CN107126850A - A kind of polysulfonamide nanofiltration or reverse osmosis composite membrane and preparation method thereof - Google Patents

A kind of polysulfonamide nanofiltration or reverse osmosis composite membrane and preparation method thereof Download PDF

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Publication number
CN107126850A
CN107126850A CN201710369366.XA CN201710369366A CN107126850A CN 107126850 A CN107126850 A CN 107126850A CN 201710369366 A CN201710369366 A CN 201710369366A CN 107126850 A CN107126850 A CN 107126850A
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polysulfonamide
nanofiltration
reverse osmosis
composite membrane
sulfonic acid
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牛青山
袁涛
胡月芳
郭鑫
李鹏
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Qingdao Zhiyong New Material Technology Co ltd
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China University of Petroleum East China
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/26—Spraying processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Nanotechnology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a kind of polysulfonamide nanofiltration or reverse osmosis composite membrane and preparation method thereof, the preparation method of the polysulfonamide nanofiltration or reverse osmosis composite membrane includes：Alternately on porous support membrane surface, reaction carries out the steps such as layer assembly, heat treatment to pretreatment, sulfonic acid chloride organic phase solution and the polyamine aqueous phase solution of porous support membrane, and heat treatment can be carried out during layer assembly or after the completion of layer assembly.Added with nano-particle, surfactant, the catalysis additive such as acid absorbent or catalyst, pore-foaming agent in sulfonic acid chloride organic phase solution or polyamine aqueous phase solution.The polysulfonamide nanofiltration or reverse osmosis composite membrane prepared using the above method, which polymerize the composite membrane desalting performance raising prepared, acid resistance relative to traditional interface, to be strengthened, while surface is more smooth, roughness is lower, had broad application prospects in nanofiltration and counter-infiltration field.

Description

A kind of polysulfonamide nanofiltration or reverse osmosis composite membrane and preparation method thereof
Technical field
The present invention relates to a kind of polymer compound film, and in particular to a kind of polysulfonamide nanofiltration or reverse osmosis composite membrane and its Preparation method.
Background technology
Since aromatic polyamide interfacial polymerization techniques prepare counter-infiltration and NF membrane material industry application, nanofiltration and reverse osmosis Permeable membrane isolation technics obtains more and more extensive in water treatment fields such as desalinization, Treated sewage reusing, sewage disposal, drinking water preparations Application.Main flow rolling nanofiltration in the market or reverse osmosis composite membrane surface functional cortex are still based on polynary acyl chlorides (such as The formyl chloride of 1,3,5- benzene three) with polyamine (such as m-phenylene diamine (MPD) or piperazine) formation polyamide cross-linked network structure prepare. Above-mentioned monomer is also considered as current interfacial polymerization preparation nanofiltration or reverse osmosis membrane is maximally effective.But the acyl in polyamide structure Amine key is hydrolyzed under the conditions of low and high ph-values, constrains application of the above-mentioned composite membrane in severe rugged environment.
A kind of preparation method of anti-acid polysulfonamide NF membrane has been documented.This method with sulfonic acid chloride monomer with it is many First amine monomers carry out interfacial polymerization, and addition acid receives agent in polyamine aqueous phase solution, and the composite membrane acid resistance of preparation is big Width is improved.But no matter the nanofiltration prepared using this method or reverse osmosis membrane are in surface roughness, desalting performance and water flux etc. Aspect, is difficult to realize the performance level of classics nanofiltration or reverse osmosis membrane.
The content of the invention
For above-mentioned the deficiencies in the prior art, the technical problem to be solved in the present invention is to provide a kind of polysulfonamide nanofiltration or Reverse osmosis composite membrane and preparation method thereof, can effectively solve the problem that composite membrane salt rejection rate is low, surface roughness is high in the prior art, rule The problem of modelling production stability is poor.
