CN103349922A - Method of surface functionalization of aramatic polyamides reverse osmosis thin film composite membrane - Google Patents
Method of surface functionalization of aramatic polyamides reverse osmosis thin film composite membrane Download PDFInfo
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- CN103349922A CN103349922A CN2013103006537A CN201310300653A CN103349922A CN 103349922 A CN103349922 A CN 103349922A CN 2013103006537 A CN2013103006537 A CN 2013103006537A CN 201310300653 A CN201310300653 A CN 201310300653A CN 103349922 A CN103349922 A CN 103349922A
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Abstract
The invention provides a method of surface functionalization of an aramatic polyamides reverse osmosis thin film composite membrane, which is particularly characterized in that (1) the method that salicylaldehyde and a quaternary ammonium salt functional group are 'cultivated' on the surface of the aramatic polyamides reverse osmosis thin film composite membrane in a dot matrix manner is simple, convenient and easy to operate, and the 'cultivation' density can be subjected to chemical regulation according to the requirement; (2) the uniformity of the surface which is modified by the quaternary ammonium salt and salicylaldehyde functional groups in a dot matrix manner of the aramatic polyamides reverse osmosis thin film composite membrane is high, and the cellular structure and permeability of the aramatic polyamides reverse osmosis thin film composite membrane are not changed; (3) the surface of the aramatic polyamides reverse osmosis thin film composite membrane is simplified by utilizing quaternary ammonium salt and salicylaldehyde functional groups, so that the hydrophilia of the aramatic polyamides reverse osmosis thin film composite membrane can be improved, the performances of antibiosis and sterilization are improved, and the aramatic polyamides reverse osmosis thin film composite membrane is protected from chemistry damage.
Description
Technical field
The present invention relates to the surface-functionalized method of a kind of aromatic polyamides reverse osmosis composite membrane, particularly the method for quaternary ammonium salt and salicylide functional group surface modification aromatic polyamides reverse osmosis composite membrane belongs to functional high polymer material field.
Technical background
Aromatic polyamides reverse osmosis composite membrane (aromatic polyamides reverse osmosis thin film composite membrane) is large with its water flux, salt rejection rate is high, resistance to bacteria can be good, the characteristics such as alkaline-resisting have become the main product in desalinization field.Such reverse osmosis composite membrane is to be compounded in porous polysulfones or polyether sulfone by the ultra-thin aromatic polyamide membrane of one deck to support on the counterdie and make.Yet aromatic polyamides reverse osmosis composite membrane thorny problem in use is exactly membrane biological pollution and membrance chemistry degraded.Described membrane biological pollution refers to multiple seawater microorganism in the adhesion on reverse osmosis composite membrane surface, grows, breeds and the unusual obstinate biosphere of formation, is difficult to the labor cleaning, has a strong impact on the operating efficiency of reverse osmosis composite membrane; Marine microorganism must lead to the chlorine preliminary treatment to seawater to the microbial contamination of aromatic polyamides reverse osmosis composite membrane in the desalting process in order to solve.Yet, because remaining Micro Amounts of Chlorine and oxychloride have shortened again serviceability and the life-span of aromatic polyamides reverse osmosis composite membrane greatly to the chemical depletion of aromatic polyamides reverse osmosis composite membrane in the seawater.Therefore, how can effectively control and alleviate the aromatic polyamides reverse osmosis composite membrane and pollute, can improve again the chemical stability of aromatic polyamides reverse osmosis composite membrane, become the important subject in aromatic polyamides reverse osmosis technology field.
In recent years, people are in order to obtain surface depolluting properties excellence, aromatic polyamides reverse osmosis composite membrane that the chlorine oxidative stability is high, to aromatic polyamides reverse osmosis composite membrane modifying surface be flexibly, simply, method efficiently, mainly contain: (1) surface coating is covered with paint, lacquer, colour wash, etc., (2) surface aggregate deposition, and (3) surface graft modification, wherein film surface access water-soluble polyethylene glycol (PEG), quaternary ammonium salt, chlordantoin or ion side chain etc. are all to improving the antifouling and stable positive role that produced of film.But adopt said method that lack of homogeneity is modified on aromatic polyamides reverse osmosis composite membrane surface; Be easy to cause aromatic polyamides reverse osmosis composite membrane micropore to stop up, penetrating ability reduces; In addition aromatic polyamides reverse osmosis composite membrane surface is being carried out in the graft copolymerization modification, the monomer waste of raw materials that is caused by the monomer homopolymerization is serious.
