CN108939932B - Preparation method of high-performance aromatic polyamide composite membrane - Google Patents

Preparation method of high-performance aromatic polyamide composite membrane Download PDF

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CN108939932B
CN108939932B CN201811011240.6A CN201811011240A CN108939932B CN 108939932 B CN108939932 B CN 108939932B CN 201811011240 A CN201811011240 A CN 201811011240A CN 108939932 B CN108939932 B CN 108939932B
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aromatic polyamide
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polyamide composite
composite membrane
diisocyanate
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CN108939932A (en
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张田林
樊变花
班鑫鑫
陈枫
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Huaihai Institute of Techology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention provides a preparation method of a high-performance aromatic polyamide composite membrane, the density of PEO chains, quaternary ammonium cations and salicylaldehyde grafted on the surface of the high-performance aromatic polyamide composite membrane is high, and the hydrophilicity of the surface of the membrane is high; the surface of the membrane is not only grafted with the functional group, but also is connected with an aromatic diamide structural unit, the chemical property of the membrane is similar to that of the aromatic diamide structural unit in the aromatic polyamide active layer of the membrane, and the membrane can be used as a sacrificial material to generate chemical reaction with residual chlorine or chlorine-oxygen compounds in seawater in advance, so that the chemical damage of the residual chlorine or chlorine-oxygen compounds in the seawater to the aromatic polyamide active layer of the membrane is effectively prevented, and the long-term stability of the membrane structure is ensured; the even distribution of the salicylaldehyde monomolecular layer of grafting on the membrane surface can high-efficient filtration adsorb the heavy metal ion in the sea water, produces antibiotic biocidal function, has positive meaning to guaranteeing the cleanness on membrane surface.

Description

Preparation method of high-performance aromatic polyamide composite membrane
Technical Field
The invention relates to a preparation method of a high-performance aromatic polyamide composite membrane, in particular to a preparation method of a high-performance aromatic polyamide composite membrane with a surface grafted with PEG chains, quaternary ammonium cations and salicylaldehyde functional groups, which is applied to a seawater desalination process and belongs to the field of functional high polymer materials.
Background
An aromatic polyamide composite membrane (APA-TFC membrane) is formed by depositing an ultrathin aromatic polyamide membrane on a porous polysulfone or polyether sulfone supporting base membrane, wherein the aromatic polyamide is a polymer taking m-phenylenediamine and trimesoyl chloride as monomers. The membrane has large water flux and high desalination rate, and becomes a mainstream product for desalinating seawater. However, the aromatic polyamide composite membrane has the troublesome problems of membrane pollution caused by marine organisms and chemical degradation of the membrane caused by active chlorine during the use of the aromatic polyamide composite membrane for nearly two decades. The membrane marine organism pollution refers to that an abnormal and stubborn biological layer is formed by adhesion, growth and reproduction of marine microorganisms on the surface of the composite membrane, the artificial cleaning is difficult, and the working efficiency of the composite membrane is seriously influenced; in order to solve the problem of biological pollution of marine microorganisms to the aromatic polyamide composite membrane in the seawater desalination process, the seawater needs to be pretreated by introducing chlorine. However, the chemical damage of the residual trace chlorine and oxychloride in the seawater to the aromatic polyamide composite membrane greatly shortens the service performance and the service life of the aromatic polyamide composite membrane. Therefore, how to effectively control and reduce the pollution of the aromatic polyamide composite membrane and ensure the chemical stability of the aromatic polyamide composite membrane is an important research topic in the technical field of aromatic polyamide membranes.
For more than twenty years, in order to obtain an aromatic polyamide composite membrane with excellent comprehensive performances such as high surface antifouling performance, high stability of chlorine and oxygen, high surface hydrophilicity, large water flux and the like, the method for modifying the surface of the aromatic polyamide composite membrane is an effective, quick, simple and flexible method, and mainly comprises the following steps: (1) surface coating, (2) surface polymerization and deposition, and (3) surface grafting modification, wherein the coating or grafting of water-soluble polyethylene glycol (PEG), polyacrylic acid, polyacrylamide, quaternary ammonium salt, chlorohydantoin, a zwitterionic polymer brush, graphene oxide or carbon nanotubes on the surface of the membrane has a positive effect on improving the antifouling performance and the chlorine resistance stability of the membrane. However, the uniformity of the modification of the membrane surface by adopting the method is poor, the blockage of the micropores of the membrane is easy to cause, and the permeability is reduced; in addition, the density of functional groups introduced into the surface of the membrane is low, so that the hydrophilicity of the surface of the membrane is not high, and the water flux is not changed greatly; in addition, in the process of graft copolymerization modification of the membrane surface, monomer raw material waste caused by monomer homopolymerization is serious; finally, the existing surface modification technology has the outstanding defect that the performance improvement of the aromatic polyamide composite membrane is single, and the comprehensive performance of the membrane is not improved comprehensively.