In order to achieve the above object, the technical solution adopted in the present invention is：A kind of new preparation technology, the technique are provided Comprise the following steps：
A. porous support membrane is washed for 30~50wt% alcohol/aqueous solution with alcohol content, then it is totally standby with pure water rinsing With；
B. the porous support membrane of washes clean is pre-processed, the pretreatment is in the larger support membrane table of hole defect Face coated polymer coating；
C. by sulfonic acid chloride organic phase solution and polyamine aqueous phase solution by pretreated porous support membrane at least Alternately haptoreaction once, forms at least one layer of nascent state polysulfonamide nanofiltration by molecule layer assembly or counter-infiltration is compound Film；
D. at a temperature of 40~110 DEG C, the nanofiltration of nascent state polysulfonamide or reverse osmosis composite membrane are carried out heat treatment 1~ 20min, the heat treatment is carried out or carried out after finishing assembly in an assembling process；
E. it is 3~5 abundant washing step d gained composite film surface of hydrochloric acid or aqueous sulfuric acid with pH value, obtains film forming.
The beneficial effects of the invention are as follows：The composite membrane prepared has very high salt rejection rate, and the removal efficiency of monovalent salt exists More than 90%, the removal efficiency of divalent salts is more than 99%；The composite film surface roughness prepared is less than 20nm；And according to not Same processing requirement, can control to prepare the different numbers of plies, to obtain the composite membrane of different separating properties.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further, porous support membrane can be sub- for high-molecular porous supporting layer such as polysulfones, polyether sulfone, polyacrylonitrile or polyamides Amine etc., or inorganic porous membrane such as ceramic membrane such as silica, titanium oxide, zirconium oxide etc..
Further, sulfonic acid chloride organic phase solution includes 0.001~5wt% sulfonic acid chloride monomer (one or more mixing), 0 ~10wt% additive and 85~99.999wt% organic solvent；The sulfonic acid chloride monomer has following structure：
Wherein, A is aliphatic group, benzene, biphenyl or naphthalene, R1、R2And R3It is-SO2Cl ,-SO2Cl number is at least Two；The additive includes 0~5wt% nano-particle and 0~5wt% surfactant, and the organic solvent is by second One or more of compositions in acetoacetic ester, chloroform, toluene, dimethylbenzene, Isopar series, n-hexane, heptane and n-dodecane；
The polyamine aqueous phase solution solution includes 0.001~15wt% polynary amine monomers, 0~25wt% additive With 60~99.999wt% aqueous phase solvent；The polynary amine monomers have following structure：
Wherein, R in cyclic structure monomer1And R2It is-NH- or-CH2-, substituent R3、R4And R5It is-CH3Or-NH2；B For fatty full carbon or the miscellaneous linear segment of carbon, substituent R6、R7And R8For-NH2Or-CH3,-NH2Number at least two；B is fat The full carbon of fat or the miscellaneous linear segment of carbon, substituent R6、R7And R8For-NH2Or-CH3,-NH2Number at least two；The addition The acid absorbent or catalyst of agent including 0~5wt%, 0~10wt% pore-foaming agent, 0~5wt% nano-particle and 0~ 5wt% surfactant, the aqueous phase solvent is the mixed solvent of water or water and organic solvent, and the in the mixed solvent is organic Solvent is made up of the one or more in acetone, methanol, ethanol, isopropanol.
Beneficial effect using above-mentioned further technical scheme is：By the increase of the number of plies, composite membrane can be effectively improved Desalination property, reduces the surface roughness of film；Sulfonic acid chloride group is more, and the cross-linked structure on composite membrane is finer and close, crosslinking Spend more high desalination effect better；Monomer and additive are evenly spread in out of phase solvent, can when two phase liquid is contacted Quickly generate homogeneous composite membrane；Addition nano-particle can significantly improve the water flux of composite membrane, add surface-active Agent, can promote the reaction between two-phase, improve the degree of cross linking；Addition acid absorbent or catalyst can significantly improve composite membrane Prepare speed and film properties.
Further, sulfonic acid chloride monomer is the sulfonic acid chloride of 1,3,6- naphthalene three, the sulfonic acid chloride of 2,4,6- benzene three or 2, the sulphonyl of 4,6- benzene three 1 bit derivant of chlorine；Polynary amine monomers are ethylenediamine, piperazine, trien, m-xylene diamine, 2,5- lupetazins Or N, N`- diaminopiperazine.
