CN103349922B - 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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- CN103349922B CN103349922B CN201310300653.7A CN201310300653A CN103349922B CN 103349922 B CN103349922 B CN 103349922B CN 201310300653 A CN201310300653 A CN 201310300653A CN 103349922 B CN103349922 B CN 103349922B
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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 a kind of method that aromatic polyamides reverse osmosis composite membrane is surface-functionalized, 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 filmcomposite membrane) is large with its water flux, salt rejection rate is high, resistance to bacteria can be good, the feature such as alkaline-resisting, has become the main product of field of seawater desalination.Such reverse osmosis composite membrane is compounded on porous polysulfones or polyether sulfone support counterdie by the ultra-thin aromatic polyamide membrane of one deck and makes.But aromatic polyamides reverse osmosis composite membrane thorny problem is in use exactly membrane biological pollution and membrance chemistry degraded.Described membrane biological pollution refers to the adhesion of multiple seawater microorganism on reverse osmosis composite membrane surface, grows, breeds and form abnormal obstinate biosphere, be difficult to labor cleaning, have a strong impact on the operating efficiency of reverse osmosis composite membrane; To the microbial contamination of aromatic polyamides reverse osmosis composite membrane, logical chlorine pretreatment must be carried out to seawater to solve marine microorganism in desalting process.But, because Micro Amounts of Chlorine remaining in seawater and oxychloride are to the chemical depletion of aromatic polyamides reverse osmosis composite membrane, substantially reduce again serviceability and the life-span of aromatic polyamides reverse osmosis composite membrane.Therefore, how can effectively control and alleviate aromatic polyamides reverse osmosis composite membrane and pollute, the chemical stability of aromatic polyamides reverse osmosis composite membrane can be improved again, 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 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 ionic side chains etc. all create positive role to the antifouling and stability improving film.But adopt said method to carry out modification lack of homogeneity to aromatic polyamides reverse osmosis composite membrane surface; Be easy to cause aromatic polyamides reverse osmosis composite membrane micropore to block, transparency reduces; Carrying out in graft copolymerization modification to aromatic polyamides reverse osmosis composite membrane surface in addition, the monomer raw material waste caused by monomer homopolymerization is serious.
For the defect of existing aromatic polyamides reverse osmosis composite membrane surface modification technology and method of modifying, present inventors have proposed the method using the construction unit surface modification aromatic polyamides reverse osmosis composite membrane containing quaternary ammonium salt and salicylide functional group, adopt " plantation " technology by the construction unit " plantation " containing quaternary ammonium salt and salicylide functional group at aromatic polyamides reverse osmosis composite membrane on the surface.The effect that the present invention will realize to keep the clean surface 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 the effect utilizing heavy metal ion in the different mechanisms sterilizing effect of killing livestock of quaternary ammonium salt and salicylide functional group, hydrophilic interaction, selective complexation adsorbing seawater, produce collaborative efficient anti-marine biological polution function, ensure the cleaning on aromatic polyamides reverse osmosis composite membrane surface; Secondly, in the salicylide functional group that aromatic polyamides reverse osmosis composite membrane surface is abundant and pre-treating seawater, the chemical reaction of remaining Micro Amounts of Chlorine and oxychloride is more quick, remaining Micro Amounts of Chlorine and oxychloride in seawater is prevented to the chemical depletion effect of aromatic polyamides reverse osmosis composite membrane, to ensure serviceability and the life-span of polyamide reverse osmosis composite film.
Summary of the invention
The invention provides a kind of method of salicylide and the surface-functionalized aromatic polyamides reverse osmosis composite membrane of quaternary ammonium salt, carry out condensation reaction, in aromatic polyamides reverse osmosis composite membrane surface " plantation " tertiary amine groups by the acid chloride groups of aromatic polyamides reverse osmosis composite membrane surface exposure and tertiary amine groups alcohol or tertiary amine groups organic amine; Secondly, the quaternization of aromatic polyamides reverse osmosis composite membrane and 5-chloromethyl salicylaldehyde that tertiary amine groups is contained on described surface reacts, thus on aromatic polyamides reverse osmosis composite membrane surface " 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 chloride, and described aromatic polyamides reverse osmosis composite membrane refers to the composite film material of support membrane (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, polyvinyl chloride fibre fabric, acrylic fabric, vinylon fabric, RIPSTOP, spandex fabric, glass fabric, cotton fiber nonwoven paper cloth, the fine non-woven fabrics of fiber crops, nonwoven polypropylene fabric, polyvinyl chloride fibre non-woven fabrics, acrylic fibers non-woven fabrics, dimension Buddhist nun non-woven fabrics, nylon nonwoven fabrics, one in spandex non-woven fabrics or glass fibre non-woven.
