CN103464011A - Aroma polyamide composite membrane with surface containing salicylaldehyde and quaternary ammonium salt and preparing method of aroma polyamide composite membrane - Google Patents
Aroma polyamide composite membrane with surface containing salicylaldehyde and quaternary ammonium salt and preparing method of aroma polyamide composite membrane Download PDFInfo
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- CN103464011A CN103464011A CN2013104493412A CN201310449341A CN103464011A CN 103464011 A CN103464011 A CN 103464011A CN 2013104493412 A CN2013104493412 A CN 2013104493412A CN 201310449341 A CN201310449341 A CN 201310449341A CN 103464011 A CN103464011 A CN 103464011A
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Abstract
The invention provides an aroma polyamide composite membrane with the surface containing salicylaldehyde and quaternary ammonium salt and a preparing method of the aroma polyamide composite membrane. The condensation reaction is carried out on the acyl chloride perssad on the surface of the aroma polyamide composite membrane and the organic polyamine to produce the aroma polyamide composite membrane with the surface containing amidogen; The Mannich reaction is carried out on the aroma polyamide composite membrane with the surface containing amidogen, the formaldehyde and the salicylaldehyde to produce the aroma polyamide composite membrane with the surface containing salicylaldehyde and tertiary amine; the aroma polyamide composite membrane with the surface containing the salicylaldehyde and the tertiary amine is reacted with the quaternary ammonium salt of the alkylate reagent to produce the aroma polyamide composite membrane with the surface containing the quaternary ammonium salt and the salicylaldehyde. The aroma polyamide composite membrane with the surface containing the salicylaldehyde and the quaternary ammonium salt is characterized in that the salicylaldehyde and the quaternary ammonium salt are distributed on the surface of the aroma polyamide composite membrane in a lattice mode; the quaternary ammonium salt functional group and the salicylaldehyde functional group are used for modifying the surface of the aroma polyamide composite membrane so that the hydrophilia of the surface of the aroma polyamide composite membrane can be improved, and the killing and antibiosis performance of the aroma polyamide composite membrane can be improved; the aroma polyamide composite membrane can be prevented from being subjected to chemical destruction.
Description
Technical field
The present invention relates to a kind of surface-functionalized aromatic polyamides composite membrane, be particularly related to the aromatic polyamides composite membrane that contains salicylide and quaternary ammonium salt in surface, can be used as the preparation and application of reverse osmosis membrane, milipore filter and NF membrane, belong to functional high polymer material field.
Technical background
In today of industry high speed development, earth surface water pollutes and is on the rise, the atrophy gradually of the source of fresh water.Therefore, obtaining enough fresh water as minimum cost how is the important issue that can continue at present development.The ultra-thin composite membrane (comprising reverse osmosis membrane, milipore filter and NF membrane etc.) that the coating of aromatic polyamides on the polyether sulfone film and interfacial polymerization form is so that its water flux is large, the salt removal efficiency is high, resistance to bacteria can be good, the characteristics such as alkaline-resisting, oneself becomes the main product of desalinization or sewage treatment area.Because aromatic polyamides composite membrane surface hydrophilicity is lower, be unfavorable for that hydrone approaches or passes through composite membrane, so improve aromatic polyamides composite membrane surface hydrophilicity, be an important technology.In recent years, people apply hydrophilic polyvinyl alcohol, polyethylene glycol and ionomer on aromatic polyamides composite membrane surface, perhaps surface grafting acrylic acid, acrylamide, maleic acid, quaternary ammonium acrylate, acrylate sulfonic acid ammonium salt, acrylate Phosphorylcholine etc., to improving composite membrane surface hydrophilicity and water flux to having produced positive role; Aromatic polyamides composite membrane thorny problem the most in use is exactly membrane biological pollution and membrance chemistry degraded.Described membrane biological pollution refers to the adhesion of various aquatic organisms on the composite membrane surface, grows, breeds and the abnormal obstinate biosphere of formation, is difficult to the labor cleaning, has a strong impact on the operating efficiency of aromatic polyamides composite membrane; In order to solve the biological pollution of microorganism to the aromatic polyamides composite membrane in water treatment procedure, it is a kind of operation technique that facilitates that water supply is led to the chlorine pretreatment.Yet remaining Micro Amounts of Chlorine and the oxychloride chemical depletion to the aromatic polyamides composite membrane in water supply, shortened again serviceability and the life-span of aromatic polyamides composite membrane greatly.Therefore, how can effectively control and alleviate the biological pollution of aromatic polyamides composite membrane, can improve again the chemical stability of aromatic polyamides composite membrane, become the important subject of aromatic polyamide membrane complex technique.
