CN114534514A - Composite solvent-resistant film containing tannic acid-copper complex network interlayer, preparation method and application - Google Patents
Composite solvent-resistant film containing tannic acid-copper complex network interlayer, preparation method and application Download PDFInfo
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Abstract
The invention discloses an ultrathin composite solvent-resistant film taking a complex network generated by tannic acid and copper ions in situ as an intermediate layer and a preparation method thereof; the preparation method of the ultrathin composite solvent-resistant film with the tannic acid and copper ion in-situ generated complexing network as the intermediate layer comprises the steps of in-situ generation of the tannic acid-copper complexing intermediate layer, interfacial polymerization reaction, chemical crosslinking and solvent activation; the invention obviously improves the flux and rejection rate of the membrane by introducing the tannin-copper complex network intermediate layer, and can use water phase and oil phase monomer solution with extremely low concentration; the tannic acid has a large amount of phenolic hydroxyl groups, so that the hydrophilicity of a basement membrane can be increased, and the storage of a water phase monomer is increased; the tannic acid and the copper ions are complexed to generate a complex network, so that the stability of the middle layer can be increased, the interfacial polymerization reaction is facilitated, and the separation performance of the membrane is effectively improved. The preparation method is simple in preparation process and has good application prospect in the field of organic solution system separation.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a composite solvent-resistant membrane containing a TA-Cu complex network interlayer, a preparation method and application thereof.
Background
The membrane separation technology is a potential technology capable of effectively replacing the existing traditional high-energy-consumption separation technology. Membrane separation technology, while having been in the past for decades, remains a novel, pre-developed technology whose development, popularity, and replacement of traditional energy-intensive separation operations has a profound effect on the development of the global sustainable industry.
The Membrane Separation process mainly comprises Microfiltration (Microfiltration), Ultrafiltration (Ultrafiltration), Nanofiltration (nanofiltraction), Reverse Osmosis (Reverse Osmosis), Electrodialysis (Electrodialysis), Gas Separation (Gas Separation), Membrane Distillation (Membrane Distillation) and other processes. .
Nanofiltration (NF) is a novel pressure-driven membrane separation technology between Ultrafiltration (UF) and Reverse Osmosis (RO), the pore diameter range is 0.5-2.0 nm, the cutting molecular weight is 200-1000 Da, the energy consumption in the separation process is low, no phase change exists, and the original properties of separated substances are not influenced. Nanofiltration has a high solvent flux and low operating pressure compared to reverse osmosis techniques, and is also known as low pressure reverse osmosis or loose reverse osmosis.
Nanofiltration membranes play an important role from seawater desalination, reclaimed water recycling and wastewater treatment, and are gradually concerned by enterprises and scientific researchers since the beginning of the century when solvent-resistant nanofiltration (OSN) is started. OSN is a separation and purification technology aiming at an organic solvent system, which requires that an organic solvent nanofiltration membrane has very good solvent stability and can realize long-term operation in the organic solvent system. The rise of the OSN technology effectively makes up the defects of the traditional separation method. Compared with rectification, the OSN technology has no phase change process, so that a large amount of energy is not needed to heat the feed liquid, and the purification of the thermosensitive drug is facilitated; compared with extraction, the method has the advantages that one step is realized, and the later separation process of the extracting agent and the product is not needed; compared with the traditional separation method, the OSN technology can be scaled at will, the processing capacity is changed by increasing or reducing the number of membrane modules at will in a module mode, and the amplification problem of technologies such as a rectifying tower does not exist.
Although the OSN technology has a lot of advantages, the quantity of organic solvent nanofiltration membranes produced in a very small amount is only abroad, and the quantity of industrialized organic solvent nanofiltration membranes in China is almost zero. The commercial organic solvent nanofiltration membrane at present also has the defects of poor solvent resistance, small solvent flux and low rejection rate, and researchers are also trying to solve the problems.
In order to improve the performance of the membrane, researchers mainly adopt the following ways: adding organic or inorganic nanoparticles (such as MOFs, COFs, GO, etc.) into the separation layer, mixing nanoparticles or other polymers into the base film, introducing an intermediate layer, etc. The introduction of these nanoparticles has an agglomeration problem, so the in-situ generation of nanoparticles or intermediate layers is an important research direction.