In order to overcome the defects of the surface modification technology and the graft modification method of the existing aromatic polyamide composite membrane, the inventor proposes a method for uniformly planting structural units containing quaternary ammonium salt and salicylaldehyde functional groups on the surface of the membrane through chemical reaction (see CN 103349922B). The principle is that the sterilization and biocidal effects of different mechanisms of quaternary ammonium salt and salicylaldehyde functional groups and the effect of selective complexing adsorption of heavy metal ions in seawater are utilized to generate a synergistic and efficient marine organism fouling prevention function, so that the cleanness of the membrane surface is ensured; secondly, the chemical reaction between the abundant salicylaldehyde functional groups on the surface of the aromatic polyamide composite membrane and the residual trace chlorine and oxychloride in the pretreated seawater is more rapid, the chemical damage effect of the residual trace chlorine and oxychloride in the seawater on the membrane is prevented, and the service performance and the service life of the aromatic polyamide composite membrane are ensured; moreover, the quaternary ammonium salt is grafted on the surface of the membrane, so that the hydrophilic performance of the membrane can be effectively improved, and the method is beneficial to ensuring the water flux of the membrane. However, as the membrane is used for a longer period of time, the problem of fouling by marine organisms still remains. In 2015, the inventor modifies a fresh aromatic polyamide composite membrane in CN105251372B through organic polyamine, and then performs condensation reaction with N, N, N-trihydrocarbyl-N- (4-hydroxy-3-aldehyde benzyl) ammonium chloride to prepare a method for grafting salicylaldehyde Schiff base and quaternary ammonium cation on the surface of the membrane, wherein the density is higher, however, the hydrophilicity of the surface of the membrane is changed, and the water flux is improved. Aiming at the defects of the prior functionalization technology and method of the aromatic polyamide composite membrane, the invention provides a preparation method of a high-performance aromatic polyamide composite membrane.
Disclosure of Invention
The invention provides a preparation method of a high-performance aromatic polyamide composite membrane, in particular to a preparation method of a high-performance aromatic polyamide composite membrane with a surface grafted with a polyethylene glycol chain, a quaternary ammonium cation and a salicylaldehyde functional group; firstly, carrying out esterification reaction on exposed acyl chloride groups on the surface of a newly-generated aromatic polyamide composite membrane and dialkyl amino-terminated polyethylene glycol (commonly also called monoamino polyethylene glycol and amino-terminated PEG) to prepare an aromatic polyamide composite membrane with a surface grafted with a terminal tertiary amino-terminated PEG chain; secondly, performing addition reaction on the aromatic polyamide composite membrane with the surface grafted with the tertiary amino PEG chain and diisocyanate to prepare an aromatic polyamide composite membrane with the surface grafted with the tertiary amino PEG chain and isocyanate group; thirdly, the aromatic polyamide composite membrane with the surface grafted with the terminal tertiary amino PEG chain and the isocyanate group is respectively mixed with N, N-dialkyl ethanolamine or 3-dialkyl aminopropylamine to prepare the aromatic polyamide composite membrane with the surface grafted with the terminal tertiary amino PEG chain and the tertiary amine group; and finally, performing quaternary salinization reaction on the aromatic polyamide composite membrane with the surface grafted with the terminal tertiary amino PEG chain and the tertiary amino and the 5-chloromethyl salicylaldehyde to prepare the high-performance aromatic polyamide composite membrane with the surface grafted with the PEG chain, the quaternary ammonium cation and the salicylaldehyde.