Closely during the last ten years, people are in order to obtain surface depolluting properties excellence, aromatic polyamides composite membrane that the chlorine oxidative stability is high, to aromatic polyamides composite membrane modifying surface be flexibly, simply, method efficiently, mainly contain: (1) surface coating is covered with paint, lacquer, colour wash, etc., (2) surface graft modification.Wherein aromatic polyamides composite membrane surface bond polyethylene glycol (PEG), quaternary ammonium salt, chlordantoin or ion side chain etc. are all remarkable to the antifouling ability effect that improves film.But this class technology does not solve the chlorine oxidative stability problem of aromatic polyamides composite membrane.Adopt in addition said method to be modified lack of homogeneity to aromatic polyamides composite membrane surface, be easy to cause aromatic polyamides composite membrane micropore to stop up, penetrating ability reduces; Use epoxy polymer, polyisocyanates and chloride compounds to react with the acid amides N-H on aromatic polyamides composite membrane surface, can effectively increase film surface hydrophilicity and chlorine oxidative stability, but this method exists, the crosslinked of film surface exaggerated, the side effect that membrane flux reduces.
For the defect of existing aromatic polyamides composite membrane surface modification technology and method of modifying, the inventor has proposed the method on salicylide and quaternary ammonium salt functional group modified aromatic polyamide composite membrane surface.Utilize interfacial polymerization to manufacture remaining acid chloride functional groups in the aromatic polyamides composite membrane, with organic polyamine, advance the amidatioon condensation reaction, at the aromatic polyamides composite membrane, introduce amino N-H; Amino N-the H introduced carries out Mannich with formaldehyde and salicylide and reacts introducing salicylide unit; The amino of introducing by amidation process is converted into tertiary amine groups, continues to react with the quaternary ammonium salinization of alkylating reagent, and so-called tertiary amine groups is converted into to the quaternary ammonium salt unit.
The invention has the beneficial effects as follows:
1. introduce salicylide on aromatic polyamides composite membrane surface and there is high sterilization and anticorrosion function, can prevent that aquatic organism is in the lip-deep adhesion of aromatic polyamides composite membrane and procreation.
2. introduce salicylide on aromatic polyamides composite membrane surface in water, be easy to supply water in remaining chlorine or hypochlorite react, thereby stop chlorine remaining in supplying water or the hypochlorite chlorizating depolymerization to the aromatic polyamides composite membrane, generation protective effect.
3. the quaternary ammonium salt of introducing on aromatic polyamides composite membrane surface is a kind of high-efficiency sterilizing and disinfecting agent, can kill the microorganism with joint, aromatic polyamides composite membrane surface, produces the antifouling function of sterilizing.
In sum; the aromatic polyamides composite membrane that salicylide and quaternary ammonium salt are contained in the surface that the present invention proposes; both can improve the hydrophilicity of aromatic polyamides composite membrane; can keep again the surface cleaning of aromatic polyamides composite membrane in water treatment procedure; protection aromatic polyamides composite membrane exempts from chemical depletion, ensures film serviceability and life-span.
Summary of the invention
The invention provides the aromatic polyamides composite membrane that contains salicylide and quaternary ammonium salt in a kind of surface, is to carry out the amidatioon condensation reaction by the lip-deep acid chloride groups of aromatic polyamides composite membrane and organic polyamine, at the aromatic polyamides composite membrane, introduces amino N-H; Secondly, the aromatic polyamides composite membrane that amino N-H is contained on described surface carries out Mannich with formaldehyde and salicylide and reacts, and on aromatic polyamides composite membrane surface, introduces salicylide and tertiary amine groups; The aromatic polyamides composite membrane that contains salicylide and tertiary amine groups on surface reacts with the quaternary ammonium salinization of alkylating reagent again, thereby introduces salicylide and two kinds of functional groups of quaternary ammonium salt on aromatic polyamides composite membrane surface.
Described aromatic polyamides refers to the copolymer of aromatic diamine or aliphatic diamine and fragrant dimethyl chloride and fragrant three formyl chlorides, and described aromatic polyamides composite membrane refers to the composite film material of the upper coating in support membrane surface (also referred to as counterdie) or aggregation deposition aromatic polyamides.
Described aromatic diamine or aliphatic diamine are selected from respectively structure shown in general formula (I), general formula (II), general formula (III) or general formula (IV):
Z in its formula of (I), general formula (II), general formula (III) or general formula (IV) is selected from H, methyl, ethyl, Cl, Br, F, NO
2, SO
3a kind of in H or COOH, E is selected from CH
2, CH
2cH
2, a kind of in O or S, R is selected from
or
in a kind of, described p is selected from 1～20 positive integer.