Tannic Acid (TA), also known as tannic acid and tannin, belongs to a polyphenol compound, has certain adhesiveness, can perform a complex reaction with metal ions, and has a large amount of phenolic hydroxyl groups, good hydrophilicity and water solubility. Based on the properties of TA, the composite solvent-resistant membrane containing the intermediate layer is developed, so that the concentration of the interfacial polymerization monomer is greatly reduced, and the composite solvent-resistant membrane has higher flux and rejection rate and has good value.
Disclosure of Invention
The invention provides a composite solvent-resistant membrane containing an intermediate layer, a preparation method and application thereof, aiming at the technical problems of poor solvent resistance of a nanofiltration membrane facing an organic solvent system, low flux of a polyimide solvent-resistant nanofiltration membrane by a phase inversion method, easy agglomeration of nano particles and high use concentration of monomers in interfacial polymerization reaction in the prior art.
In order to achieve the above object, the technical scheme of the invention is as follows.
The invention discloses a composite solvent-resistant membrane containing an intermediate layer, which is prepared by generating a complexing network intermediate layer on the surface of an ultrafiltration or microfiltration basal membrane in situ and forming a layer of separation cortex on a nanometer intermediate layer through interfacial polymerization, wherein:
(1) the complex network interlayer is composed of Tannic Acid (TA) and copper ions (Cu)2+) The complex reactant composition of (1);
(2) the TA-Cu complex network intermediate layer is modified on the base film by the following method: soaking TA water solution on the base film for 1-120 s, removing excessive solution on the surface of the base film, and adding anhydrous copper chloride (CuCl)2) Soaking the aqueous solution on the surface of the base film for 1-120 s, removing the redundant solution on the surface, and drying to obtain a TA-Cu complex network intermediate layer;
(3) the concentration of the TA aqueous solution is 0.01 mM-1.0 mM; the CuCl2The concentration of the aqueous solution is 0.03 mM-3.0 mM;
(4) the composite solvent-resistant film also comprises an ultrathin polyamide separation skin layer which is prepared in situ on the ultrathin and uniform TA-Cu complex network intermediate layer in an interfacial polymerization mode;
(5) the ultra-thin polyamide separation skin layer is formed by polymerizing an ultra-low concentration monomer interface;
(6) The thickness of the polyamide separation skin layer is less than 30 nm, the average roughness is less than 5 nm, preferably, the thickness of the polyamide separation skin layer is less than 10 nm, and the average roughness of the polyamide separation skin layer is less than 2 nm.
Preferably, the composite solvent-resistant film containing the TA-Cu complex network interlayer is a solvent-resistant composite solvent-resistant film.
Preferably, the base film contains an imide group capable of undergoing a crosslinking reaction with the aliphatic polyamine compound or the aromatic polyamine compound.
Preferably, the base membrane and the TA-Cu complex network intermediate layer are connected through hydrogen bonds and pi-pi bonds or covalent bonds.
Preferably, the TA-Cu complex network intermediate layer and the separation layer are connected through covalent bonds.
Preferably, the ultrathin composite solvent-resistant film after the interfacial polymerization is crosslinked entirely with an aliphatic polyamine compound or an aromatic polyamine compound, and more preferably, the ultrathin composite solvent-resistant film after the interfacial polymerization is crosslinked with hexamethylenediamine.
Preferably, the membrane after bulk crosslinking is further subjected to a polar aprotic solvent activation treatment.
The second aspect of the invention discloses a preparation method of a composite solvent-resistant film containing a TA-Cu complex network interlayer, which comprises the following steps:
The method comprises the following steps: soaking TA water solution in the base film for 1 min, removing excessive solution on the surface of the base film, and adding copper chloride (CuCl)2) And (3) soaking the aqueous solution on the surface of the base film for 1-120 s, removing the redundant solution on the surface, and airing to obtain the base film modified by the TA-Cu complex network layer.