The invention has the advantages that the density of the surface grafting PEG chain, quaternary ammonium cation and salicylaldehyde of the aromatic polyamide composite membrane is greatly improved compared with CN103349922B or CN 105251372B; the hydrophilicity of the membrane surface is correspondingly greatly improved; the surface of the membrane is not only grafted with salicylaldehyde groups, but also connected with an aromatic diamide structural unit, the chemical property of the aromatic diamide structural unit is similar to that of the aromatic diamide structural unit in the aromatic polyamide active layer of the membrane, and the aromatic diamide structural unit can be used as a sacrificial material to generate chemical reaction with residual chlorine or chlorine-oxygen compounds in seawater in advance, so that the chemical damage of the residual chlorine or chlorine-oxygen compounds in the seawater to the active layer of the aromatic polyamide composite membrane is effectively prevented, and the long-term stability of the structure of the aromatic polyamide composite membrane is ensured; the salicylic aldehyde monomolecular layer grafted on the membrane surface is uniformly distributed, so that heavy metal ions in seawater can be efficiently filtered and adsorbed, an antibacterial and biocidal function in cooperation with quaternary ammonium cations and the salicylic aldehyde is generated, and the membrane surface cleaning agent has positive significance for ensuring the cleaning of the membrane surface.
The preparation method of the high-performance aromatic polyamide composite membrane provided by the invention is specifically described as follows:
preparation method of aromatic polyamide composite membrane with surface grafted with terminal tertiary amino polyethylene glycol chain
The method comprises the steps of dipping a fresh aromatic polyamide composite membrane with acyl chloride groups on the surface in a dialkyl amino-terminated polyethylene glycol solution with the mass percentage concentration of 1.5-25%, controlling the temperature of the dialkyl amino-terminated polyethylene glycol solution to be 60-90 ℃, carrying out esterification reaction for 2-24 hours, taking out the membrane, washing the membrane to be neutral by sequentially using ethanol, a sodium carbonate aqueous solution with the mass percentage of 10% and deionized water, and drying the membrane to obtain the aromatic polyamide composite membrane with the surface grafted with tertiary amino-terminated PEG chains, wherein the reaction formula is shown in the drawing (I).
The nascent aromatic polyamide composite membrane with the surface containing the acyl chloride groups is prepared by taking m-phenylenediamine and trimesoyl chloride as monomers and carrying out interfacial polymerization on the surface of a microporous polysulfone support membrane or a microporous polyethersulfone support membrane according to the method and the steps disclosed by J.Membr.Sci.428(2013) 403-409 or J.Membr.Sci.457(2014) 88-97, CN103349922B or CN 105251372B;
the chemical structure of the terminal dihydrocarbylaminopolyethylene glycol is shown by a general formula (A):
Figure GDA0001800232510000031
wherein R1 and R2 in the general formula (A) are respectively selected from C1-C18 alkyl, and n is an integer of 3-3000;
the dihydrocarbylaminopolyethylene glycol terminated solution is prepared by dissolving dihydrocarbylaminopolyethylene glycol terminated in a solvent; the dosage of the dihydrocarbylaminopolyethylene glycol solution is 1-10 times of the mass of the nascent aromatic polyamide composite membrane with the acyl chloride group on the surface;
the solvent is one or more than two of ethyl acetate, acetone, 1, 4-dioxane, tetrahydrofuran, triethylamine, triethylene diamine, N-methylmorpholine, pyridine, 4-dimethylaminopyridine, 1, 2-dichloroethane, carbon tetrachloride or chloroform; preparation method of aromatic polyamide composite membrane with secondary surface grafted with terminal tertiary amino polyethylene glycol chain and isocyanate group
Weighing diisocyanate and organic tin, dissolving the diisocyanate and the organic tin in an organic solvent to prepare a diisocyanate solution, controlling the mass percentage concentration of the diisocyanate in the diisocyanate solution to be 1.5-25%, and controlling the use amount of the organic tin to be 0.05-5% of the mass of the diisocyanate; and (3) controlling the temperature of the diisocyanate solution to be 0-90 ℃, soaking the aromatic polyamide composite membrane with the surface grafted with the tertiary amino group-terminated PEG chain prepared in the step one in the diisocyanate solution, reacting for 0.5-8 hours, taking out the membrane, washing the membrane with chloroform or ethyl acetate, and preparing the aromatic polyamide composite membrane with the surface grafted with the tertiary amino group-terminated PEG chain and the isocyanate group according to a reaction formula.