Described aromatic dimethyl chloride and aromatic series three formyl chlorides are selected from respectively structure shown in general formula (V), general formula (VI), general formula (VII) or general formula (VIII):
Z in its formula of (V), general formula (VI), general formula (VII) or general formula (VIII) is selected from methyl, ethyl, Cl, Br, F, NO
2, SO
3a kind of in H or COOH, E is selected from CH
2, a kind of in O or S.
Described support membrane is selected from polyethylene film, polypropylene screen, polyacrylonitrile film, polychloroethylene film, polystyrene film, polyurethane film, PS membrane, poly (ether sulfone) film, polycarbonate membrane, polyester film, poly tetrafluoroethylene, cotton fabric, hemp fabric, polypropylene fabric, the polyvinyl chloride fibre fabric, acrylic fabric, the vinylon fabric, RIPSTOP, spandex fabric, cotton fiber nonwoven paper cloth, bast fiber nonwoven fabric, nonwoven polypropylene fabric, the polyvinyl chloride fibre nonwoven, the acrylic fibers nonwoven, the vinylon nonwoven, a kind of in nylon nonwoven fabrics or spandex nonwoven,
Described organic polyamine is selected from structure shown in general formula (IX) or general formula (X):
N in described general formula (IX) or general formula (X) is selected from 0～20 positive integer, and m is selected from a kind of in 0,1,2 or 3;
Described formaldehyde refers to paraformaldehyde or mass percent is 36～68% formalins;
Described alkylating reagent is selected from dimethyl suflfate, dithyl sulfate, iodomethane, 1-iodobutane, dodecyl bromide, benzyl chloride, cylite, a kind of in nitro benzyl chloride, p-chloromethyl benzoic acid, monoxone, 5-chloromethyl salicylaldehyde, propane sultone or epoxychloropropane;
The preparation process of the aromatic polyamides composite membrane that contains salicylide and quaternary ammonium salt for clear statement surface, 1. express the lip-deep acid chloride groups of aromatic polyamides composite membrane and described organic polyamine carries out the amidation process process with reaction equation:
The professional knows, and the Mannich reaction can occur for primary amine and secondary amine, and twice Mannich reaction occurs described primary amine, and primary amine is converted into to tertiary amine; A Mannich reaction occurs in described secondary amine, and secondary amine is converted into to tertiary amine.2. explain the lip-deep Mannich course of reaction of aromatic polyamides composite membrane with reaction equation:
The professional knows tertiary amine groups and has the nucleophilic substitution activity; Alkylating reagent can complete the quaternary ammonium salinization with tertiary amine groups and react, and on the aromatic polyamides composite membrane surface of containing tertiary amine groups, introduces quaternary ammonium salt again, 3. expresses the process of described quaternary ammonium salinization reaction with reaction equation:
The concrete preparation method of the aromatic polyamides composite membrane that salicylide and quaternary ammonium salt are contained in surface provided by the invention is as described below:
The aromatic polyamides reverse osmosis composite membrane that acid chloride groups is contained on step 1 preparation surface
Get support membrane and be immersed in aromatic diamine or aliphatic diamine solution, pull out air-dry; Aromatic dimethyl chloride and aromatic series three formyl chlorides and promoter mixed solution are sprayed on the support membrane that deposits aromatic diamine or aliphatic diamine, through heat treatment, can make the aromatic polyamides reverse osmosis composite membrane that contains acid chloride groups in surface.
Described support membrane is selected from polyethylene film, polypropylene screen, polyacrylonitrile film, polychloroethylene film, polystyrene film, polyurethane film, PS membrane, poly (ether sulfone) film, polycarbonate membrane, polyester film, poly tetrafluoroethylene, cotton fabric, hemp fabric, polypropylene fabric, the polyvinyl chloride fibre fabric, acrylic fabric, the vinylon fabric, RIPSTOP, spandex fabric, cotton fiber nonwoven paper cloth, bast fiber nonwoven fabric, nonwoven polypropylene fabric, the polyvinyl chloride fibre nonwoven, the acrylic fibers nonwoven, the vinylon nonwoven, a kind of in nylon nonwoven fabrics or spandex nonwoven.