Described " plantation " concept refers to by regulation and control chemical reaction condition, utilize condensation reaction between acid chloride groups on aromatic polyamides reverse osmosis composite membrane and tertiary amine groups alcohol or 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, be similar to earth surface afforestation; It can thus be appreciated that described " plantation " is exactly the bare spots that aromatic polyamides reverse osmosis composite membrane has acid chloride groups on the surface, tertiary amine groups or quaternary ammonium salt and salicylide functional group just can be accessed in described bare spots.
Described tertiary amine groups alcohol or tertiary amine groups organic amine are selected from structure shown in general formula (I), general formula (II), general formula (III) or general formula (IV) respectively:
R in described general formula (I), general formula (II), general formula (III) or general formula (IV)
1, R
2and R
3be selected from C respectively
1~ C
20alkyl, n is selected from the positive integer of 1 ~ 20;
1. reaction equation have expressed acid chloride groups on aromatic polyamides reverse osmosis composite membrane surface and described tertiary amine groups alcohol or tertiary amine groups organic amine and carries out condensation reaction, connects the process of tertiary amine groups on aromatic polyamides reverse osmosis composite membrane surface " plantation ":
Wherein reaction equation 1. in tertiary amine groups alcohol or tertiary amine groups organic amine be selected from structure shown in general formula (I), general formula (II), general formula (III) or general formula (IV) respectively:
R in described general formula (I), general formula (II), general formula (III) or general formula (IV)
1, R
2and R
3be selected from C respectively
1~ C
20alkyl, n is selected from the positive integer of 1 ~ 20, 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.Professional knows tertiary amine groups and has nucleophilic substitution activity; Containing chemically active chloromethyl in 5-chloromethyl salicylaldehyde molecular structure, quaternization can be completed with tertiary amine groups and react, introduce quaternary ammonium salt and salicylide functional group on the aromatic polyamides reverse osmosis composite membrane surface containing tertiary amine groups simultaneously, see that reaction equation is 2.:
Wherein reaction equation 2. in R
1, R
2and R
3be selected from C respectively
1~ C
20alkyl, n is selected from the positive integer of 1 ~ 20; 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 salicylide provided by the invention and quaternary ammonium salt surface-functionalized aromatic polyamides reverse osmosis composite membrane is as described below:
Step one prepares the method for the aromatic polyamides reverse osmosis composite membrane of surface containing acid chloride groups
Get support membrane to be immersed in aromatic diamine or aliphatic diamine solution, pull out air-dry; Aromatic dimethyl chloride and aromatic series three formyl chloride and promoter mixed solution are sprayed on support membrane, through heat treatment, the aromatic polyamides reverse osmosis composite membrane of surface containing acid chloride groups can be obtained.
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, polyvinyl chloride fibre fabric, acrylic fabric, vinylon fabric, RIPSTOP, spandex fabric, glass fabric, cotton fiber nonwoven paper cloth, the fine non-woven fabrics of fiber crops, nonwoven polypropylene fabric, polyvinyl chloride fibre non-woven fabrics, acrylic fibers non-woven fabrics, dimension Buddhist nun non-woven fabrics, nylon nonwoven fabrics, one in spandex non-woven fabrics or glass fibre non-woven.
Described aromatic diamine or aliphatic diamine are selected from structure shown in general formula (V), general formula (VI), general formula (VII) or general formula (VIII) respectively:
Z in its formula of (V), general formula (VI), general formula (VII) or general formula (VIII) is selected from H, methyl, ethyl, Cl, Br, F or NO
2in one, E is selected from CH
2, one in O or S, R is selected from (CH
2cH
2)
m,
or
in one, described m is selected from the positive integer of 1 ~ 20.
Described aromatic dimethyl chloride and aromatic series three formyl chloride are selected from structure shown in general formula (IX), general formula (X), general formula (XI) or general formula (XII) respectively:
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 one, E is selected from CH
2, one 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 ', one or more in N '-tetramethyl Alkylenediamine, N-ethylmorpholine, N-methylmorpholine, N, N '-diethyl piperazine.