Wherein the diisocyanate is selected from p-phenylene diisocyanate (PPDI), m-phenylene diisocyanate (MPDI), toluene diisocyanate (m-phenylene diisocyanate)TDI), cyclohexane-1, 4-diisocyanate (CHDI), diphenylmethane-4, 4 '-diisocyanate (MDI), 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4, 4' -diisocyanate (H)12MDI), trimethylhexane diisocyanate (TMDI) or tetramethylxylene diisocyanate (TMXDI).
The organic tin refers to one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dialkyl tin dimaleate, dibutyltin didodecyl sulfide or dibutyltin diacetate;
the organic solvent refers to one or more than two of ethyl acetate, propyl acetate, butyl acetate, acetone, 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or 1, 2-dichloroethane;
preparation method of aromatic polyamide composite membrane with surface grafted with terminal tertiary amino PEG chain and tertiary amino
Weighing N, N-dialkyl ethanolamine or 3-dialkyl aminopropylamine, dissolving in a solvent to prepare a tertiary amine solution, controlling the mass percentage concentration of the N, N-dialkyl ethanolamine or 3-dialkyl aminopropylamine to be 1.5-25%, controlling the temperature of the tertiary amine solution to be 25-90 ℃, soaking the aromatic polyamide composite membrane with the surface grafted with the tertiary amino-terminated PEG chain and the isocyanate group prepared in the second step in the tertiary amine solution, reacting for 0.5-8 hours, taking out the membrane, washing the membrane with ethanol, and drying the membrane to prepare the aromatic polyamide composite membrane with the surface containing the tertiary amino-terminated PEG chain and the tertiary amino group, wherein the schematic diagram of the reaction formula is shown in the third step.
Wherein the chemical structure of the N, N-dihydrocarbylethanolamine is represented by the general formula (B):
Figure GDA0001800232510000041
wherein R in the general formula (B)1And R2Are respectively selected from C1～C18A hydrocarbon group of (1).
The chemical structure of the 3-dihydrocarbylaminopropylamine is represented by the general formula (C):
Figure GDA0001800232510000042
wherein R in the general formula (C)1And R2Are respectively selected from C1～C18A hydrocarbon group of (1).
The amount of the tertiary amine solution is 1-10 times of the mass of the aromatic polyamide composite film with the surface grafted tertiary amino group, the polyethylene glycol chain and the isocyanate group;
the solvent is one or more than two of ethyl acetate, acetone, 1, 4-dioxane, tetrahydrofuran, triethylamine, triethylene diamine, N-methylmorpholine, pyridine, 4-dimethylaminopyridine, 1, 2-dichloroethane, carbon tetrachloride or chloroform; preparation method of high-performance aromatic polyamide composite membrane with surfaces grafted with polyethylene glycol chain, quaternary ammonium cation and salicylaldehyde in four steps
Weighing 5-chloromethyl salicylaldehyde and dissolving in a solvent to prepare a 5-chloromethyl salicylaldehyde solution, wherein the mass percentage concentration of the 5-chloromethyl salicylaldehyde solution is controlled to be 3-30%; and (3) controlling the temperature of the 5-chloromethyl salicylaldehyde solution to-5-65 ℃, soaking the aromatic polyamide composite membrane with the surface containing the terminal tertiary amine group PEG chain and the tertiary amine group prepared in the step three in the 5-chloromethyl salicylaldehyde solution, reacting for 2-12 hours, taking out the membrane, washing and drying to obtain the high-performance aromatic polyamide composite membrane with the surface grafted with the polyethylene glycol chain, the quaternary ammonium cation and the salicylaldehyde functional group, and referring to a reaction formula schematic diagram (IV).
The amount of the 5-chloromethyl salicylaldehyde is 3-30% of the mass of the aromatic polyamide composite membrane with the surface grafted with the terminal tertiary amino group, the PEG chain and the tertiary amino group.
The solvent is one or more than two of ethyl acetate, propyl acetate, butyl acetate, acetone, 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or 1, 2-dichloroethane;
the high-performance chlorine aromatic polyamide composite membrane provided by the invention has the following characteristics:
the high-performance polyaromatic amide composite membrane provided by the invention has high surface hydrophilicity, high marine organism fouling resistance, strong chlorine and oxygen resistance and stable and durable seawater desalination operation performance.
Secondly, most of the raw materials for preparing the high-performance polyaromatic amide composite membrane are commercial products, and the preparation method is simple and easy to implement and easy to industrialize.