Described aromatic diamine or aliphatic diamine are selected from respectively structure shown in general formula (I), general formula (II), general formula (III) or general formula (IV):
Z in its formula of (I), general formula (II), general formula (III) or general formula (IV) is selected from H, methyl, ethyl, Cl, Br, F, NO
2, SO
3a kind of in H or COOH, E is selected from CH
2, CH
2cH
2, a kind of in O or S, R is selected from
or
in a kind of, described p is selected from 1～20 positive integer.
Described aromatic dimethyl chloride and aromatic series three formyl chlorides are selected from respectively structure shown in general formula (V), general formula (VI), general formula (VII) or general formula (VIII):
Z in its formula of (V), general formula (VI), general formula (VII) or general formula (VIII) is selected from methyl, ethyl, Cl, Br, F, NO
2, SO
3a kind of in H or COOH, E is selected from CH
2, CH
2cH
2, a kind of in O or S.
Described promoter is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, N, N-dimethyl benzylamine, pyridine, DMAP, N, N-dimethyl cyclohexyl amine, two (2-dimethylaminoethyl) ether, N, N, N ', N '-tetramethyl Alkylenediamine, N-ethylmorpholine, N-methylmorpholine, N, one or more in N '-diethyl piperazine.
Described aromatic diamine or aliphatic diamine: aromatic dimethyl chloride: aromatic series three formyl chlorides: the mol ratio of promoter is 1:0～0.6:0.5～1.0:0～5.0.
Step 2 prepares on surface and contains amino aromatic polyamides composite membrane
Getting surface that step 1 makes contains acid chloride groups aromatic polyamides composite membrane to be immersed in mass percent is in 1～25% organic polyamine aqueous solution, temperature control-10～90 ℃, react after 2～24 hours, pull out, the aqueous sodium carbonate washing that service property (quality) percentage is 10%, the deionized water washing is to neutral, and vacuum drying, can make on surface and contain amino aromatic polyamides composite membrane.
Wherein said organic polyamine is selected from structure shown in general formula (IX) or general formula (X):
N in described general formula (IX) or general formula (X) is selected from 0～20 positive integer, and m is selected from a kind of in 0,1,2 or 3;
The consumption of described organic polyamine solution is 1～20 times that acid chloride groups aromatic polyamides composite membrane quality is contained on surface;
The aromatic polyamides composite membrane that salicylide and tertiary amine groups are contained in step 3 preparation surface
Getting formaldehyde and salicylide is dissolved in solvent, and add in reactive tank, it is 1.0～4.5 that the hydrochloric acid that service property (quality) percentage is 20～30% is adjusted the pH value, containing amino aromatic polyamides composite membrane on the surface that step 2 is made adds in reactive tank, control temperature to-15～85 ℃, after reacting 2～12 hours, washing after taking out, dry, make the aromatic polyamides composite membrane that contains salicylide and tertiary amine groups in surface.
Wherein said formaldehyde refers to paraformaldehyde or mass percent is 36～68% formalins;
Described solvent is selected from a kind of in water, methyl alcohol or ethanol, and the consumption of described solvent is 0～200% of formaldehyde quality;
Described formaldehyde: salicylide: containing amino aromatic polyamides composite membrane mass ratio on surface is 50～250:50～250:100;
The aromatic polyamides composite membrane that salicylide and quaternary ammonium salt are contained in step 4 preparation surface
Take alkylating reagent and be dissolved in organic solvent, make alkylating reagent solution; Control the alkylating reagent solution temperature between-5～95 ℃, contain the aromatic polyamides composite membrane of salicylide and tertiary amine groups and alkylating reagent solution haptoreaction on the surface that step 3 is made after 2～12 hours, washing after taking out, dry, make the aromatic polyamides composite membrane that contains salicylide and quaternary ammonium salt in surface.
Wherein said alkylating reagent is selected from dimethyl suflfate, dithyl sulfate, iodomethane, 1-iodobutane, dodecyl bromide, benzyl chloride, cylite, a kind of in nitro benzyl chloride, p-chloromethyl benzoic acid, monoxone, 5-chloromethyl salicylaldehyde, propane sultone or epoxychloropropane;
Described organic solvent refers to ethanol, propyl alcohol, butanols, ethyl acetate, propyl acetate, butyl acetate, acetone, butanone, 1, one or more in 4-dioxane, oxolane, glycol dimethyl ether, ethylene glycol diethyl ether or 1,2-dichloroethanes;
The aromatic polyamides that contains salicylide and tertiary amine groups on described surface: alkylating reagent: the mass ratio of organic solvent is 100:10～200:50～500.
The aromatic polyamides composite membrane that salicylide and quaternary ammonium salt are contained in surface provided by the invention has following characteristics:
The methodological science of the aromatic polyamides composite membrane that 1. salicylide and quaternary ammonium salt are contained in preparation of the present invention surface, the membrane surface modification technology simply is easy to industrialization.