Defective for existing aromatic polyamides reverse osmosis composite membrane surface modification technology and method of modifying, the inventor has proposed to use the method for the construction unit surface modification aromatic polyamides reverse osmosis composite membrane that contains quaternary ammonium salt and salicylide functional group, and " plantation " technology of employing will contain the construction unit " plantation " of quaternary ammonium salt and salicylide functional group on aromatic polyamides reverse osmosis composite membrane surface.The effect that the present invention will realize is to keep the surface cleaning of aromatic polyamides reverse osmosis composite membrane in desalting process, can exempt from chemical depletion by diaphragm again, ensures film serviceability and life-span.Its principle is to utilize the kill livestock effect of heavy metal ion in effect, hydrophilic interaction, the selective complexation adsorbing seawater of the different mechanisms sterilization of quaternary ammonium salt and salicylide functional group, produce collaborative efficiently anti-marine biological polution function, guarantee the cleaning on aromatic polyamides reverse osmosis composite membrane surface; Secondly, the chemical reaction of remaining Micro Amounts of Chlorine and oxychloride is more quick in the salicylide functional group that aromatic polyamides reverse osmosis composite membrane surface is abundant and the pre-treating seawater, stoped that remaining Micro Amounts of Chlorine and oxychloride have ensured serviceability and the life-span of polyamide reverse osmosis composite film to the chemical depletion effect of aromatic polyamides reverse osmosis composite membrane in the seawater.
Summary of the invention
The invention provides the method for the surface-functionalized aromatic polyamides reverse osmosis composite membrane of a kind of salicylide and quaternary ammonium salt, that acid chloride groups by aromatic polyamides reverse osmosis composite membrane surface exposure and tertiary amine groups alcohol or tertiary amine groups organic amine carry out condensation reaction, in aromatic polyamides reverse osmosis composite membrane surface " plantation " tertiary amine groups; Secondly, the quaternary ammonium salinization reaction of aromatic polyamides reverse osmosis composite membrane with the 5-chloromethyl salicylaldehyde of tertiary amine groups is contained on described surface, thus at aromatic polyamides reverse osmosis composite membrane surperficial " plantation " salicylide and quaternary ammonium salt functional group.
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 reverse osmosis composite membrane refers to the composite film material of support membrane (being also referred to as counterdie) surface deposition aromatic polyamides.
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, glass fabric, cotton fiber nonwoven paper cloth, the fine nonwoven of fiber crops, nonwoven polypropylene fabric, the polyvinyl chloride fibre nonwoven, the acrylic fibers nonwoven, dimension Buddhist nun nonwoven, nylon nonwoven fabrics, a kind of in spandex nonwoven or the glass fibre non-woven.
Described " plantation " concept refers to by the regulation and control chemical reaction condition, utilize condensation reaction between acid chloride groups on the aromatic polyamides reverse osmosis composite membrane and tertiary amine groups alcohol or the tertiary amine groups organic amine, tertiary amine groups or quaternary ammonium salt and salicylide functional group on aromatic polyamides reverse osmosis composite membrane surface point configuration connects are similar to the earth surface afforestation; Hence one can see that, and described " plantation " is exactly the bare spots that acid chloride groups is arranged on the aromatic polyamides reverse osmosis composite membrane surface, just can be at described bare spots access tertiary amine groups or quaternary ammonium salt and salicylide functional group.