Drawings
FIG. 1 is a schematic diagram of a reaction scheme (i);
FIG. 2 is a schematic diagram of the reaction scheme;
FIG. 3 is a schematic diagram of a reaction formula (c);
FIG. 4 is a schematic diagram (iv) of the reaction scheme.
Detailed Description
The preparation of the high performance aromatic polyamide composite membrane provided by the present invention is further illustrated by the following examples, which are intended to provide a better understanding of the present invention.
Example 1 preparation of high-Performance aromatic Polyamide composite film (1)
Step one preparation of aromatic polyamide composite membrane with dimethylamino PEG chain grafted on surface
According to the methods and procedures disclosed in Journal of Membrane Science 428(2013) 403-, on the surface of a square 10cm 10 h microporous polysulfone supporting membrane, through the interfacial polymerization of m-phenylenediamine and trimesoyl chloride, a fresh aromatic polyamide composite membrane with acyl chloride groups on the surface is prepared, the fresh aromatic polyamide composite membrane with acyl chloride groups on the surface is immersed in 30mL of mixed solution of 1, 4-dioxane (20mL) with the mass percentage concentration of 5.5 percent of dimethylamino polyethylene glycol-600 (also called DMA-PEG-600) and triethylamine (10mL), controlling the temperature to be 60-65 ℃, completing esterification reaction after 6 hours, taking out the membrane, washing the membrane to be neutral by using ethanol, sodium carbonate aqueous solution and deionized water in sequence, and drying the membrane to obtain the aromatic polyamide composite membrane with the dimethylamino PEG chain grafted on the surface.
Preparation of aromatic polyamide composite membrane with dimethylamino PEG chain and isocyanate group grafted on secondary surface
Weighing 6.5 g of p-phenylene diisocyanate and a small amount of organic tin, dissolving in 30mL of acetone to prepare a p-phenylene diisocyanate solution, controlling the temperature to be 25-35 ℃, soaking the aromatic polyamide composite membrane with the dimethylamino PEG chain grafted on the surface prepared in the step one in the p-phenylene diisocyanate solution, reacting for 3.5 hours, taking out the membrane, and cleaning the membrane by using chloroform to prepare the aromatic polyamide composite membrane with the dimethylamino PEG chain and the isocyanate group grafted on the surface.
Preparation method of aromatic polyamide composite membrane with dimethylamino PEG chain and dimethylamino grafted on three surfaces
Weighing 10 g of N, N-dimethylethanolamine and dissolving in 30mL of 1, 4-dioxane to prepare a 1, 4-dioxane solution of the N, N-dimethylethanolamine; and then, dipping the aromatic polyamide composite membrane with the dimethylamino PEG chain and the isocyanate group grafted on the surface prepared in the second step into a 1, 4-dioxane solution of N, N-dimethylethanolamine, controlling the temperature to be 60-65 ℃ to react for 4 hours, taking out the membrane, washing the membrane to be neutral by sequentially using ethanol, a sodium carbonate aqueous solution with the mass percent of 10% and deionized water, and drying the membrane to prepare the aromatic polyamide composite membrane with the dimethylamino PEG chain and the dimethylamino group grafted on the surface.
Preparation method of high-performance aromatic polyamide composite membrane by using step four
Weighing 10 g of 5-chloromethyl salicylaldehyde and dissolving in 40mL of ethyl acetate to prepare a 5-chloromethyl salicylaldehyde solution; and (3) dipping the aromatic polyamide composite membrane with the dimethylamino PEG chain and the dimethylamino grafted on the surface, which is prepared in the third step, in a 5-chloromethyl salicylaldehyde solution at the temperature of 25-30 ℃, reacting for 2 hours, taking out the membrane, cleaning the membrane with ethyl acetate, and drying to obtain the high-performance aromatic polyamide composite membrane (1).
Example 2 preparation of high-Performance aromatic Polyamide composite film (2)
According to the method and the operation steps of the embodiment 1, the p-phenylene diisocyanate in the step two of the embodiment 1 is changed into the toluene diisocyanate, and the N, N-dimethylethanolamine in the step three is changed into the 3-dimethylaminopropylamine, so that the high-performance aromatic polyamide composite membrane (2) is prepared.