Further, nano-particle is the inorganic or organic nano level particle for having hole or non-porous, ring-type or non-annularity pattern；Institute The surfactant stated includes anion surfactant, cationic surfactant, zwitterionic surfactant and polyoxy Ethylene type surfactant；The acid absorbent or catalyst are lutidines, triethylamine, sodium hydroxide or sodium carbonate；Institute The pore-foaming agent stated is camphorsulfonic acid or its triethylamine salt.
The polymer coating introduced in further step b is polyvinyl alcohol or polyethyleneimine or PLA or polyacrylic acid Or poly- (2- alkyl -2- oxazolines).
Beneficial effect using above-mentioned further technical scheme is：Applied for the larger porous support membrane of pore defect The addition of layer, is more beneficial for preparing high-performance desalination composite membrane.
Further, the layer assembly has following several ways：
By porous support membrane alternate immersion in sulfonic acid chloride organic phase solution and polyamine aqueous phase solution；
Uniform alternating spray sulfonic acid chloride organic phase solution and polyamine aqueous phase solution on porous support membrane surface；
Replace spin coating sulfonic acid chloride organic phase solution and polyamine aqueous phase on open support tunic surface using spin coating spin-coating method Solution.
Beneficial effect using above-mentioned further technical scheme is：Alternately contact starts assembling in interface instead to two kinds of solution Answer, occur assembling reaction by the multiple alternating sorbent deposition of two kinds of monomers, ultimately produce thickness uniformly, finer and close polysulfonate acyl Amine composite membrane.And using alternating spray or alternating spin coating two ways, the controllable thin layer of excellent performance, thickness can be prepared Composite membrane.
Polysulfonamide nanofiltration or reverse osmosis composite membrane are prepared for using above-mentioned preparation method, and by obtained polysulfonamide Nanofiltration or reverse osmosis composite membrane are used in traditional nanofiltration and counter-infiltration field and acidic separating medium field.By experimental verification, Polysulfonamide NF membrane or reverse osmosis membrane that the polysulfonamide nanofiltration or reverse osmosis composite membrane are manufactured compared to conventional method, surface Roughness is extremely low, acid resistance is strong, and separating property is higher, while the separating property and permeance property of composite membrane prepared by this method Reach the performance of classical nanofiltration or reverse osmosis composite membrane.
Embodiment
In the polysulfonamide nanofiltration of the present invention or reverse osmosis composite membrane preparation method, porous support membrane is washed first Wash.Washing methods is：Porous support membrane is washed with alcohol content for 30~50wt% alcohol/aqueous solution, pure water rinsing is then used Standby afterwards, the alcohol/aqueous solution used is preferably the aqueous solution of isopropanol or ethanol, and porous support membrane can be high-molecular porous branch Support layer such as polysulfones, polyether sulfone, polyacrylonitrile or polyimides, or inorganic porous membrane such as silica, titanium oxide, zirconium oxide Deng ceramic membrane.Then sulfonic acid chloride organic phase solution and polyamine aqueous phase solution are prepared., will when preparing sulfonic acid chloride organic phase solution 0.001~5wt% sulfonic acid chloride monomer, 0~5wt% nano-particles, 0~5wt% surfactant is dissolved in solvent, molten It is sufficiently stirred in solution preocess, each component fully dissolved, mixed.Sulfonic acid chloride monomer has following in sulfonic acid chloride organic phase solution Structure：