2. on aromatic polyamides composite membrane provided by the invention surface, " bonding " salicylide and quaternary ammonium salt have monolayer and dot matrix arrangement characteristics, and " bonding " density can be carried out Chemical Regulation according to needs.
Specific embodiment
Aromatic polyamides composite membrane that salicylide and quaternary ammonium salt is contained in surface provided by the invention by following embodiment and preparation method thereof further illustrates, and its purpose is to understand better content of the present invention.
Embodiment contains on 1 surface the preparation of the aromatic polyamides of salicylide and quaternary ammonium salt/polysulfone composite membrane sheet
The preparation of the aromatic polyamides that acid chloride groups is contained on the step 1 surface/polysulfone composite membrane sheet
The polysulfones support membrane of getting the molecular cut off 20000～50000 after purge drying is immersed in the dichloromethane solution that mass percentage concentration is 0.5～15% m-phenylene diamine (MPD), under room temperature, dipping is 24 hours, take out air-dry, the dichloromethane solution that contains m-phthaloyl chloride and pyromellitic trimethylsilyl chloride and triethylamine that under room temperature, the coating quality percentage concentration is 0.5～15%, under room temperature, reaction is after 0.2 hour, improve temperature to 50～90 ℃ and continue reaction after 2 hours, the washing of use acetone, vacuum drying, make the aromatic polyamides that contains acid chloride groups in surface/polysulfone composite membrane sheet (referred to as APA/PSF-acyl chlorides compound film sheet), standby.
" bonding " amino on step 2 APA/PSF compound film sheet
Take ethylenediamine 4.5 grams and be dissolved in 10 ml waters, be deployed into ethylenediamine solution; The APA/PSF-acyl chlorides compound film sheet that step 1 is made is immersed in ethylenediamine solution, control temperature to 35～55 ℃, react after 2.5 hours, pull reacted diaphragm out, the aqueous sodium carbonate washing that service property (quality) percentage is 10%, rear use deionized water washing, to neutral, is dried, and is that amino aromatic polyamides/polysulfone composite membrane sheet " bonding " (referred to as APA/PSF-NH in surface
2compound film sheet).
Step 3 APA/PSF-NH
2introduce salicylide and tertiary amine groups on the compound film sheet surface
The formalin and the 12 gram salicylides that take 13 grams 37% add in reactive tank, and it is 2.0～2.5 that the hydrochloric acid with 30% is adjusted the pH value, the APA/PSF-NH that step 2 is made
2compound film sheet adds in reactive tank, and 60～65 ℃ of reactions of temperature control, after 4 hours, after taking-up, are used the deionized water washing to neutral, dry, and make the aromatic polyamides compound film sheet that contains salicylide and tertiary amine groups in surface.
Introduce salicylide and quaternary ammonium salt on the aromatic polyamides composite membrane that salicylide and tertiary amine groups are contained in the step 4 surface
Take 18 gram 5-chloromethyl salicylaldehydes and be dissolved in 25 milliliters of acetone solvents, be deployed into 5-chloromethyl salicylaldehyde solution; The aromatic polyamides compound film sheet that salicylide and tertiary amine groups are contained in the surface that step 3 is made is immersed in 5-chloromethyl salicylaldehyde solution, control temperature to 5～15 ℃, react after 2.5 hours, use 1 after taking out, the reacted diaphragm of 4-dioxane solvent wash, eliminating free 5-chloromethyl salicylaldehyde, dry, is the surface aromatic polyamides that contains salicylide and quaternary ammonium salt functional group/polysulfone composite membrane sheet (referred to as the APA/PSF-1-QAS compound film sheet).
Embodiment contains on 2 surfaces the preparation of the aromatic polyamides of salicylide and quaternary ammonium salt/nonwoven polypropylene fabric compound film sheet
Method and operating procedure according to embodiment 1, polysulfones support membrane in embodiment 1 step 1 is changed as nonwoven polypropylene fabric, make on surface the aromatic polyamides that contains salicylide and quaternary ammonium salt functional group/nonwoven polypropylene fabric compound film sheet (referred to as the APA/PP-1-QAS compound film sheet).
Embodiment contains on 3 surfaces the preparation of the aromatic polyamides of salicylide and quaternary ammonium salt/cotton fiber filter paper compound film sheet
Method and operating procedure according to embodiment 1, polysulfones support membrane in embodiment 1 step 1 is changed as cotton fiber filter paper, the ethylenediamine base of step 2 changes as diethylenetriamine, makes the aromatic polyamides that contains salicylide and quaternary ammonium salt in surface/cotton fiber filter paper compound film sheet (referred to as the APA/FP-2-QAS compound film sheet).