Step two: fully contacting the modified base membrane surface obtained in the step one with an aqueous phase monomer solution containing an aromatic diamine compound for 1-120 s, removing the aqueous phase monomer solution on the membrane surface, and airing; and (3) fully contacting the dried membrane surface with a solution of a first organic solvent containing aromatic polybasic acyl chloride for 1-60 s, removing an organic phase monomer solution on the membrane surface, carrying out heat treatment on the membrane at a certain temperature for 10-300 s, and cooling to room temperature in a dry environment to obtain the composite solvent-resistant membrane containing the TA-Cu complex network intermediate layer.
Preferably, the preparation method of the composite solvent-resistant film containing the TA-Cu complex network interlayer further comprises the following steps:
step three: crosslinking the composite solvent-resistant membrane containing the TA-Cu complex network interlayer in the step two by a crosslinking agent solution at a certain temperature for a certain time, and then washing the membrane surface by a second organic solvent to obtain the crosslinked composite solvent-resistant membrane containing the TA-Cu complex network interlayer;
Step four: and (4) activating the cross-linked composite solvent-resistant membrane containing the TA-Cu complex network interlayer in the third step by using an activating solvent at a certain temperature for a certain time, airing, replacing with a third organic solvent, and storing in the third organic solvent to obtain the final composite solvent-resistant membrane.
Preferably, the basement membrane comprises an ultrafiltration membrane and a microfiltration membrane, and more preferably, the basement membrane is an ultrafiltration membrane.
Preferably, the concentration of TA is 0.01 mM-1.0 mM, Cu2+The concentration of (b) is 0.03 mM to 3.0 mM.
Preferably, the aqueous monomer solution contains: an aromatic diamine compound.
Preferably, the aromatic diamine compound comprises m-phenylenediamine, p-phenylenediamine, other aromatic compounds containing two amine groups, or a combination of any of the above.
Preferably, the concentration of the aromatic diamine compound is 0.01-1.0% by mass.
Preferably, the organic phase monomer solution contains: aromatic tribasic acyl chloride or mixed aromatic polybasic acyl chloride and first organic solvent.
Preferably, the aromatic polybasic acyl chloride comprises 1,3, 5-trimesoyl chloride, and the mixed aromatic polybasic acyl chloride is a combination of aromatic tribasic acyl chloride and 1,2,4, 5-benzene tetracarboxyl chloride or other aromatic polybasic acyl chlorides.
Preferably, the crosslinking agent solution contains: one or more crosslinkers and a second organic solvent.
Preferably, the crosslinking agent comprises an aromatic diamine compound, an aliphatic diamine compound, or a mixture thereof.
Preferably, the aliphatic diamine compound comprises ethylenediamine, hexamethylenediamine, other aliphatic compound containing two amine groups, or a combination of any of the above.
Preferably, the crosslinking agent is ethylenediamine or hexamethylenediamine.
Preferably, the activating solvent comprises N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), Dimethylsulfoxide (DMSO), Tetrahydrofuran (THF), or a combination of any of the foregoing.
Preferably, the first organic solvent includes hydrocarbons such as alkanes and other non-polar and weakly polar solvents.
Preferably, the second organic solvent comprises isopropanol.
Preferably, the third organic solvent comprises ethanol.
Preferably, the crosslinking temperature range is from room temperature to the bubble point temperature of the crosslinking agent solution, and the crosslinking time is 5 min-4 h.
Preferably, the activation temperature range is from room temperature to the bubble point temperature of the activating reagent, and the activation time is 5 min-120 min.
Preferably, the mass percentage concentration range of the aromatic ternary acyl chloride is 0.001% -0.1%.
Preferably, the mass percentage concentration range of the cross-linking agent is 1.0% -20.0%.
The third aspect of the invention discloses an application of a composite solvent-resistant membrane containing an intermediate layer, which is characterized by being used for separating and purifying an organic solvent system and simultaneously separating and purifying a solute and a solvent of a solution system containing water and the organic solvent, wherein the molecular weight of the solute is 200-1000 daltons;
the technical scheme of the invention achieves obvious technical effect and progress and has substantive characteristics.