Wherein, A is aliphatic group, benzene, biphenyl or naphthalene, R1、R2And R3It is-SO2Cl ,-SO2Cl number is at least two It is individual, such as：The sulfonic acid chloride of 2,4,6- benzene three, the sulfonic acid chloride of 1,3,6- naphthalene three etc.；The nano-particle is using well known in the prior art There is the inorganic or organic nano level particle of hole or non-porous, ring-type or non-annularity pattern；The range of choice of surfactant is wider, can To be anion surfactant such as dodecyl sodium sulfate or cationic surfactant such as quaternary ammonium compound, may be used also Equally can be that polyoxyethylene-type surface is lived to be zwitterionic surfactant such as lecithin, amino acid pattern and betaine type Property agent such as long-chain fatty acid ester, aliphatic alcohol ester, phosphate ester etc.；The solvent of sulfonic acid chloride organic phase solution from ethyl acetate, chloroform, Chosen in toluene, dimethylbenzene, Isopar series, n-hexane, heptane and n-dodecane equal solvent, can be that one kind can also be several Plant the mixed solvent constituted after solvent mixing.When preparing polyamine aqueous phase solution, by 0.001~15wt% polynary amine monomers, 0 ~25wt% additive is dissolved in solvent, is sufficiently stirred in course of dissolution, each component fully dissolved, mixed.It is polynary Polynary amine monomers have following structure in amine aqueous phase solution：
Wherein, R in cyclic structure monomer1And R2It is-NH- or-CH2-, substituent R3、R4And R5It is-CH3Or-NH2；B For fatty full carbon or the miscellaneous linear segment of carbon, substituent R6、R7And R8For-NH2Or-CH3,-NH2Number at least two；B is fat The full carbon of fat or the miscellaneous linear segment of carbon, substituent R4、R5And R6- NH2,-NH2Number at least two；Additive is absorbed by acid One or more of compositions in agent or catalyst, pore-foaming agent, nano-particle, surfactant, acid absorbent or catalyst can be with With lutidines, triethylamine, sodium hydroxide or sodium carbonate etc., acid absorbent or catalyst account for total solution weight 0~ 5wt%, pore-foaming agent be camphorsulfonic acid or its triethylamine salt or other play material of same purpose etc., pore-foaming agent accounts for solution gross weight 0~5wt% of amount, nano-particle, the species of surfactant and consumption are as in sulfonic acid chloride organic phase solution；Polyamine The solvent of aqueous phase solution can be that water can also be water and the mixed mixed solvent of organic solvent, when for mixed solvent, mix One or more of the organic solvent in acetone, methanol, ethanol and isopropanol in bonding solvent.
What the layer assembly was commonly used has following several ways, and one kind is that porous support membrane alternate immersion is being contained into sulphur respectively Reacted in the organic phase solution of acyl chlorides and the aqueous phase solution of polyamine.This mode is easy to operate, only need to be by open support Film alternating alternate immersion, soak time 30s~5min in above-mentioned two phase liquid；Before alternately another solution is immersed, Purged by gas, rubber stick wipe etc. mode, remove residual solvent.Second is uniformly alternately sprayed on porous support membrane surface Apply sulfonic acid chloride organic phase solution and polyamine aqueous phase solution.This method is that two kinds of solution are individually positioned in flusher, The surface of solution alternating spray to porous support membrane is subjected to layer assembly in vaporific form.This method can be for preparation The composite membrane of very thin thickness, and two kinds of solution are individually present, and will not cause cross pollution.The third is to utilize spin coating spin-coating method Replace spin coating sulfonic acid chloride organic phase solution and polyamine aqueous phase solution in open support film surface.Spin coating can drip solution Fall on porous support membrane can also be after porous support membrane is soaked in the solution again under 1000~10000rmp rotating speed The surface for making solution uniformly be spun to support membrane carries out layer assembly.It can prepare that the uniformity is very high, thickness in this way The controllable composite membrane of degree.Progress can be repeated several times in the step of above-mentioned several method, and completion once produces one layer of composite membrane, such as The polysulfonamide nanofiltration of 30 layers of preparation or reverse osmosis composite membrane, only need to repeat 30 above-mentioned steps.Above-mentioned several method is only It is that other can realize identical purpose in order to preferably realize layer assembly, but layer assembly is not limited to above-mentioned several method Method it is also possible.
