CN113617233B - Preparation method of novel nano-structure composite film - Google Patents
Preparation method of novel nano-structure composite film Download PDFInfo
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- CN113617233B CN113617233B CN202010381437.XA CN202010381437A CN113617233B CN 113617233 B CN113617233 B CN 113617233B CN 202010381437 A CN202010381437 A CN 202010381437A CN 113617233 B CN113617233 B CN 113617233B
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- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000012528 membrane Substances 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012071 phase Substances 0.000 claims abstract description 19
- 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 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 229920000768 polyamine Polymers 0.000 claims abstract description 14
- 239000008346 aqueous phase Substances 0.000 claims abstract description 13
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 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
- 238000000926 separation method Methods 0.000 claims abstract description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 34
- 239000012074 organic phase Substances 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- 230000004907 flux Effects 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 6
- 238000000108 ultra-filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 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
- 238000010612 desalination reaction Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000004885 piperazines Chemical class 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 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
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 230000010355 oscillation Effects 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
- 230000000694 effects Effects 0.000 abstract description 12
- 239000013543 active substance Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 31
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000012466 permeate Substances 0.000 description 4
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 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
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application 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
- 238000005516 engineering process 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
- 125000000542 sulfonic acid group Chemical group 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 films, and relates to a preparation method of a novel nano-structure composite film. According to the preparation method of the novel nano-structure composite membrane, the sodium p-styrenesulfonate monomer is added into the aqueous phase solution subjected to interfacial polymerization to serve as the reactive active agent, so that the para-sulfonic acid group of the sodium p-styrenesulfonate monomer can not only effectively improve the polymerization degree and rate, but also obviously strengthen the hydrophilicity of the membrane. The thermal stability of the sodium p-styrenesulfonate monomer can also improve the thermal stability of the polymerized structure after polymerization; in the polymerization process during the reaction, copolycondensation reaction is carried out between the polyamine in the water phase and the trimesoyl chloride in the oil phase, so as to generate the Turing nano structure, and the separation layer can provide more excellent and stable molecular interception effect. The preparation method provided by the invention realizes a preparation process with high performance and low cost under the condition that the raw materials and parameter variables are greatly reduced through simpler operation steps, and greatly widens the application range of the composite membrane.
Description
Technical Field
The invention belongs to the technical field of films, and relates to a preparation method of a nano-structure composite film.
Background
The interfacial polymerization method is used as a very common preparation process of the composite film, not only can prepare a polymer layer with good performance by virtue of simple and convenient process steps and excellent polymerization degree, but also can realize the improvement of the original composite film on one or more performance parameters 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 interfacial polymerization not only needs a complex aqueous phase solution system and even needs pretreatment of an aqueous phase or a base membrane, but also can not avoid the trade-off relation between the interception rate and the membrane flux in performance of the prepared membrane.
With the continuous development of membrane preparation technology in recent years, the discovery of the nano-polymeric structure enables the interfacial polymerization method to have greater application potential and further enhances the interception effect of the composite membrane, but the formation of the nano-structure in the polymerization process still needs to involve a plurality of monomers and the increase of 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, which further improves the interception effect, strengthens the hydrophilicity, simplifies the preparation process, reduces the monomers involved in the polymerization process, and creates a preparation process of the nano-structure composite membrane 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 existing in the prior art and methods.
For this purpose, 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 polyamine and sodium p-styrenesulfonate as water phase mixture, and carries out impregnation on a polymerization layer and under a pressurized environment, and carries out polymerization under a negative pressure environment, and the specific operation steps are as follows:
1) The total mass fraction of piperazine and its derivatives in the water phase is 0.15-2%, the mass fraction of non-piperazine polyamine in the water phase is 0.01-1%, the mass fraction of sodium p-styrenesulfonate is 0.5-5%, and the mixture is uniformly mixed by magnetic stirring or ultrasonic oscillation under the condition that the solution temperature is 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 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 condition that the solution temperature is more than or equal to 25 ℃, removing superfluous aqueous phase solution on the surface by 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, putting the soaked base film in an oven at 50-100 ℃ and carrying out heat treatment for 2-15 minutes under the pressure of minus 0.01-minus 0.03Mpa, and washing and soaking in deionized water after the heat treatment is finished to obtain the novel nano-structure composite film.
The invention can also adopt or combine the following technical proposal when adopting the technical proposal:
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 to 0.3% of trimesoyl chloride organic solution; the organic phase solvent is normal or isoparaffin solvent.
Preferably, the bottom membrane in the step (3) is an ultrafiltration membrane prepared by one or more of polysulfone, polyethersulfone, sulfonated polyethersulfone, polyimide, polypropylene, polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene and polyetherketone.
Preferably, the molecular weight cut-off of the ultrafiltration base membrane is 20000-50000Da.
Preferably, the desalination rate of the nano-structure composite membrane to 2000mg/L magnesium sulfate is more than or equal to 99%, the sodium chloride desalination rate is more than or equal to 45%, and the water flux is more than or equal to 40L/(m 2. H) under the conditions of 25 ℃ and the operating pressure of 0.7 MPa.