Described aromatic diamine or aliphatic diamine: aromatic dimethyl chloride: aromatic series three formyl chloride: the mol ratio of promoter is 1: 0 ~ 0.5: 0.5 ~ 0.8: 0 ~ 5.0.
Step 2 aromatic polyamides reverse osmosis composite membrane connects the method for tertiary amine groups on the surface
Get the obtained surface of step one to contain acid chloride groups aromatic polyamides reverse osmosis composite membrane and be immersed in tertiary amine groups alcohol or tertiary amine groups organic amine, temperature control-10 ~ 90 DEG C reaction is after 2 ~ 24 hours, leach, service property (quality) percentage is the aqueous sodium carbonate washing of 10%, 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 structure shown in general formula (I), general formula (II), general formula (III) or general formula (IV) respectively:
R in described general formula (I), general formula (II), general formula (III) or general formula (IV)
1, R
2and R
3be selected from C respectively
1~ C
20alkyl, n is selected from the positive integer of 1 ~ 20;
Wherein said tertiary amine groups alcohol or the consumption of tertiary amine groups organic amine are 1 ~ 20 times that acid chloride groups aromatic polyamides reverse osmosis composite membrane quality is contained on surface;
Step 3 aromatic polyamides reverse osmosis composite membrane surface connects the method for quaternary ammonium salt and salicylide
Take 5-chloromethyl salicylaldehyde to dissolve in organic solvent, obtained 5-chloromethyl salicylaldehyde solution; Control 5-chloromethyl salicylaldehyde solution temperature is between-5 ~ 95 DEG C, by the step 2 aromatic polyamides reverse osmosis composite membrane of " plantation " tertiary amine groups and 5-chloromethyl salicylaldehyde solution haptoreaction after 2 ~ 12 hours, filter, washing, dry, namely complete the process of aromatic polyamides reverse osmosis composite membrane surface " plantation " quaternary ammonium salt and salicylide functional group, also namely make quaternary ammonium salt and the surface-functionalized aromatic polyamides reverse osmosis composite membrane of salicylide.
Wherein said organic solvent refer in ethyl acetate, propyl acetate, butyl acetate, acetone, Isosorbide-5-Nitrae-dioxane, oxolane, glycol dimethyl ether, ethylene glycol diethyl ether or 1,2-dichloroethanes one or more;
Described surface " plantation " the aromatic polyamides reverse osmosis composite membrane of tertiary amine groups: 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 membrane surface modification technology is easy to industrialization.
2. adopt method provided by the invention aromatic polyamides reverse osmosis composite membrane on the surface " plantation " salicylide and quaternary ammonium salt function base there is lattice arrangement feature, " plantation " density can carry out Chemical Regulation according to needs.
Specific embodiment
Further illustrated by the method for embodiment to salicylide provided by the invention and quaternary ammonium salt functional group surface modification aromatic polyamides reverse osmosis composite membrane below, its object is to understand content of the present invention better.
The preparation of the aromatic polyamides-polysulfone composite membrane sheet of quaternary ammonium salt and salicylide functional group is contained on embodiment 1 surface
The preparation of the aromatic polyamides-polysulfone composite membrane sheet of step one surface containing acid chloride groups
It is in the dichloromethane solution of 3 ~ 15% m-phenylene diamine (MPD)s that the polysulfones support membrane getting the molecular cut off 20000 ~ 50000 after purge drying is immersed in mass percentage concentration, flood 24 hours under room temperature, take out air-dry, under room temperature, coating quality percentage concentration is the dichloromethane solution containing m-phthaloyl chloride and pyromellitic trimethylsilyl chloride and triethylamine of 3 ~ 15%, react under room temperature after 0.2 hour, improve temperature to 50 ~ 90 DEG C and continue reaction after 2 hours, use acetone washs, vacuum drying, i.e. aromatic polyamides-polysulfone composite membrane the sheet (referred to as ClOC-PA/PS compound film sheet) of obtained surface containing acid chloride groups, for subsequent use.