Described tertiary amine groups alcohol or tertiary amine groups organic amine are selected from respectively structure shown in general formula (I), general formula (II), general formula (III) or the general formula (IV):
R in described general formula (I), general formula (II), general formula (III) or the general formula (IV)
1, R
2And R
3Be selected from respectively C
1～C
20Alkyl, n are selected from 1～20 positive integer;
1. reaction equation has been expressed the lip-deep acid chloride groups of aromatic polyamides reverse osmosis composite membrane and described tertiary amine groups alcohol or tertiary amine groups organic amine and has been carried out condensation reaction, connects the process of tertiary amine groups on aromatic polyamides reverse osmosis composite membrane surface " plantation ":
Wherein tertiary amine groups alcohol or the tertiary amine groups organic amine of reaction equation in 1. is selected from respectively structure shown in general formula (I), general formula (II), general formula (III) or the general formula (IV):
R in described general formula (I), general formula (II), general formula (III) or the general formula (IV)
1, R
2And R
3Be selected from respectively C
1～C
20Alkyl, n are selected from 1～20 positive integer, and described X is selected from O, NH or R
3N, described Y do not choose any or are selected from O.
Through reaction equation chemical reaction process 1., tertiary amine groups has been accessed on aromatic polyamides reverse osmosis composite membrane surface.The professional knows tertiary amine groups and has the nucleophilic substitution activity; Contain chemically active chloromethyl in the 5-chloromethyl salicylaldehyde molecular structure, can finish quaternary ammonium salinization reaction with tertiary amine groups, introduce simultaneously quaternary ammonium salt and salicylide functional group on the aromatic polyamides reverse osmosis composite membrane surface of containing tertiary amine groups, see that reaction equation is 2.:
The R of reaction equation in 2. wherein
1, R
2And R
3Be selected from respectively C
1～C
20Alkyl, n are selected from 1～20 positive integer; Described X is selected from O, NH or R
3N, described Y do not choose any or are selected from O.
The concrete grammar of the surface-functionalized aromatic polyamides reverse osmosis composite membrane of salicylide provided by the invention and quaternary ammonium salt is as described below:
The method of the aromatic polyamides reverse osmosis composite membrane of acid chloride groups is contained on step 1 preparation surface
Get support membrane and be immersed in aromatic diamine or the 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, through heat treatment, can make the aromatic polyamides reverse osmosis composite membrane that acid chloride groups is contained on the 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, glass fabric, cotton fiber nonwoven paper cloth, the fine nonwoven of fiber crops, nonwoven polypropylene fabric, the polyvinyl chloride fibre nonwoven, the acrylic fibers nonwoven, dimension Buddhist nun nonwoven, nylon nonwoven fabrics, a kind of in spandex nonwoven or the glass fibre non-woven.
Described aromatic diamine or aliphatic diamine are selected from respectively structure shown in general formula (V), general formula (VI), general formula (VII) or the general formula (VIII):
Z in its formula of (V), general formula (VI), general formula (VII) or the general formula (VIII) is selected from H, methyl, ethyl, Cl, Br, F or NO
2In a kind of, E is selected from CH
2, a kind of among O or the S, R is selected from (CH
2CH
2)
m,
Or
In a kind of, described m 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 (IX), general formula (X), general formula (XI) or the general formula (XII):
Its formula of (IX), general formula (X), general formula (XI) or general formula (XII) Z are selected from methyl, ethyl, Cl, Br, F or NO
2In a kind of, E is selected from CH
2, a kind of among O or the 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: 0～0.5: 0.5～0.8: 0～5.0.
The method that connects tertiary amine groups on the step 2 aromatic polyamides reverse osmosis composite membrane surface
Getting surface that step 1 makes contains acid chloride groups aromatic polyamides reverse osmosis composite membrane and is immersed in tertiary amine groups alcohol or the tertiary amine groups organic amine, temperature control-10～90 ℃ reaction is after 2～24 hours, leach, service property (quality) percentage is 10% aqueous sodium carbonate washing, the deionized water water washing is to neutral, vacuum drying can connect tertiary amine groups on aromatic polyamides reverse osmosis composite membrane surface.