The invention belongs to the technical field of films, and relates to a preparation method of a novel nano-structure composite film. According to the preparation method of the novel nano-structure composite membrane, the sodium p-styrenesulfonate monomer is added into the aqueous phase solution subjected to interfacial polymerization to serve as the reactive active agent, so that the para-sulfonic acid group of the sodium p-styrenesulfonate monomer can not only effectively improve the polymerization degree and rate, but also obviously strengthen the hydrophilicity of the membrane. The thermal stability of the sodium p-styrenesulfonate monomer can also improve the thermal stability of the polymerized structure after polymerization; the preparation method provided by the invention realizes a preparation process with high performance and low cost under the condition that the raw materials and parameter variables are greatly reduced through simpler operation steps, and greatly widens the application range of the composite membrane.
Detailed Description
The invention will be described in further detail with reference to specific examples.
The nanostructured composite membranes prepared by the invention were pre-pressed with MgSO 4 and NaCl solutions at 0.7MPa for 25 minutes, and tested for membrane flux and rejection performance with 2000ppm MgSO 4 solution and 2000ppm NaCl solution. The calculation formula of the membrane flux is shown in (1).
Where J is the flux of the membrane (L/(m 2. H)), V is the volume of permeate collected (L), A is the effective area of the membrane (m 2), and T is the time (h) required to collect the permeate in V volume.
The method for calculating the rejection 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 first measured by conductivity meter to determine the conductivity of the permeate side and the feed side, then fitted by standard curve of the electrolyte solution to calculate the concentration and then the rejection rate. All films were measured 3 times and averaged to obtain the results.
Examples 1 to 5
A30000 molecular weight cut-off ultrafiltration membrane made of a polyethersulfone material is selected as a base membrane, and the nano-structure composite membrane is prepared according to the following steps:
(1) Preparing a water phase monomer solution, wherein the mass fraction of piperazine in the water phase is 0.15-0.4%, the mass fraction of o-phenylenediamine is 0.15-0.4%, the specific relation is shown in a table 1, the mass fraction of sodium p-styrenesulfonate is 2.0%, and the water phase monomer solution is uniformly mixed by magnetic stirring or ultrasonic vibration under the condition that the temperature of the solution is 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 isopar L isoparaffin solvent oil;
(3) Interfacial polymerization reaction, at 0.1Mpa pressure, impregnating the base film in the prepared aqueous phase monomer solution for 3 minutes, pouring out the aqueous phase solution, removing superfluous liquid on the surface, then impregnating the base film in the prepared organic phase monomer solution for 60 seconds, pouring out the organic phase solution, putting the impregnated base film into a 90 ℃ oven, carrying out heat treatment for 2 minutes at-0.01 Mpa pressure, washing with deionized water after the heat treatment is finished, and soaking in the deionized water to obtain the novel nano-structure composite film, and testing the interception effect and flux of the novel nano-structure composite film on 2000mg/L MgSO4 aqueous solution and 2000mg/L NaCl aqueous solution at the operation pressure of 0.7MPa and 25 ℃, wherein the interception effect and flux are shown in table 1.
TABLE 1 effects of the products of examples 1-5 on the entrapment and flux data for 2000mg/L MgSO4 aqueous solution and NaCl aqueous solution
Examples 6 to 12
A30000 molecular weight cut-off ultrafiltration membrane made of polysulfone material is selected as a base membrane, and the nano-structure composite membrane is prepared according to the following steps:
(1) Preparing a water phase monomer solution, wherein the mass fraction of N-aminoethylpiperazine in the water phase is 0.35%, the mass fraction of o-phenylenediamine is 0.15%, the mass fraction of sodium p-styrenesulfonate is 0.5-6.5%, and the water phase monomer solution is uniformly mixed by magnetic stirring or ultrasonic vibration under the condition that the temperature of the solution is more than or equal to 25 ℃ as shown in a table 2;
(2) Preparing an organic phase monomer solution, wherein the mass fraction of trimesoyl chloride in the organic phase is 0.3%, and the solvent is isopar L isoparaffin solvent oil;
(3) Interfacial polymerization reaction, at 0.1Mpa pressure, impregnating the base film in the prepared aqueous phase monomer solution for 3 minutes, pouring out the aqueous phase solution, removing superfluous liquid on the surface, then impregnating the base film in the prepared organic phase monomer solution for 60 seconds, pouring out the organic phase solution, putting the impregnated base film into a 90 ℃ oven, carrying out heat treatment for 2 minutes at-0.01 Mpa pressure, washing with deionized water after the heat treatment is finished, and soaking in the deionized water to obtain the novel nano-structure composite film, and testing the interception effect and flux of the novel nano-structure composite film on 2000mg/L MgSO4 aqueous solution and 2000mg/L NaCl aqueous solution at the operation pressure of 0.7MPa and 25 ℃, wherein the interception effect and flux are shown in table 1.