The polyamide material composite membrane performance that embodiment contains salicylide and quaternary ammonium salt in 4 surfaces
Get respectively commodity polysulfones support membrane and APA/PSF-1-QAS compound film sheet in embodiment 1, commodity nonwoven polypropylene fabric in embodiment 2 and APA/PP-1-QAS compound film sheet, and the commodity cotton fiber filter paper in embodiment 3 and APA/FP-2-QAS compound film sheet, observation water contact angle θ is respectively 103.5 °, 53.5 °, 107.0 °, 56.0 °, 43.3 °, 37.5 °.Result shows can effectively improve through technology provided by the invention and method the hydrophilicity of described aromatic polyamides composite film material.
Claims (2)
1. the aromatic polyamides composite membrane that salicylide and quaternary ammonium salt are contained in surface, is characterized in that carrying out the amidatioon condensation reaction by the lip-deep acid chloride groups of aromatic polyamides composite membrane and organic polyamine, makes surface and contain amino aromatic polyamides composite membrane; Thereafter, described surface is contained amino aromatic polyamides composite membrane and is carried out Mannich with formaldehyde and salicylide and react, and makes the aromatic polyamides composite membrane that contains salicylide and tertiary amine groups in surface; The aromatic polyamides composite membrane that salicylide and tertiary amine groups are contained in described surface reacts with the quaternary ammonium salinization of alkylating reagent, makes the aromatic polyamides composite membrane that contains salicylide and quaternary ammonium salt in surface;
Described aromatic polyamides refers to the copolymer of aromatic diamine or aliphatic diamine and aromatic dimethyl chloride and aromatic series three formyl chlorides, and described aromatic polyamides composite membrane refers on the support membrane surface and to apply or the composite film material of aggregation deposition aromatic polyamides;
Described aromatic diamine or aliphatic diamine are selected from respectively structure shown in general formula (I), general formula (II), general formula (III) or general formula (IV):
Z in its formula of (I), general formula (II), general formula (III) or general formula (IV) is selected from H, methyl, ethyl, Cl, Br, F, NO
2, SO
3a kind of in H or COOH, E is selected from CH
2, CH
2cH
2, a kind of in O or S, R is selected from
or
in a kind of, described p is selected from 1～20 positive integer;
Described aromatic dimethyl chloride and aromatic series three formyl chlorides are selected from respectively structure shown in general formula (V), general formula (VI), general formula (VII) or general formula (VIII):
Z in its formula of (V), general formula (VI), general formula (VII) or general formula (VIII) is selected from methyl, ethyl, Cl, Br, F, NO
2, SO
3a kind of in H or COOH, E is selected from CH
2, a kind of in O or S;
Described support membrane is selected from polyethylene film, polypropylene screen, polyacrylonitrile film, polychloroethylene film, polystyrene film, polyurethane film, PS membrane, poly (ether sulfone) film, polycarbonate membrane, polyester film, poly tetrafluoroethylene, cotton fabric, hemp fabric, polypropylene fabric, the polyvinyl chloride fibre fabric, acrylic fabric, the vinylon fabric, RIPSTOP, spandex fabric, cotton fiber nonwoven paper cloth, bast fiber nonwoven fabric, nonwoven polypropylene fabric, the polyvinyl chloride fibre nonwoven, the acrylic fibers nonwoven, the vinylon nonwoven, a kind of in nylon nonwoven fabrics or spandex nonwoven,
Described organic polyamine is selected from structure shown in general formula (IX) or general formula (X):
N in described general formula (IX) or general formula (X) is selected from 0～20 positive integer, and m is selected from a kind of in 0,1,2 or 3;
Described formaldehyde refers to paraformaldehyde or mass percent is 36～68% formalins;
Described alkylating reagent is selected from dimethyl suflfate, dithyl sulfate, iodomethane, 1-iodobutane, dodecyl bromide, benzyl chloride, cylite, a kind of in nitro benzyl chloride, p-chloromethyl benzoic acid, monoxone, 5-chloromethyl salicylaldehyde, propane sultone or epoxychloropropane.