According to the preparation method of the composite solvent-resistant membrane containing the intermediate layer, the separation performance of the membrane is improved by a method of firstly generating a TA-Cu complex network intermediate layer in situ on the ultrafiltration and microfiltration base membrane and then carrying out interfacial polymerization, and the stability and permeability of the membrane are greatly improved through the steps of chemical crosslinking and solvent activation, and meanwhile, the application system of the nanofiltration membrane is expanded.
The invention has the obvious technical advantages that the TA-Cu complex network intermediate layer is prepared on the polyimide base film in an in-situ generation mode, the in-situ preparation method overcomes the agglomeration phenomenon when the intermediate layer is prepared by nano particles, so that the intermediate layer is uniformly distributed and is beneficial to interface polymerization, and the in-situ generation mode of the intermediate layer is more beneficial to realizing industrialization.
The second significant technical advantage of the present invention is that TA is widely distributed in natural plants and is low cost.
The third significant technical advantage of the invention is that TA has the functions of diminishing inflammation, sterilizing and resisting oxidation, and Cu2+The composite solvent-resistant film containing the TA-Cu complex network interlayer has higher antibacterial activity and oxidation resistance in the using process.
The fourth significant technical advantage of the invention is that the TA molecules have a large number of phenolic hydroxyl groups, so that the hydrophilicity of the base membrane can be improved, the storage and diffusion of the aqueous phase monomer can be controlled to a certain extent, and the interfacial polymerization is facilitated.
The fifth significant technical advantage of the present invention is that the present invention uses ultra low concentration water phase monomers and oil phase monomers, resulting in a very thin separation layer, reduced flow resistance of the solvent, and improved flux.
A sixth significant technical advantage of the present invention is that solvent resistance of the film is effectively improved by performing a chemical crosslinking step after interfacial polymerization. Post-crosslinking is adopted, and a crosslinking agent reacts with the polyimide base film to form polyamide which is more solvent-resistant; the polyimide base film and the intermediate layer network structure can be combined together in a covalent bond mode through a cross-linking agent, and the effect between the separation layer and the TA-Cu complex network intermediate layer is increased; can also react with free acyl chloride to play a role in surface modification and greatly improve the separation performance of the membrane.
The seventh significant technical advantage of the present invention is that, by further solvent activation treatment, a small amount of uncrosslinked small molecular weight polymer is dissolved, and the spatial configuration of the polymer is automatically adjusted and optimized, so that the energy of the spatial configuration of the polymer molecule is lower, and the polymer mesopore structure is more uniform, thereby further improving the permeability of the membrane, and simultaneously maintaining the chemical and mechanical stability of the membrane.
Through the technical innovation, the method provided by the invention achieves a remarkable technical progress, and has a good application prospect in the fields of organic solution system separation and water treatment containing organic solvents.
Detailed Description
The invention is further illustrated by the following specific comparative examples and examples.
The basement membrane is a Polyimide (PI) flat ultrafiltration membrane, and the cut-off molecular weight is 50000 Da;
the aromatic diamine compound is metaphenylene diamine (MPD);
the aromatic ternary acyl chloride is 1,3, 5-trimesoyl chloride (TMC);
the used crosslinking agent of the basement membrane is hexamethylene diamine;
the first organic solvent is n-hexane;
the second organic solvent is isopropanol;
the third organic solvent is ethanol;
the activating solvent is N, N-Dimethylformamide (DMF);
at 25 ℃ and a transmembrane pressure difference of 1.0 MPa, at 100 mg L −1The prepared membrane was tested for rejection and corresponding solvent flux in rhodamine B (479 daltons) -ethanol solution. At 25 ℃ and a transmembrane pressure difference of 0.5 MPa, at 100 mg L−1The prepared membrane was tested for rejection and corresponding solvent flux in a solution of tiger red sodium salt (1017 daltons) in DMF.
Comparative example:
and dissolving the aromatic diamine compound in deionized water to obtain an aqueous monomer solution, wherein the mass percent concentration of the aromatic diamine compound is 0.1%.
And dissolving the aromatic ternary acyl chloride in a first organic solvent, wherein the mass percentage concentration of the aromatic ternary acyl chloride is 0.005%, and preparing an organic phase monomer solution.