Wherein said tertiary amine groups alcohol or tertiary amine groups organic amine are selected from respectively structure shown in general formula (I), general formula (II), general formula (III) or the general formula (IV):
R in described general formula (I), general formula (II), general formula (III) or the general formula (IV)
1, R
2And R
3Be selected from respectively C
1～C
20Alkyl, n are selected from 1～20 positive integer;
The consumption of wherein said tertiary amine groups alcohol or tertiary amine groups organic amine is 1～20 times that acid chloride groups aromatic polyamides reverse osmosis composite membrane quality is contained on the surface;
Step 3 aromatic polyamides reverse osmosis composite membrane surface connects the method for quaternary ammonium salt and salicylide
Take by weighing the 5-chloromethyl salicylaldehyde and be dissolved in the organic solvent, make 5-chloromethyl salicylaldehyde solution; Control 5-chloromethyl salicylaldehyde solution temperature is between-5～95 ℃, with step 2 " plantation " the aromatic polyamides reverse osmosis composite membrane of tertiary amine groups and 5-chloromethyl salicylaldehyde solution haptoreaction after 2～12 hours, filter, washing, oven dry, namely finish the process of aromatic polyamides reverse osmosis composite membrane surface " plantation " quaternary ammonium salt and salicylide functional group, also namely made the surface-functionalized aromatic polyamides reverse osmosis composite membrane of quaternary ammonium salt and salicylide.
Wherein said organic solvent refers to one or more in ethyl acetate, propyl acetate, butyl acetate, acetone, Isosorbide-5-Nitrae-dioxane, oxolane, glycol dimethyl ether, ethylene glycol diethyl ether or 1, the 2-dichloroethanes;
Described surface " plantation " the aromatic polyamides reverse osmosis composite membrane of tertiary amine groups: the 5-chloromethyl salicylaldehyde: the mass ratio of solvent is 100: 10～200: 50～500.
The method of salicylide provided by the invention and quaternary ammonium salt functional group surface modification aromatic polyamides reverse osmosis composite membrane has following characteristics:
1. the method for salicylide of the present invention and quaternary ammonium salt functional group surface modification aromatic polyamides reverse osmosis composite membrane is simple, and the membrane surface modification technology is easy to industrialization.
2. adopt method provided by the invention " plantation " salicylide and quaternary ammonium salt function base on aromatic polyamides reverse osmosis composite membrane surface to have dot matrix and arrange characteristics, " plantation " density can be carried out Chemical Regulation according to needs.
Specific embodiment
By following embodiment the method for salicylide provided by the invention and quaternary ammonium salt functional group surface modification aromatic polyamides reverse osmosis composite membrane is further specified, its purpose is to understand better content of the present invention.
Embodiment contains on 1 surface the preparation of the aromatic polyamides of quaternary ammonium salt and salicylide functional group-polysulfone composite membrane sheet
The preparation of the aromatic polyamides of acid chloride groups-polysulfone composite membrane sheet is contained on the step 1 surface
The polysulfones support membrane of getting the molecular cut off 20000～50000 behind the purge drying is immersed in the dichloromethane solution that mass percentage concentration is 3～15% m-phenylene diamine (MPD)s, dipping is 24 hours under the room temperature, take out air-dry, the coating quality percentage concentration is 3～15% the dichloromethane solution that contains m-phthaloyl chloride and pyromellitic trimethylsilyl chloride and triethylamine under the room temperature, reaction is after 0.2 hour under the room temperature, improve temperature to 50～90 ℃ continuation reaction after 2 hours, the washing of use acetone, vacuum drying, namely make the surface and contain the aromatic polyamides of acid chloride groups-polysulfone composite membrane sheet (referred to as the ClOC-PA/PS compound film sheet), for subsequent use.