TABLE 2 interception 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 the different ratios of the piperazine-based polyamine and the non-piperazine-based 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 film performance can be gradually improved, and the proportion between the piperazine polyamine and the non-piperazine polyamine can be optimized according to the evaluation effect; when the mass fraction of the sodium p-styrenesulfonate is between 0 and 3.5 percent, the film performance can be improved along with the increase of the sodium p-styrenesulfonate, and when the mass fraction of the sodium p-styrenesulfonate is between 3.5 and 7 percent, the film performance can be reduced along with the increase of the sodium p-styrenesulfonate, but the optimal content of the sodium p-styrenesulfonate has close relation with other monomers in the water phase.
The preparation method of the invention is as follows: in the polymerization process during the reaction, as a reactive agent, sodium styrene sulfonate, polyamine in a water phase and trimesoyl chloride in an oil phase are subjected to copolycondensation reaction to generate a turing nano structure, the separation layer can provide a more excellent and stable molecular interception effect, and the sulfonic acid group on the para position of the sodium styrene sulfonate can effectively promote the hydrophilicity and the polymerization degree of the separation layer. Pressurization in the impregnation process can effectively improve the impregnation effect, and can more effectively impregnate sodium p-styrenesulfonate into an ultrafiltration base membrane structure; the negative pressure state in the polymerization process can minimize the collapse degree of the polymerized polymer skeleton, and a good Turing nano structure is formed. The preparation process of the nano-structure composite film is simplified and improved by common and common chemical reagents, so that the composite film with higher comprehensive performance can be obtained, and the process amplification is easy, so that the preparation process has remarkable industrial practical application value.
The above detailed description is intended to illustrate the present invention by way of example only and not to limit the invention to the particular embodiments disclosed, but to limit the invention to the precise embodiments disclosed, and any modifications, equivalents, improvements, etc. that fall within the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. The preparation method of the novel nano-structure composite film is characterized by using piperazine or piperazine derivatives, non-piperazine polyamine and sodium p-styrenesulfonate as water phase mixtures, and carrying out impregnation on a polymerization layer and in a pressurized environment, and carrying out polymerization in a negative pressure environment, wherein the specific operation steps are as follows:
(1) Preparing an aqueous phase solution: the total mass fraction of piperazine and its derivatives in the water phase is 0.15-2%, the mass fraction of non-piperazine polyamine in the water phase is 0.01-1%, the mass fraction of sodium p-styrenesulfonate is 0.5-7%, and the mixture is uniformly mixed by magnetic stirring or ultrasonic oscillation under the condition that the solution temperature is 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 ℃; an organic solution of trimesic acid chloride with the mass fraction of the organic phase monomer of 0.1-0.3%; the organic phase solvent is normal or isoparaffin solvent;
(3) The interfacial polymerization reaction, firstly washing the base film with deionized water and soaking in 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 condition that the solution temperature is more than or equal to 25 ℃, removing superfluous aqueous phase solution on the surface by 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, putting the soaked base film in an oven at 50-100 ℃ and carrying out heat treatment for 2-15 minutes under the pressure of minus 0.01-minus 0.03Mpa, and washing and soaking in deionized water after the heat treatment is finished to obtain the novel nano-structure composite film.
2. The method of claim 1, wherein 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.
3. The method for preparing a novel nano-structure composite membrane according to claim 1, wherein the base membrane in the step (3) is an ultrafiltration membrane prepared by one or more of polysulfone, polyethersulfone, sulfonated polyethersulfone, polyimide, polypropylene, polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene and polyetherketone.
4. The method for preparing a novel nano-structured composite membrane according to claim 3, wherein the molecular weight cut-off of the base membrane is 20000-50000Da.
5. The method for preparing a novel nano-structured composite membrane according to claim 1, wherein the desalination rate of 2000mg/L magnesium sulfate of the nano-structured composite membrane is more than or equal to 98.5%, the sodium chloride desalination rate is more than or equal to 45% and the water flux is more than or equal to 40L/(m 2. H) respectively under the conditions of 25 ℃ and 0.7MPa operating pressure.
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| RU2074020C1 (en) * | 1993-11-22 | 1997-02-27 | Акционерное общество "Полимерсинтез" | Method of preparing pervaporation membrane |
| CN102773024A (en) * | 2012-05-07 | 2012-11-14 | 苏州信望膜技术有限公司 | Method for preparing hollow fiber type forward osmotic membrane |
| CN103977718A (en) * | 2014-06-06 | 2014-08-13 | 中国科学技术大学 | High-water-flux forward-osmosis composite membrane and preparation method thereof |
| CN104707767A (en) * | 2014-12-30 | 2015-06-17 | 杨峥雄 | Production method for reverse osmosis membrane and device |
| CN205700460U (en) * | 2016-04-09 | 2016-11-23 | 宁波大学 | A kind of use for laboratory membrane for water treatment interface polymerization reaction device |
| CN109647199A (en) * | 2018-12-20 | 2019-04-19 | 时代沃顿科技有限公司 | A kind of preparation method of reverse osmosis membrane and thus obtained reverse osmosis membrane |
| CN110449040A (en) * | 2019-08-01 | 2019-11-15 | 蓝星（杭州）膜工业有限公司 | A kind of preparation method that polyamide composite nanofiltration membrane is blended |
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