The preparation method of the polyamide composite nanofiltration membrane comprises the following steps and conditions:
and (2) soaking the water-phase monomer solution on the surface of the base membrane for 120s, removing the water-phase monomer solution on the surface of the base membrane, naturally drying in the air at room temperature, fully contacting the dried surface of the base membrane with the organic-phase monomer solution for 60s, removing the organic-phase monomer solution on the surface of the membrane, quickly putting the membrane into a drying oven at 80 ℃ for drying for 5min, taking out the membrane, and naturally cooling in a dry environment to obtain the dry composite nanofiltration membrane.
Putting the obtained dry nanofiltration membrane into a cross-linking agent solution with the mass percentage concentration of 10% and the temperature of 60 ℃ for cross-linking for 30min to obtain a cross-linked composite nanofiltration membrane; and then placing the nanofiltration membrane into an activating reagent DMF at 80 ℃ for activation for 30min to obtain the final composite nanofiltration membrane.
The prepared polyamide composite nanofiltration membrane is used at the temperature of 25 ℃ and the transmembrane pressure difference of 1.0 MPa and the dosage of 100 mg.L−1The separation performance test is carried out on the rhodamine B-ethanol solution. The retention rate of rhodamine B is 82.5 percent, and the ethanol flux is 40.4L m−2 h−1(abbreviated as LMH), the retention rate is not high, which indicates that the prepared membrane has more defects.
Example 1
Dissolving a certain amount of TA in deionized water to prepare 1 mM TA aqueous solution, and adding a certain amount of CuCl2Dissolving in deionized water to prepare a solution with the concentration of 3 mM, and performing ultrasonic treatment for 10 min for later use.
And preparing MPD aqueous solution with the concentration of 0.1 wt%, performing ultrasonic treatment for 10 min, preparing TMC n-hexane solution with the concentration of 0.005 wt%, and performing ultrasonic treatment for 10 min for later use.
The film preparation steps are as follows:
the method comprises the following steps: soaking TA water solution on the base film for 1 min, removing excessive solution on the surface of the base film, and adding anhydrous copper chloride (CuCl)2) Water (W)And (3) soaking the solution on the surface of the base film for 1 min, removing the redundant solution on the surface, and airing to obtain the base film modified by the TA-Cu complex network layer.
Step two: fully contacting the modified base membrane surface obtained in the step one with an aqueous phase monomer solution containing an aromatic diamine compound for 120s, removing the aqueous phase monomer solution on the membrane surface, and airing; and (3) fully contacting the dried membrane surface with a solution of a first organic solvent containing aromatic polybasic acyl chloride for 60s, removing an organic phase monomer solution on the membrane surface, carrying out heat treatment on the membrane at a certain temperature for 5 min, and cooling to room temperature in a dry environment to obtain the composite solvent-resistant membrane containing the TA-Cu complex network intermediate layer.
Step three: putting the composite solvent-resistant membrane containing the TA-Cu complex network intermediate layer in the step two into a cross-linking agent solution with the concentration of 10 wt% and the temperature of 60 ℃ for cross-linking for 30min to obtain a cross-linked composite solvent-resistant membrane containing the TA-Cu complex network intermediate layer;
step four: and (3) activating the cross-linked composite solvent-resistant membrane containing the TA-Cu complex network intermediate layer at the third step by using an activating solvent DMF at the temperature of 80 ℃ for 30min, and airing to obtain the final composite solvent-resistant membrane.
The test conditions were the same as in the comparative example.
The prepared composite solvent-resistant membrane containing the TA-Cu complex network intermediate layer has the rejection rate of 97.6 percent on rhodamine B and the ethanol flux of 40.9L m−2 h−1(abbreviated as LMH), the retention rate is much higher than that of the comparative example, and the introduction of the TA-Cu complex network intermediate layer improves the separation performance of the membrane.
Example 2
The only difference from example 1 is: cupric chloride (CuCl)2) The aqueous solution is soaked on the surface of the base film for 20 s, so that the complexing reaction time for preparing the intermediate layer is reduced.
All other steps are the same as in example 1; the test conditions were the same as in example 1.
