables are greatly reduced through simpler and more convenient operation steps, and greatly widens the application range of the composite membrane.
Detailed Description
The present invention is further described in detail with reference to specific examples.
The nano-structure composite membranes prepared by the invention are all MgSO with MgSO 0.7MPa4Prepressing with NaCl solution for 25 minutes, and adding 2000ppm MgSO4The solution and 2000ppm NaCl solution were tested for membrane flux and rejection performance. The formula for calculating the membrane flux is shown in (1).
Wherein J is the flux of the membrane (L/(m)2H)), V is the volume (L) of the collected permeate, and A is the effective area (m) of the membrane2) And T is the time (h) required for collecting V volumes of permeate.
The method for calculating the retention performance of the membrane is shown in (2).
Where R is the rejection of the membrane, Cp is the concentration on the permeate side and Cf is the concentration on the feed side.
The concentration of the electrolyte solution is measured by the conductivity meter at first, and then the concentration is calculated by fitting the standard curve of the electrolyte solution, and the rejection rate is calculated. All membranes were measured 3 times and the results were averaged.
Examples 1 to 5
Selecting a 30000 cut-off molecular weight ultrafiltration membrane made of polyether sulfone material as a base membrane, and preparing the nano-structure composite membrane according to the steps of claim 1:
(1) preparing an aqueous phase monomer solution, wherein the mass fraction of piperazine in the aqueous phase is 0.15-0.4%, the mass fraction of o-phenylenediamine is 0.15-0.4%, the concrete relation is shown in table 1, the mass fraction of sodium p-styrene sulfonate is 2.0%, and the mixture is uniformly mixed by magnetic stirring or ultrasonic oscillation at the solution temperature of more than or equal to 25 ℃;
(2) preparing an organic phase monomer solution, wherein the mass fraction of trimesoyl chloride (TMC) in the organic phase is 0.30%, and the solvent is isoparL isoparaffin solvent oil;
(3) interfacial polymerization, immersing a base membrane in a prepared aqueous phase monomer solution for 3 minutes under the pressure of 0.1MPa, pouring out the aqueous phase solution, removing redundant liquid on the surface, then immersing the base membrane in the prepared organic phase monomer solution for 60 seconds, pouring out the organic phase solution, putting the immersed base membrane into a drying oven at 90 ℃, carrying out heat treatment for 2 minutes under the pressure of-0.01 MPa, cleaning with deionized water after the heat treatment is finished, immersing in the deionized water to obtain a novel nano-structure composite membrane, and testing the interception effect and flux of the novel nano-structure composite membrane on 2000mg/L MgSO4 aqueous solution and 2000mg/L NaCl aqueous solution under the operation pressure of 0.7MPa and 25 ℃, wherein the interception effect and flux are shown in Table 1.
TABLE 1 retention and flux data for the products of examples 1-5 on 2000mg/L MgSO4 aqueous solution and NaCl aqueous solution
Examples 6 to 12
Selecting a 30000 cut-off molecular weight ultrafiltration membrane made of polysulfone material as a base membrane, and preparing the nano-structure composite membrane according to the steps of claim 1:
(1) preparing an aqueous phase monomer solution, wherein the mass fraction of N-aminoethyl piperazine, the mass fraction of o-phenylenediamine and the mass fraction of sodium p-styrene sulfonate in the aqueous phase are respectively 0.35%, 0.15% and 0.5-6.5%, and specifically, as shown in table 2, the aqueous phase monomer solution is uniformly mixed by magnetic stirring or ultrasonic oscillation at the solution temperature of more than or equal to 25 ℃;
(2) preparing an organic phase monomer solution, wherein the mass fraction of trimesoyl chloride in the organic phase is 0.3 percent, and the solvent is isoparL isoparaffin solvent oil;
(3) interfacial polymerization, immersing a base membrane in a prepared aqueous phase monomer solution for 3 minutes under the pressure of 0.1MPa, pouring out the aqueous phase solution, removing redundant liquid on the surface, then immersing the base membrane in the prepared organic phase monomer solution for 60 seconds, pouring out the organic phase solution, putting the immersed base membrane into a drying oven at 90 ℃, carrying out heat treatment for 2 minutes under the pressure of-0.01 MPa, cleaning with deionized water after the heat treatment is finished, immersing in the deionized water to obtain a novel nano-structure composite membrane, and testing the interception effect and flux of the novel nano-structure composite membrane on 2000mg/L MgSO4 aqueous solution and 2000mg/L NaCl aqueous solution under the operation pressure of 0.7MPa and 25 ℃, wherein the interception effect and flux are shown in Table 1.