2. the preparation method of the aromatic polyamides composite membrane that contains quaternary ammonium salt and salicylide according to the described surface of claim 1 is characterized in that comprising step as described below:
The aromatic polyamides composite membrane that acid chloride groups is contained on step 1 preparation surface
Get support membrane and be immersed in aromatic diamine or aliphatic diamine solution, pull out air-dry; Aromatic dimethyl chloride and aromatic series three formyl chlorides and promoter mixed solution are sprayed on the support membrane that deposits aromatic diamine or aliphatic diamine, through heat treatment, can make the aromatic polyamides composite membrane that contains acid chloride groups in surface;
Wherein said support membrane is selected from as claimed in claim 1;
Described aromatic diamine or aliphatic diamine are selected from respectively as claimed in claim 1;
Described aromatic dimethyl chloride and aromatic series three formyl chlorides are selected from respectively as claimed in claim 1;
Described promoter is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, N, N-dimethyl benzylamine, pyridine, DMAP, N, N-dimethyl cyclohexyl amine, two (2-dimethylaminoethyl) ether, N, N, N ', N '-tetramethyl Alkylenediamine, N-ethylmorpholine, N-methylmorpholine, N, one or more in N '-diethyl piperazine;
Described aromatic diamine or aliphatic diamine: aromatic dimethyl chloride: aromatic series three formyl chlorides: the mol ratio of promoter is 1:0～0.6:0.5～1.0:0～5.0;
Step 2 prepares on surface and contains amino aromatic polyamides composite membrane
Getting surface that step 1 makes contains acid chloride groups aromatic polyamides composite membrane to be immersed in mass percent is in 1～25% organic polyamine aqueous solution, control temperature to-10～90 ℃, react after 2～24 hours, pull out, the aqueous sodium carbonate washing that service property (quality) percentage is 10%, the deionized water washing is to neutral, and vacuum drying, can make on surface and contain amino aromatic polyamides composite membrane;
Wherein said organic polyamine is selected from as claimed in claim 1;
The consumption of described organic polyamine solution is 1～20 times that acid chloride groups aromatic polyamides composite membrane quality is contained on surface;
The aromatic polyamides composite membrane that salicylide and tertiary amine groups are contained in step 3 preparation surface
Getting formaldehyde and salicylide is dissolved in solvent, and add in reactive tank, it is 1.0～4.5 that the hydrochloric acid that service property (quality) percentage is 20～30% is adjusted the pH value, containing amino aromatic polyamides composite membrane on the surface that step 2 is made adds in reactive tank, control temperature to-15～85 ℃, after reacting 2～12 hours, washing after taking out, dry, make the aromatic polyamides composite membrane that contains salicylide and tertiary amine groups in surface;
Wherein said formaldehyde refers to as claimed in claim 1;
Described solvent is selected from a kind of in water, methyl alcohol or ethanol, and the consumption of described solvent is 0～200% of formaldehyde quality;
Described formaldehyde: salicylide: containing amino aromatic polyamides composite membrane mass ratio on surface is 50～250:50～250:100;
The aromatic polyamides composite membrane that salicylide and quaternary ammonium salt are contained in step 4 preparation surface
Take alkylating reagent and be dissolved in organic solvent, make alkylating reagent solution; Control the alkylating reagent solution temperature between-5～95 ℃, contain the aromatic polyamides composite membrane of salicylide and tertiary amine groups and alkylating reagent solution haptoreaction on the surface that step 3 is made after 2～12 hours, washing after taking out, dry, make the aromatic polyamides composite membrane that contains salicylide and quaternary ammonium salt in surface;
Wherein said alkylating reagent is selected from as claimed in claim 1;
Described organic solvent refers to ethanol, propyl alcohol, butanols, ethyl acetate, propyl acetate, butyl acetate, acetone, butanone, 1, one or more in 4-dioxane, oxolane, glycol dimethyl ether, ethylene glycol diethyl ether or 1,2-dichloroethanes;
The aromatic polyamides that contains salicylide and tertiary amine groups on described surface: alkylating reagent: the mass ratio of organic solvent is 100:10～200:50～500.