" plantation " tertiary amine groups on the step 2 ClOC-PA/PS compound film sheet
Take by weighing mean molecule quantity and be single diethylin polyethylene glycol 4.5 grams of 800 and be dissolved in 5 milliliters of Isosorbide-5-Nitraes-dioxane solvent, be deployed into single diethylin polyglycol solution; The ClOC-PA/PS compound film sheet that step 1 is made is immersed in single diethylin polyglycol solution, control temperature to 55～75 ℃, behind the confined reaction 2.5 hours, pull reacted diaphragm out, use Isosorbide-5-Nitrae-dioxane solvent wash, re-use mass percent and be 10% aqueous sodium carbonate washing, use at last deionized water washing to neutral, oven dry namely is surface " plantation " aromatic polyamides of tertiary amine groups-polysulfone composite membrane sheet is (referred to as Et
2The N-PEG-PA/PS compound film sheet).
Step 3 Et
2" plantation " quaternary ammonium salt and salicylide on the N-PEG-PA/PS compound film sheet surface
Take by weighing 5.2 gram 5-chloromethyl salicylaldehydes and be dissolved in 5.5 milliliters of Isosorbide-5-Nitraes-dioxane solvent, be deployed into 5-chloromethyl salicylaldehyde solution; The Et that step 2 is made
2The N-PEG-PA/PS compound film sheet is immersed in the 5-chloromethyl salicylaldehyde solution, control temperature to 5～15 ℃, behind the confined reaction 2.5 hours, use 1 after taking out, the reacted diaphragm of 4-dioxane solvent wash, eliminate free 5-chloromethyl salicylaldehyde, oven dry namely is the surface aromatic polyamides that contains quaternary ammonium salt and salicylide functional group-polysulfone composite membrane sheet (referred to as the QS-PEG-PA/PS compound film sheet).
Embodiment contains on 2 surfaces the preparation of the aromatic polyamides of quaternary ammonium salt and salicylide functional group-nonwoven polypropylene fabric compound film sheet
Method and operating procedure according to embodiment 1, polysulfones support membrane in embodiment 1 step 1 changed be nonwoven polypropylene fabric, namely make the aromatic polyamides of surface " plantation " quaternary ammonium salt and salicylide-nonwoven polypropylene fabric compound film sheet (referred to as the QS-PEG-PA/PP compound film sheet).
Embodiment contains on 3 surfaces the preparation of the aromatic polyamides of quaternary ammonium salt and salicylide functional group-cotton fiber filter paper compound film sheet
Method and operating procedure according to embodiment 1, it is cotton fiber filter paper that polysulfones support membrane in embodiment 1 step 1 is changed, the single diethylin polyethylene glycol of step 2 changes and is 2-(dimethylamino) ethamine, namely makes the aromatic polyamides of surface " plantation " quaternary ammonium salt and salicylide-cotton fiber filter paper compound film sheet (referred to as the QS-DMA-PA/FP compound film sheet).
The polyamide material composite membrane performance that embodiment 4 quaternary ammonium salts and salicylide are surface-functionalized
Get respectively commodity polysulfones support membrane and QS-PEG-PA/PS composite membrane among the embodiment 1, commodity nonwoven polypropylene fabric among the embodiment 2 and QS-PEG-PA/PP composite membrane, and the commodity cotton fiber filter paper among the embodiment 3 and QS-DMA-PA/FP composite membrane, observation water contact angle θ is respectively 103.5 °, 37.4 °, 107.8 °, 33.1 °, 43.3 °, water parent profit.The result shows the hydrophilicity that can efficiently improve described aromatic polyamides composite film material through technology provided by the invention and method.
Claims (2)
1. method that the aromatic polyamides reverse osmosis composite membrane is surface-functionalized, it is characterized in that carrying out condensation reaction by the lip-deep acid chloride groups of aromatic polyamides reverse osmosis composite membrane and tertiary amine groups alcohol or tertiary amine groups organic amine, make the aromatic polyamides reverse osmosis composite membrane that tertiary amine groups is contained on the surface; Thereafter the quaternary ammonium salinization reaction of the aromatic polyamides reverse osmosis composite membrane of tertiary amine groups and 5-chloromethyl salicylaldehyde is contained on described surface, has made the aromatic polyamides reverse osmosis composite membrane that quaternary ammonium salt and salicylide functional group are contained in the film 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 reverse osmosis composite membrane refers to the composite membrane of support membrane surface aggregate deposition aromatic polyamides.