" plantation " tertiary amine groups on step 2 ClOC-PA/PS compound film sheet
Take mean molecule quantity be 800 single diethylin polyethylene glycol 4.5 grams be dissolved in 5 milliliters of Isosorbide-5-Nitrae-dioxane solvent, be deployed into single diethylin polyglycol solution; The ClOC-PA/PS compound film sheet that step one is obtained is immersed in single diethylin polyglycol solution, control temperature to 55 ~ 75 DEG C, confined reaction is after 2.5 hours, pull reacted diaphragm out, use Isosorbide-5-Nitrae-dioxane solvent washing, re-use the aqueous sodium carbonate washing that mass percent is 10%, finally use deionized water washing to neutral, dry, the aromatic polyamides of the tertiary amine groups-polysulfone composite membrane sheet that has namely been surface " plantation " is (referred to as Et
2n-PEG-PA/PS compound film sheet).
Step 3 Et
2n-PEG-PA/PS compound film sheet is " plantation " quaternary ammonium salt and salicylide on the surface
Take 5.2 grams of 5-chloromethyl salicylaldehydes to be dissolved in 5.5 milliliters of Isosorbide-5-Nitrae-dioxane solvent, be deployed into 5-chloromethyl salicylaldehyde solution; The Et obtained by step 2
2n-PEG-PA/PS compound film sheet is immersed in 5-chloromethyl salicylaldehyde solution, control temperature to 5 ~ 15 DEG C, confined reaction is after 2.5 hours, 1 is used after taking out, diaphragm after 4-dioxane solvent washing reaction, eliminating free 5-chloromethyl salicylaldehyde, dry, is namely aromatic polyamides-polysulfone composite membrane sheet (referred to as QS-PEG-PA/PS compound film sheet) that quaternary ammonium salt and salicylide functional group are contained in surface.
The preparation of the aromatic polyamides-nonwoven polypropylene fabric compound film sheet of quaternary ammonium salt and salicylide functional group is contained on embodiment 2 surface
According to method and the operating procedure of embodiment 1, polysulfones support membrane in embodiment 1 step one is changed for nonwoven polypropylene fabric, i.e. aromatic polyamides-nonwoven polypropylene fabric the compound film sheet (referred to as QS-PEG-PA/PP compound film sheet) of obtained surface " plantation " quaternary ammonium salt and salicylide.
The preparation of the aromatic polyamides-cotton fiber filter paper compound film sheet of quaternary ammonium salt and salicylide functional group is contained on embodiment 3 surface
According to method and the operating procedure of embodiment 1, polysulfones support membrane in embodiment 1 step one is changed for cotton fiber filter paper, single diethylin polyethylene glycol of step 2 changes as 2-(dimethylamino) ethamine, i.e. aromatic polyamides-cotton fiber filter paper the compound film sheet (referred to as QS-DMA-PA/FP compound film sheet) of obtained surface " plantation " quaternary ammonium salt and salicylide.
Embodiment 4 quaternary ammonium salt and the surface-functionalized polyamide material composite membrane performance of salicylide
Commodity polysulfones support membrane respectively in Example 1 and QS-PEG-PA/PS composite membrane, commodity nonwoven polypropylene fabric in embodiment 2 and QS-PEG-PA/PP composite membrane, and commodity cotton fiber filter paper in 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.Result shows the hydrophilicity that efficiently can improve described aromatic polyamides composite film material through techniques and methods provided by the invention.
Claims (2)
1. the method that an aromatic polyamides reverse osmosis composite membrane is surface-functionalized, it is characterized in that carrying out condensation reaction by the acid chloride groups on aromatic polyamides reverse osmosis composite membrane surface and tertiary amine groups alcohol or tertiary amine groups organic amine, the aromatic polyamides reverse osmosis composite membrane of obtained surface containing tertiary amine groups; Thereafter the quaternization of the described surface aromatic polyamides reverse osmosis composite membrane and 5-chloromethyl salicylaldehyde that contain tertiary amine groups reacts, and has obtained the aromatic polyamides reverse osmosis composite membrane of film surface containing quaternary ammonium salt and salicylide functional group;
Described aromatic polyamides refers to the copolymer of aromatic diamine or aliphatic diamine and aromatic dimethyl chloride and aromatic series three formyl chloride, 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 structure shown in general formula (I), general formula (II), general formula (III) or general formula (IV) respectively:
R in described general formula (I), general formula (II), general formula (III) or general formula (IV)
1, R
2and R
3be selected from C respectively
1~ C
20alkyl, n is selected from the positive integer of 1 ~ 20;
Described aromatic diamine or aliphatic diamine are selected from structure shown in general formula (V), general formula (VI), general formula (VII) or general formula (VIII) respectively:
Z in its formula of (V) ~ general formula (VIII) is selected from H, methyl, ethyl, Cl, Br, F, NO
2in one, E is selected from CH
2, one in O or S, R is selected from (CH
2cH
2)
m,
in one, described m is selected from the positive integer of 1 ~ 20;
Described aromatic dimethyl chloride and aromatic series three formyl chloride are selected from structure shown in general formula (IX), general formula (X), general formula (XI) or general formula (XII) respectively:
Z in its formula of (IX) ~ general formula (XII) is selected from methyl, ethyl, Cl, Br, F or NO
2in one, E is selected from CH
2, one 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, polyvinyl chloride fibre fabric, acrylic fabric, vinylon fabric, RIPSTOP, spandex fabric, glass fabric, cotton fiber nonwoven paper cloth, the fine non-woven fabrics of fiber crops, nonwoven polypropylene fabric, polyvinyl chloride fibre non-woven fabrics, acrylic fibers non-woven fabrics, vinylon non-woven fabrics, polyamide fibre non-woven fabrics, one in spandex non-woven fabrics or glass fibre non-woven.