In the preparation process of film, performance is obtained in order to improve polysulfonamide nanofiltration or reverse osmosis composite membrane, surface is prepared more Plus smooth nanofiltration or reverse osmosis composite membrane, polymer coating can be introduced.The introducing of the polymer coating can be layer by layer Assemble and carried out before preparation process, be now the surface that polymer coating is coated to porous support membrane；Can also be in layer assembly Carried out in preparation process, be now the surface that polymer coating is coated to nascent state nanofiltration or reverse osmosis membrane, can be assembling Complete once to introduce one layer of coating or assembling is re-introduced into one layer of coating afterwards several times；It can also be and completed in layer assembly After carry out, be now the surface that polymer coating is coated to the nanofiltration of outermost layer nascent state or reverse osmosis membrane.Before assembling or group Coating is introduced after dress, the number of plies of coating should not be excessive, in order to avoid the ion or water flux of influence composite membrane, now preferably 1~ 3 layers.
Polysulfonamide nanofiltration or the reverse osmosis composite membrane of nascent state are produced after the completion of layer assembly, also to carry out one to it is The subsequent treatment of row can just obtain film forming.The subsequent treatment is polysulfonamide nanofiltration or the reverse osmosis for the nascent state that will be obtained first Saturating composite membrane is heat-treated at a certain temperature, and heat treatment temperature is 40~110 DEG C, and heat treatment time is complete in 1~20min Into.In order to improve the degree of cross linking of multilayer complex films, heat treatment can be carried out during layer assembly.To compound after heat treatment Film carries out washing by soaking, and the washing can be organic solvent such as alcohol solution or directly be soaked or rinsed with water.
Polysulfonamide nanofiltration or reverse osmosis composite membrane are prepared for using above-mentioned preparation method, and obtained polysulfonamide is answered Close nanofiltration and counter-infiltration field that film is used in tradition or acid medium.By experimental verification, the polysulfonamide nanofiltration or reverse osmosis Polysulfonamide NF membrane or reverse osmosis membrane that saturating composite membrane is manufactured compared to conventional method, desalting performance are increased substantially, simultaneously The surface roughness of polysulfonamide film prepared by this method is low, acid resistance is high, stability good, wherein desalting performance and permeability It can reach the level of classical polyamide composite reverse osmosis membrane.
The following examples are only intended to describe the present invention in detail, and the scope of invention is not limited in any way.
(1) embodiment 1：
After polysulfones support membrane is fully washed with 30wt% ethanol water, the 1% piperazine aqueous solution and 2% 3 second are put into 2min is soaked in the mixed solution of amine, then 0.02%1,1min is soaked in the toluene solution of the sulfonic acid chloride of 3,6- naphthalene three, passes through Reaction carries out layer assembly；Repeat the above steps 8 times, the nanofiltration of nascent state polysulfonamide or the reverse osmosis composite membrane of 8 thickness be made, It is heat-treated after 15min and is washed with pH for 3 aqueous hydrochloric acid solution at 90 DEG C.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(2) embodiment 2：
After polysulfones support membrane is fully washed with 30wt% ethanol water, the 1% piperazine aqueous solution and 2% 3 second are put into The mixed solution of amine is sprayed on polysulfones support membrane, and the toluene solution that the sulfonic acid chloride of 0.02%1,3,6- naphthalene three is sprayed after 2min is carried out Reaction；Alternately above-mentioned steps 8 times, are made the nanofiltration of nascent state polysulfonamide or the reverse osmosis composite membrane of 8 thickness, at 90 DEG C Washed after heat treatment 15min with pH for 3 aqueous hydrochloric acid solution.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(3) embodiment 3：