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| CN103908900A (en) * | 2014-03-05 | 2014-07-09 | 淮海工学院 | Hydrophilic polyaramid composite membrane capable of resisting stain and chlorine, and preparation method thereof |
| CN103908902A (en) * | 2014-03-05 | 2014-07-09 | 淮海工学院 | Preparation method of aromatic polyamide composite membrane with surface grafted pyridinium ions and salicylaldehyde |
| CN104650372A (en) * | 2015-01-30 | 2015-05-27 | 华南理工大学 | Thermosetting polymer compound, poly-half-amide supermolecular film and preparation method thereof |
| CN104693463A (en) * | 2015-01-30 | 2015-06-10 | 华南理工大学 | Thermosetting polymer compound, thin film and preparation method thereof |
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| CN105237786A (en) * | 2015-10-22 | 2016-01-13 | 南阳师范学院 | Method for preparing quaternization polyphenyl ether anion exchange membrane |
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| CN108939932A (en) * | 2018-08-31 | 2018-12-07 | 淮海工学院 | A kind of preparation method of high-performance aromatic polyamides composite membrane |
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| CN115025632A (en) * | 2022-06-21 | 2022-09-09 | 浙江美易膜科技有限公司 | Alkali-resistant composite nanofiltration membrane, and preparation method and application thereof |
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| CN103908902A (en) * | 2014-03-05 | 2014-07-09 | 淮海工学院 | Preparation method of aromatic polyamide composite membrane with surface grafted pyridinium ions and salicylaldehyde |
| CN103908900A (en) * | 2014-03-05 | 2014-07-09 | 淮海工学院 | Hydrophilic polyaramid composite membrane capable of resisting stain and chlorine, and preparation method thereof |
| CN103908900B (en) * | 2014-03-05 | 2016-02-10 | 淮海工学院 | Aromatic polyamides composite membrane that a kind of antifouling chlorine-resistant is hydrophilic and preparation method thereof |
| CN103908902B (en) * | 2014-03-05 | 2016-05-18 | 淮海工学院 | The preparation method of the aromatic polyamides composite membrane of surface grafting pyridinium ion and salicylide |
| CN104650372A (en) * | 2015-01-30 | 2015-05-27 | 华南理工大学 | Thermosetting polymer compound, poly-half-amide supermolecular film and preparation method thereof |
| CN104693463A (en) * | 2015-01-30 | 2015-06-10 | 华南理工大学 | Thermosetting polymer compound, thin film and preparation method thereof |
| CN104650372B (en) * | 2015-01-30 | 2017-10-20 | 华南理工大学 | A kind of thermosetting polymer composite, poly- half amide supermolecular film and preparation method |
| CN104876835A (en) * | 2015-04-28 | 2015-09-02 | 江苏师范大学 | Preparation method and application of Mannich double base |
| CN105251372B (en) * | 2015-07-13 | 2017-09-29 | 淮海工学院 | A kind of preparation method of anti-soil chlorine-resistant aromatic polyamides composite membrane |
| CN105251372A (en) * | 2015-07-13 | 2016-01-20 | 淮海工学院 | Preparation method of anti-pollution chlorine-resistant aromatic polyamide composite membrane |
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| CN108939932A (en) * | 2018-08-31 | 2018-12-07 | 淮海工学院 | A kind of preparation method of high-performance aromatic polyamides composite membrane |
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| CN109331667B (en) * | 2018-11-05 | 2021-01-26 | 长治学院 | Surface modification method of aromatic polyamide composite membrane |
| CN111569676B (en) * | 2020-06-02 | 2021-07-27 | 四川大学 | Ultrafiltration membrane, nanofiltration membrane, preparation method thereof and ultrafiltration-nanofiltration reversible conversion method |
| CN111569676A (en) * | 2020-06-02 | 2020-08-25 | 四川大学 | Ultrafiltration membrane, nanofiltration membrane, preparation method thereof and ultrafiltration-nanofiltration reversible conversion method |
| CN112121737A (en) * | 2020-09-24 | 2020-12-25 | 福建拓烯新材料科技有限公司 | Preparation method of antibacterial phase-change energy-storage microcapsule and fiber |
| CN112121737B (en) * | 2020-09-24 | 2022-06-03 | 福建拓烯新材料科技有限公司 | Preparation method of antibacterial phase-change energy-storage microcapsule and fiber |
| CN115025632A (en) * | 2022-06-21 | 2022-09-09 | 浙江美易膜科技有限公司 | Alkali-resistant composite nanofiltration membrane, and preparation method and application thereof |
| CN115025632B (en) * | 2022-06-21 | 2023-05-23 | 浙江美易膜科技有限公司 | Alkali-resistant composite nanofiltration membrane, preparation method and application thereof |
| CN115228291A (en) * | 2022-08-10 | 2022-10-25 | 万华化学集团股份有限公司 | Anti-pollution, antibacterial and large-flux reverse osmosis membrane and preparation method and application thereof |
| CN116283667A (en) * | 2023-03-06 | 2023-06-23 | 江苏海洋大学 | Functional isocyanate crosslinking agent and preparation method thereof |
| CN116283667B (en) * | 2023-03-06 | 2023-12-29 | 江苏海洋大学 | Functional isocyanate crosslinking agent and preparation method thereof |
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