Described tertiary amine groups alcohol or tertiary amine groups organic amine are selected from respectively structure shown in general formula (I), general formula (II), general formula (III) or the general formula (IV):
R in described general formula (I), general formula (II), general formula (III) or the general formula (IV)
1, R
2And R
3Be selected from respectively C
1～C
20Alkyl, n are selected from 1～20 positive integer;
Described aromatic diamine or aliphatic diamine are selected from respectively structure shown in general formula (V), general formula (VI), general formula (VII) or the general formula (VIII):
Z in its formula of (V)～(VIII) is selected from H, methyl, ethyl, Cl, Br, F or NO
2In a kind of, E is selected from CH
2, a kind of among O or the S, R is selected from (CH
2CH
2)
m,
Or
In a kind of, described m 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 (IX), general formula (X), general formula (XI) or the general formula (XII):
Z in its formula of (IX)～(XII) is selected from methyl, ethyl, Cl, Br, F or NO
2In a kind of, E is selected from CH
2, a kind of among O or the 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, glass fabric, cotton fiber nonwoven paper cloth, the fine nonwoven of fiber crops, nonwoven polypropylene fabric, the polyvinyl chloride fibre nonwoven, the acrylic fibers nonwoven, the vinylon nonwoven, the polyamide fibre nonwoven, a kind of in spandex nonwoven or the glass fibre non-woven.
2. according to the surface-functionalized method of the described aromatic polyamides reverse osmosis composite membrane of claim 1, it is characterized in that comprising step as described below:
The preparation of the aromatic polyamides reverse osmosis composite membrane of acid chloride groups is contained on the step 1 surface
Get support membrane and be immersed in aromatic diamine or the 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, through heat treatment, can make the aromatic polyamides reverse osmosis composite membrane that acid chloride groups is contained on the 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 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: 0～0.5: 0.5～0.8: 0～5.0;
The method that connects tertiary amine groups on the step 2 aromatic polyamides reverse osmosis composite membrane surface
Getting surface that step 1 makes contains acid chloride groups aromatic polyamides reverse osmosis composite membrane and is immersed in tertiary amine groups alcohol or the tertiary amine groups organic amine, temperature control-10～90 ℃ reaction is after 2～24 hours, leach, service property (quality) percentage is 10% aqueous sodium carbonate washing, the deionized water water washing is to neutral, vacuum drying, can be on aromatic polyamides reverse osmosis composite membrane surface connects tertiary amine groups;
Wherein said tertiary amine groups alcohol or tertiary amine groups organic amine are selected from respectively as claimed in claim 1;
The consumption of described tertiary amine groups alcohol or tertiary amine groups organic amine is 1～20 times that acid chloride groups aromatic polyamides reverse osmosis composite membrane quality is contained on the surface;
Step 3 aromatic polyamides reverse osmosis composite membrane surface connects the method for quaternary ammonium salt and salicylide
Take by weighing the 5-chloromethyl salicylaldehyde and be dissolved in the organic solvent, make 5-chloromethyl salicylaldehyde solution; Control 5-chloromethyl salicylaldehyde solution temperature is between-5～95 ℃, the surface that step 2 is made connected the aromatic polyamides reverse osmosis composite membrane of having gone up tertiary amine groups and 5-chloromethyl salicylaldehyde solution haptoreaction after 2～12 hours, filter, washing, oven dry has namely made the surperficial aromatic polyamides reverse osmosis composite membrane that contains quaternary ammonium salt and salicylide functional group;
Wherein said organic solvent refers to one or more in ethyl acetate, propyl acetate, butyl acetate, acetone, Isosorbide-5-Nitrae-dioxane, oxolane, glycol dimethyl ether, ethylene glycol diethyl ether or 1, the 2-dichloroethanes;
Described surface has connected the aromatic polyamides reverse osmosis composite membrane of tertiary amine groups: the 5-chloromethyl salicylaldehyde: the consumption mass ratio of solvent is 100: 10～200: 50～500.
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| 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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