Example 3 preparation of high-Performance aromatic Polyamide composite film (3)
According to the method and the operation steps of the embodiment 1, the dimethylamino polyethylene glycol-600 in the step one of the embodiment 1 is changed into dimethylamino polyethylene glycol-2000, the p-phenylene diisocyanate in the step two is changed into toluene diisocyanate, and the N, N-dimethylethanolamine in the step three is changed into 3-dimethylaminopropylamine, so that the high-performance aromatic polyamide composite membrane (3) is prepared.
Example 4 preparation of high-Performance aromatic Polyamide composite film (4)
According to the method and the operation steps of the example 1, the dimethylamino polyethylene glycol-600 in the first step of the example 1 is changed into dimethylamino polyethylene glycol-2000, and the p-phenylene diisocyanate in the second step is changed into toluene diisocyanate, so that the high-performance aromatic polyamide composite membrane (4) is prepared.
Example 5 Properties of high-Performance aromatic Polyamide composite films (1) to (4)
The water contact angle θ, water flux and salt rejection of the high performance aromatic polyamide composite membranes (1) to (4) were observed in the high performance aromatic polyamide composite membranes (1) to (4) of examples 1 to 4 according to the methods disclosed in Journal of Membrane Science 428(2013) 403-409 or Journal of Membrane Science 457(2014) 88-97, CN103349922B or CN105251372B, and the results are shown in Table 1.
TABLE 1 Properties of high-Performance aromatic Polyamide composite films (1) to (4)
Figure GDA0001800232510000071
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (7)

1. A preparation method of a high-performance aromatic polyamide composite membrane refers to a preparation method of an aromatic polyamide composite membrane with a surface grafted with a polyethylene glycol chain, quaternary ammonium cations and salicylaldehyde, and is characterized by comprising the following specific preparation steps:
preparation method of aromatic polyamide composite membrane with surface grafted with terminal tertiary amino polyethylene glycol chain
Dipping a fresh aromatic polyamide composite membrane containing acyl chloride groups on the surface in a dialkyl amino-terminated polyethylene glycol solution with the mass percentage concentration of 1.5-25%, controlling the temperature of the dialkyl amino-terminated polyethylene glycol solution to be 60-90 ℃, taking out the membrane after esterification reaction for 2-24 hours, washing the membrane to be neutral by sequentially using ethanol, a sodium carbonate aqueous solution with the mass percentage of 10% and deionized water, and then drying the membrane to prepare the aromatic polyamide composite membrane with the surface grafted with tertiary amino-terminated polyethylene glycol chains;
wherein the solution of the dihydrocarbylaminopolyethylene glycol is prepared by dissolving the dihydrocarbylaminopolyethylene glycol in a solvent; the dosage of the dihydrocarbylaminopolyethylene glycol solution is 1-10 times of the mass of the nascent aromatic polyamide composite membrane with the acyl chloride group on the surface;
the solvent is one or more than two of ethyl acetate, acetone, 1, 4-dioxane, tetrahydrofuran, triethylamine, triethylene diamine, N-methylmorpholine, pyridine, 4-dimethylaminopyridine, 1, 2-dichloroethane, carbon tetrachloride or chloroform;
preparation method of aromatic polyamide composite membrane with secondary surface grafted with terminal tertiary amino polyethylene glycol chain and isocyanate group
Weighing diisocyanate and organic tin, dissolving the diisocyanate and the organic tin in an organic solvent to prepare a diisocyanate solution, controlling the mass percentage concentration of the diisocyanate in the diisocyanate solution to be 1.5-25%, and controlling the use amount of the organic tin to be 0.05-5% of the mass of the diisocyanate; controlling the temperature of the diisocyanate solution to be 0-90 ℃, soaking the aromatic polyamide composite membrane with the surface grafted with the tertiary amino polyethylene glycol chain at the end in the first step into the diisocyanate solution, taking out the membrane after reacting for 0.5-8 hours, and washing the membrane with chloroform or ethyl acetate to obtain the aromatic polyamide composite membrane with the surface grafted with the tertiary amino polyethylene glycol chain at the end and the isocyanate group;
the organic solvent refers to one or more than two of ethyl acetate, propyl acetate, butyl acetate, acetone, 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or 1, 2-dichloroethane;
preparation method of aromatic polyamide composite membrane with surface grafted with terminal tertiary amino polyethylene glycol chain and tertiary amino