The prepared composite solvent-resistant membrane containing the TA-Cu complex network intermediate layer has the rejection rate of 97.7 percent on rhodamine B and the ethanol flux of 50.8L m −2 h−1(abbreviated as LMH), and practiceCompared with the comparative example, the ethanol flux is increased, the retention rate and the flux are both greatly improved, and the change of the complexing time of the TA-Cu complexing network interlayer further improves the separation performance of the membrane.
Therefore, the invention achieves remarkable technical effects and advances.
Example 3
The difference from example 2 is only: the concentration of the aqueous MPD solution was 0.025 wt%, i.e., the concentration of the aqueous phase monomer was reduced.
All other steps were the same as in example 2; the test conditions were the same as in comparative example 1.
The prepared composite solvent-resistant membrane containing the TA-Cu complex network intermediate layer has the rejection rate of 97.1 percent on rhodamine B and the ethanol flux of 57.6L m−2 h−1(abbreviated as LMH), the ethanol flux was further increased compared to example 2, indicating that the interfacial polymerization monomer concentration could be further decreased based on the presence of TA-Cu intermediate.
Example 4
The difference from example 3 is only: the concentration of the aqueous TA solution was 0.25 mM, CuCl2The concentration of the aqueous solution was 0.75 mM, i.e., the concentration of the reactant at the time of intermediate layer preparation was reduced.
All other steps are the same as in example 3. The test conditions compared to comparative example 1 increased: at 25 ℃ and a transmembrane pressure difference of 0.5 MPa, at 100 mg L −1The prepared membrane was tested for rejection and corresponding solvent flux in a solution of tiger red sodium salt (1017 daltons) in DMF.
The prepared composite solvent-resistant membrane containing the TA-Cu complex network intermediate layer is used for resisting 100 mg L of solvent at 25 ℃ and under the transmembrane pressure difference of 1.0 MPa−1The retention rate of rhodamine B in the rhodamine B ethanol solution is more than 97.7 percent, and the flux is more than 60.3L m−2h−1And the molecular weight of the rhodamine B is 479 daltons.
After the composite solvent-resistant membrane is continuously filtered and operated for 75 hours at 25 ℃ and under the transmembrane pressure difference of 0.5 MPa, 100 mg L of the composite solvent-resistant membrane is filtered−1The retention rate of RB in the solution of the tiger red sodium salt (RB 1017) DMF is still more than 98 percent.
The introduction of the TA-Cu complex network interlayer can not only improve the separation performance of the membrane, but also further reduce the concentration of the monomers in the interfacial polymerization reaction on the premise of keeping the separation performance from being reduced, thereby realizing the ultra-low concentration interfacial polymerization.
AFM images of the composite solvent-resistant films prepared in the comparative example, the example 2 and the example 4 show that the average roughness of the composite solvent-resistant film is not more than 4.5 nm when low-concentration interfacial polymerization monomers and ultra-low interfacial polymerization monomers are used, and therefore, the ultra-smooth separation skin layer is obtained and has good stain resistance; the film prepared in example 2 was analyzed for depth of probing of the polyamide material by XPS to obtain a film prepared in example 2 with a polyamide separation skin thickness of about 10 nm.
The aperture analysis result shows that the aperture of the prepared ultrathin composite nanofiltration membrane is reduced, so that the rejection rate of the membrane is increased; at the same time, the pore density and porosity are also greatly increased, resulting in a significant increase in flux.
Namely, the invention achieves remarkable technical effects and progress.
In order to compare the separation performance of the composite solvent-resistant membranes prepared in the comparative example and example, the preparation conditions and separation performance of the membranes are shown in table 1. The prepared composite solvent-resistant membrane is subjected to cross-linking by hexamethylene diamine at 60 ℃ for 30 min and activation by DMF at 80 ℃ for 30 min, the separation performance of rhodamine B-ethanol solution is tested, and the test conditions are the same as those of a comparative example.
Table 1 comparative and example preparation conditions and separation performance comparison
By comparing the membrane preparation conditions and the membrane separation performance in table 1, it can be seen that the introduction of the TA-Cu complex network interlayer greatly improves the rejection performance and the permeability of the membrane. It is worth noting that under the premise of existence of the middle layer, the concentration of the MPD of the interface polymerization water-phase monomer can be greatly reduced, and the interface polymerization with ultra-low concentration is realized.