TABLE 2 retention and flux data for the products of examples 6-12 on 2000mg/L MgSO4 aqueous solution and NaCl aqueous solution
The above examples show the effect of different ratios of piperazine polyamine and non-piperazine polyamine and the mass fraction of sodium styrene sulfonate on the performance of the prepared film. When the mass fraction ratio of the piperazine polyamine to the non-piperazine polyamine is more than or equal to 1, the membrane performance is gradually improved, and the ratio of the piperazine polyamine to the non-piperazine polyamine can be optimized according to the evaluation effect; when the mass fraction of the sodium p-styrene sulfonate is between 0 and 3.5 percent, the membrane performance can be improved along with the increase of the sodium p-styrene sulfonate, and when the mass fraction of the sodium p-styrene sulfonate is between 3.5 and 7 percent, the membrane performance can be reduced along with the increase of the sodium p-styrene sulfonate, but the optimal content of the sodium p-styrene sulfonate is closely related to other monomers in a water phase.
The principle of the preparation method of the invention is as follows: in the polymerization process during the reaction, sodium p-styrenesulfonate, polyamine in a water phase and trimesoyl chloride in an oil phase are subjected to copolycondensation reaction to generate a Tuling nano structure as a reactive active agent, the separating layer can provide a more excellent and stable molecular interception effect, and the sulfonic group on the para-position of the sodium p-styrenesulfonate can effectively promote the hydrophilicity and the polymerization degree of the separating layer. The impregnation effect can be effectively improved by pressurization in the impregnation process, and the sodium styrene sulfonate can be more effectively immersed into the ultrafiltration base membrane structure; the negative pressure state in the polymerization process can minimize the collapse degree of the polymeric framework after polymerization, and a good Tuoling nano structure is formed. The preparation process of the nano-structure composite membrane is simplified and improved by common and common chemical reagents, so that the composite membrane with higher comprehensive performance can be obtained, the process amplification is easy to carry out, and the preparation method has obvious industrial practical application value.
The above-described embodiments are intended to illustrate the present invention, but not to limit the present invention, and any modifications, equivalents, improvements, etc. made within the spirit of the present invention and the scope of the claims fall within the scope of the present invention.
Claims (6)
1. A preparation method of a novel nano-structure composite membrane is characterized in that three or more of piperazine, piperazine derivatives, non-piperazine polyamines and sodium p-styrenesulfonate are used as a water phase mixture, impregnation is carried out on a polymerization layer in a pressurized environment, polymerization is carried out in a negative pressure environment, and the specific operation steps are as follows:
(1) preparing an aqueous solution: the total mass fraction of piperazine and derivatives thereof in the water phase is 0.15-2%, the mass fraction of non-piperazine polyamine in the water phase is 0.01-1%, and the mass fraction of sodium p-styrene sulfonate is 0.5-7%, and the piperazine and the derivatives thereof are uniformly mixed by magnetic stirring or ultrasonic oscillation at the solution temperature of more than or equal to 25 ℃;
(2) preparing an organic phase monomer solution under the condition that the solution temperature is more than or equal to 25 ℃;
(3) the interfacial polymerization reaction, firstly washing the base film with deionized water and soaking in the deionized water for 24 hours, then taking out the base film, pouring the prepared aqueous phase monomer solution on the separation layer surface of the base film and soaking for 0.5-10 minutes under the conditions that the pressure is 0.1-0.4Mpa and the solution temperature is more than or equal to 25 ℃, removing the redundant aqueous phase solution on the surface by using an air knife or a rubber roller, then soaking the base film in the prepared organic phase monomer solution for 15-120 seconds, pouring out the organic phase solution, placing the soaked base film into a 50-100 ℃ oven to carry out heat treatment for 2-15 minutes under the pressure of-0.01-0.03 Mpa, washing with the deionized water after the heat treatment is finished, and soaking in the deionized water to obtain the novel nano-structure composite film.
2. The method for preparing a novel nanostructured composite membrane according to claim 1, wherein in the step (1), the piperazine derivative is one of 1, 4-diaminopiperazine, 1, 4-bis (3-aminopropyl) piperazine, N-aminoethyl piperazine or 4-aminomethyl piperazine; the non-piperazine polyamine is one of ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, o-phenylenediamine, m-phenylenediamine or p-phenylenediamine.
3. The method for preparing a novel nanostructured composite membrane according to claim 1, wherein in the step (2), the organic phase monomer is 0.1-0.3% trimesoyl chloride organic solution; the organic phase solvent is normal or isomeric alkane solvent.
4. The method according to claim 1, wherein the base membrane in step (3) is an ultrafiltration membrane prepared from one or more of polysulfone, polyethersulfone, sulfonated polyethersulfone, polyimide, polypropylene, polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, and polyetherketone.
5. The ultrafiltration membrane as defined in claim 3 having a molecular weight cut-off of 20000-50000 Da.
6. The method for preparing a novel nanostructured composite membrane according to claim 1, wherein the nanostructured composite membrane has a salt rejection rate of not less than 98.5%, a salt rejection rate of not less than 45%, and a water flux of not less than 40L/(m) under 25 ℃ and 0.7MPa operating pressure, respectively, for 2000mg/L magnesium sulfate2·h)。
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