2., according to the method that aromatic polyamides reverse osmosis composite membrane described in claim 1 is surface-functionalized, it is characterized in that comprising step as described below:
The preparation of the aromatic polyamides reverse osmosis composite membrane of step one surface containing acid chloride groups
Get support membrane to be immersed in aromatic diamine or aliphatic diamine solution, pull out air-dry; Aromatic dimethyl chloride and aromatic series three formyl chloride and promoter mixed solution are sprayed on support membrane, through heat treatment, the aromatic polyamides reverse osmosis composite membrane of surface containing acid chloride groups can be obtained;
Wherein said support membrane is selected from as claimed in claim 1;
Described aromatic diamine or aliphatic diamine are selected from as claimed in claim 1 respectively;
Described aromatic dimethyl chloride and aromatic series three formyl chloride are selected from as claimed in claim 1 respectively;
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 ', one or more in N '-tetramethyl Alkylenediamine, N-ethylmorpholine, N-methylmorpholine, N, N '-diethyl piperazine;
Described aromatic diamine or aliphatic diamine: aromatic dimethyl chloride: aromatic series three formyl chloride: the mol ratio of promoter is 1: 0 ~ 0.5: 0.5 ~ 0.8: 0 ~ 5.0;
Step 2 aromatic polyamides reverse osmosis composite membrane connects the method for tertiary amine groups on the surface
Get the obtained surface of step one to contain acid chloride groups aromatic polyamides reverse osmosis composite membrane and be immersed in tertiary amine groups alcohol or tertiary amine groups organic amine, temperature control-10 ~ 90 DEG C reaction is after 2 ~ 24 hours, leach, service property (quality) percentage is the aqueous sodium carbonate washing of 10%, deionized water water washing is to neutral, vacuum drying, can 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 as claimed in claim 1 respectively;
Described tertiary amine groups alcohol or the consumption of tertiary amine groups organic amine are 1 ~ 20 times that acid chloride groups aromatic polyamides reverse osmosis composite membrane quality is contained on surface;
Step 3 aromatic polyamides reverse osmosis composite membrane surface connects the method for quaternary ammonium salt and salicylide
Take 5-chloromethyl salicylaldehyde to dissolve in organic solvent, obtained 5-chloromethyl salicylaldehyde solution; Control 5-chloromethyl salicylaldehyde solution temperature is between-5 ~ 95 DEG C, surface step 2 obtained was connected to the aromatic polyamides reverse osmosis composite membrane of tertiary amine groups and 5-chloromethyl salicylaldehyde solution haptoreaction after 2 ~ 12 hours, filter, washing, dry, namely obtained the aromatic polyamides reverse osmosis composite membrane that quaternary ammonium salt and salicylide functional group are contained in surface;
Wherein said organic solvent refer in ethyl acetate, propyl acetate, butyl acetate, acetone, Isosorbide-5-Nitrae-dioxane, oxolane, glycol dimethyl ether, ethylene glycol diethyl ether or 1,2-dichloroethanes one or more;
Described surface is connected to the aromatic polyamides reverse osmosis composite membrane of tertiary amine groups: 5-chloromethyl salicylaldehyde: the consumption mass ratio of organic solvent is 100: 10 ~ 200: 50 ~ 500.
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