The above examples show that a TA-Cu complex network layer is generated in situ on a base film, which has a great influence on the interfacial polymerization process, and the prepared composite solvent-resistant film containing the TA-Cu complex network intermediate layer has excellent performance, and remarkable technical effects and progress are achieved.
It should be noted that the above-mentioned embodiments illustrate only preferred specific embodiments of the invention, and are not to be construed as limiting the invention, any embodiments falling within the scope of the invention, which is defined by the features of the claims or the equivalents thereof, constituting a right to infringe the invention.
Claims (18)
1. A composite solvent-resistant membrane containing a tannin-copper (TA-Cu) complex network interlayer is characterized in that,
(1) the complex network interlayer is composed of Tannic Acid (TA) and copper ions (Cu)2+) The film is formed by in-situ modification on the surface of a base film in a complexing reaction mode, and is ultrathin and uniform;
(2) the TA-Cu complex network intermediate layer is modified on the base film by the following method: soaking TA water solution on the base film for 1-120 s, removing excessive solution on the surface of the base film, and adding copper chloride (CuCl)2) Soaking the aqueous solution on the surface of the base film for 1-120 s, removing the redundant solution on the surface, and airing to obtain a TA-Cu complex network intermediate layer; the concentration of the TA aqueous solution is 0.01 mM-1.0 mM; the CuCl2The concentration of the aqueous solution is 0.03 mM-3.0 mM;
(3) the composite solvent-resistant film also comprises an ultrathin polyamide separation skin layer which is prepared in situ on the TA-Cu complex network intermediate layer in an interfacial polymerization mode; the ultra-thin polyamide separation skin layer is formed by polymerizing an ultra-low concentration monomer interface; the average thickness of the polyamide separation skin layer is less than 30 nm, the average roughness is less than 5 nm, preferably, the average thickness of the polyamide separation skin layer is less than 10 nm, and the average roughness of the polyamide separation skin layer is less than 2 nm.
2. The composite solvent-resistant membrane containing the TA-Cu complex network interlayer of claim 1 is characterized in that,
(1) the TA-Cu complex network intermediate layer composite solvent-resistant film comprises a base film and a base film, wherein the base film contains an imide group capable of performing a cross-linking reaction with an aliphatic polyamine compound or an aromatic polyamine compound;
(2) the ultra-thin composite solvent-resistant membrane after interfacial polymerization is subjected to integral crosslinking by using an aliphatic polyamine compound or an aromatic polyamine compound;
(3) the ultrathin composite solvent-resistant film after integral crosslinking is subjected to polar aprotic solvent activation treatment;
(4) the base membrane is connected with the TA-Cu complex network intermediate layer through hydrogen bonds and pi-pi bonds or covalent bonds;
(5) the TA-Cu complex network intermediate layer and the separation layer are connected through a covalent bond.
3. The composite solvent-resistant membrane containing the TA-Cu complex network interlayer as claimed in claim 2, wherein the composite solvent-resistant membrane is capable of resisting 100 mg L at 25 ℃ and a transmembrane pressure difference of 1.0 MPa−1The retention rate of rhodamine B in the rhodamine B/ethanol solution is more than 97 percent, and the ethanol flux is more than 40L m−2 h−1And the molecular weight of the rhodamine B is 479 daltons.
4. A preparation method of a composite solvent-resistant film containing a TA-Cu complex network interlayer is characterized by comprising the following steps:
the method comprises the following steps: soaking a TA aqueous solution on a base film for 1-120 s, removing redundant solution on the surface of the base film, and then using copper chloride (CuCl)2) Soaking the aqueous solution on the surface of the base film for 1-120 s, removing redundant solution on the surface, and airing to obtain the base film modified by the TA-Cu complex network layer;
step two: fully contacting the modified base membrane surface obtained in the step one with an aqueous phase monomer solution containing an aromatic diamine compound for 1-120 s, removing the aqueous phase monomer solution on the membrane surface, and airing; and (3) fully contacting the dried membrane surface with a solution of a first organic solvent containing aromatic polybasic acyl chloride for 1-120 s, removing an organic phase monomer solution on the membrane surface, carrying out heat treatment on the membrane at a certain temperature for 10-300 s, and cooling to room temperature in a dry environment to obtain the composite solvent-resistant membrane containing the TA-Cu complex network intermediate layer.