Weighing N, N-dialkyl ethanolamine or 3-dialkyl aminopropylamine, dissolving in a solvent to prepare a tertiary amine solution, and controlling the mass percentage concentration of the N, N-dialkyl ethanolamine or 3-dialkyl aminopropylamine to be 1.5-25%; controlling the temperature of the tertiary amine solution to be 25-90 ℃, soaking the aromatic polyamide composite film with the surface grafted with the tertiary amino polyethylene glycol chain and the isocyanate group prepared in the second step in the tertiary amine solution for reaction for 0.5-8 hours, taking out the film, washing the film with ethanol, and drying the film to prepare the aromatic polyamide composite film with the surface grafted with the tertiary amino polyethylene glycol chain and the tertiary amine group;
the amount of the tertiary amine solution is 1-10 times of the mass of the aromatic polyamide composite film with the surface grafted with the tertiary amino polyethylene glycol chain and the isocyanate group;
the solvent is one or more than two of ethyl acetate, acetone, 1, 4-dioxane, tetrahydrofuran, triethylamine, triethylene diamine, N-methylmorpholine, pyridine, 4-dimethylaminopyridine, 1, 2-dichloroethane, carbon tetrachloride or chloroform;
preparation method of high-performance aromatic polyamide composite membrane with quaternary ammonium cations and salicylaldehyde grafted on surface of four steps
Weighing 5-chloromethyl salicylaldehyde and dissolving in a solvent to prepare a 5-chloromethyl salicylaldehyde solution, wherein the mass percentage concentration of the 5-chloromethyl salicylaldehyde solution is controlled to be 3-30%; controlling the temperature of the 5-chloromethyl salicylaldehyde solution to-5-65 ℃, soaking the aromatic polyamide composite membrane with the surface grafted with the tertiary amino polyethylene glycol chain and the tertiary amino in the 5-chloromethyl salicylaldehyde solution, reacting for 2-12 hours, taking out the membrane, washing and drying to obtain the high-performance aromatic polyamide composite membrane with the surface grafted with the polyethylene glycol chain, the quaternary ammonium cation and the salicylaldehyde functional group;
wherein the amount of the 5-chloromethyl salicylaldehyde is 3-30% of the mass of the aromatic polyamide composite membrane with the surface grafted with the terminal tertiary amino polyethylene glycol chain and the tertiary amino;
the solvent is one or more than two of ethyl acetate, propyl acetate, butyl acetate, acetone, 1, 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or 1, 2-dichloroethane.
2. The method for preparing a high-performance aromatic polyamide composite membrane according to claim 1, wherein the nascent aromatic polyamide composite membrane having an acyl chloride group on the surface thereof is prepared by polymerizing m-phenylenediamine and trimesoyl chloride serving as monomers on the surface interface of a microporous polysulfone support membrane or a microporous polyethersulfone support membrane.
3. The method for preparing a high-performance aromatic polyamide composite membrane according to claim 1, wherein the chemical structure of the terminal dihydrocarbylaminopolyethylene glycol is represented by the general formula (a):
Figure FDA0001785097150000021
wherein R in the formula (A)1And R2Are respectively selected from C1～C18N is an integer of 3 to 3000.
4. The method of claim 1, wherein the diisocyanate is one selected from the group consisting of p-phenylene diisocyanate, m-phenylene diisocyanate, toluene diisocyanate, cyclohexane-1, 4-diisocyanate, diphenylmethane-4, 4 '-diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, trimethylhexane diisocyanate, and tetramethylxylylene diisocyanate.
5. The method for preparing a high-performance aromatic polyamide composite membrane according to claim 1, wherein:
the organic tin refers to one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dialkyl tin dimaleate, dibutyltin bis (dodecyl sulfur) or dibutyltin diacetate.
6. The method for preparing a high-performance aromatic polyamide composite membrane according to claim 1, wherein the chemical structure of the N, N-dihydrocarbylethanolamine is represented by the general formula (B):
Figure FDA0001785097150000031
wherein R in the general formula (B)1And R2Are respectively selected from C1～C18A hydrocarbon group of (1).
7. The method of claim 1, wherein the chemical structure of the 3-dihydrocarbylaminopropylamine is represented by the general formula (C):
Figure FDA0001785097150000032
wherein R in the general formula (C)1And R2Are respectively selected from C1～C18A hydrocarbon group of (1).
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