5. The method for preparing the composite solvent-resistant film containing the TA-Cu complex network interlayer as claimed in claim 4, wherein the composite solvent-resistant film is further processed by the following steps:
Step three: crosslinking the composite solvent-resistant membrane containing the TA-Cu complex network interlayer of claim 4 by a crosslinking agent solution at a certain temperature for a certain time, and then washing the membrane surface by a second organic solvent to obtain the crosslinked composite solvent-resistant membrane containing the TA-Cu complex network interlayer;
step four: and (3) activating the cross-linked composite solvent-resistant membrane containing the TA-Cu complex network interlayer at a certain temperature for a certain time, airing, replacing with a third organic solvent, and storing in the third organic solvent to obtain the final composite solvent-resistant membrane.
6. The method for preparing a composite solvent-resistant membrane containing a TA-Cu complex network interlayer according to claim 4 or claim 5, wherein the aqueous monomer solution comprises: an aromatic diamine compound.
7. The method of claim 6, wherein the aromatic diamine compound comprises m-phenylenediamine, p-phenylenediamine, other aromatic compounds containing two amine groups, or any combination thereof.
8. The method for preparing a composite solvent-resistant membrane containing a TA-Cu complex network interlayer as claimed in claim 6, wherein the concentration of the aromatic diamine compound is 0.01-1.0% by mass.
9. The method for preparing a composite solvent-resistant membrane containing a TA-Cu complex network interlayer according to claim 4 or claim 5, wherein the organic phase monomer solution contains: aromatic tribasic acyl chloride or mixed aromatic polybasic acyl chloride, and first organic solvent.
10. The method according to claim 9, wherein the aromatic triacyl chloride comprises 1,3, 5-trimesoyl chloride, and the mixed aromatic triacyl chloride is a combination of aromatic triacyl chloride and 1,2,4, 5-benzene tetracarboxyl chloride or other aromatic triacyl chlorides.
11. The method for preparing a composite solvent-resistant membrane containing a TA-Cu complex network interlayer as claimed in claim 5, wherein the cross-linking agent solution comprises: one or more crosslinkers and a second organic solvent.
12. The method as claimed in claim 11, wherein the cross-linking agent comprises aromatic diamine compound, aliphatic diamine compound, or their mixture.
13. The method of claim 12, wherein the aliphatic diamine compound comprises ethylenediamine, hexamethylenediamine, other aliphatic compound containing two amine groups, or a combination thereof.
14. The method for preparing a composite solvent-resistant membrane containing a TA-Cu complex network interlayer according to claim 13, wherein the cross-linking agent is ethylenediamine or hexamethylenediamine.
15. The method of claim 5, wherein the activating solvent comprises N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), Dimethylsulfoxide (DMSO), Tetrahydrofuran (THF), or any combination thereof.
16. The method for preparing the composite solvent-resistant membrane containing the TA-Cu complex network interlayer as claimed in claim 10, wherein the concentration of the aromatic ternary acyl chloride is 0.001% -0.1% by mass.
17. The method for preparing the composite solvent-resistant membrane containing the TA-Cu complex network interlayer as claimed in claim 5, wherein the mass percentage concentration of the cross-linking agent is 1.0-20.0%.
18. An application of a composite solvent-resistant membrane containing a TA-Cu complex network interlayer is characterized by being used for separation and purification of an organic solvent system and an aqueous solution system, and separation and purification of a solute and a solvent of the aqueous solution system and the organic solvent at the same time, wherein the composite solvent-resistant membrane containing the TA-Cu complex network interlayer is the composite solvent-resistant membrane containing the TA-Cu complex network interlayer in any one of claims 1 to 3, or the composite solvent-resistant membrane prepared by the preparation method in any one of claims 4 to 17.
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