After polysulfones support membrane is fully washed with 30wt% ethanol water, the 1% piperazine aqueous solution and 2% 3 second are put into 2min is soaked in the mixed solution of amine, then 20s is rotated under 2000rmp rotating speeds, the sulphonyl of 0.02%1,3,6- naphthalene three is placed into 1min is soaked in the toluene solution of chlorine, 20s is rotated under 2000rmp rotating speeds；Alternately above-mentioned steps 8 times, are made 8 thickness The nanofiltration of nascent state polysulfonamide or reverse osmosis composite membrane, are heat-treated after 15min at 90 DEG C and are washed with pH for 3 aqueous hydrochloric acid solution Wash.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(4) embodiment 4：
After polysulfones support membrane is fully washed with 30wt% ethanol water, the 0.5% piperazine aqueous solution and 1% 3 are put into 2min is soaked in the mixed solution of ethamine, then 20s is rotated under 2000rmp rotating speeds, the sulphur of 0.01%1,3,6- naphthalene three is placed into 1min is soaked in the toluene solution of acyl chlorides, 20s is rotated under 2000rmp rotating speeds；Alternately above-mentioned steps 8 times, often complete one Secondary assembling is just heat-treated 1min at 60 DEG C, and the nanofiltration of nascent state polysulfonamide or the reverse osmosis composite membrane of 8 thickness is made, is with pH 3 aqueous sulfuric acid washing.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(5) embodiment 5：
After polyether sulfone support membrane is fully washed with 50wt% ethanol water, the 1% piperazine aqueous solution and 2% 3 are put into 2min is soaked in the mixed solution of ethamine, then 20s is rotated under 2000rmp rotating speeds, the sulphur of 0.02%1,3,6- naphthalene three is placed into 1min is soaked in the toluene solution of acyl chlorides, 20s is rotated under 2000rmp rotating speeds；Alternately above-mentioned steps 10 times, are made 10 layers Thick nascent state polysulfonamide nanofiltration or reverse osmosis composite membrane, are heat-treated after 15min at 90 DEG C with the aqueous sulfuric acid that pH is 5 Washing.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(6) embodiment 6：
After Pan Supporting Membranes are fully washed with 50wt% ethanol water, the 1% piperazine aqueous solution and 2% are put into 2min is soaked in the mixed solution of triethylamine, then 20s is rotated under 2000rmp rotating speeds, 0.02%1,3,6- naphthalenes three are placed into 1min is soaked in the toluene solution of sulfonic acid chloride, 20s is rotated under 2000rmp rotating speeds；Alternately above-mentioned steps 10 times, are made 10 The nascent state polysulfonamide nanofiltration of thickness or reverse osmosis composite membrane, are heat-treated water-soluble for 5 hydrochloric acid with pH after 15min at 90 DEG C Liquid is washed.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(7) embodiment 7：
After polysulfones support membrane is fully washed with 30wt% ethanol water, be put into the 0.25% piperazine aqueous solution and 2min is soaked in the mixed solution of 0.5% triethylamine, then 20s is rotated under 3000rmp rotating speeds, places into 0.01%1,3,6- 1min is soaked in the toluene solution of the sulfonic acid chloride of naphthalene three, 20s is rotated under 2000rmp rotating speeds；Alternately above-mentioned steps 50 times, make The nanofiltration of nascent state polysulfonamide or the reverse osmosis composite membrane of 25 thickness are obtained, it is 5 hydrochloric acid waters to be heat-treated at 90 DEG C after 15min with pH Solution is washed.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(8) embodiment 8：
After polysulfones support membrane is fully washed with 30wt% ethanol water, the 1% piperazine aqueous solution, 2% camphor are put into 2min, Ran Hou are soaked in sulfonic acid, 1% triethylamine, 0.01% molecular sieve of Nano zeolite and 0.5%SDS mixed solution 40s is rotated under 7000rmp rotating speeds, 1min is soaked in the toluene solution for placing into the sulfonic acid chloride of 0.02%1,3,6- naphthalene three, 40s is rotated under 7000rmp rotating speeds；Alternately above-mentioned steps 8 times, are made the nanofiltration of nascent state polysulfonamide or the reverse osmosis of 8 thickness Saturating composite membrane, is washed after being heat-treated 20min at 110 DEG C with hydrochloric acid or aqueous sulfuric acid.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(9) embodiment 9：
After polysulfones support membrane is fully washed with 30wt% ethanol water, 0.3% polyvinyl alcohol water solution list is put into Face immersion treatment 3min, soaks 2min, so in the 0.5% piperazine aqueous solution, 2% camphorsulfonic acid, the mixed solution of 1% triethylamine 20s is rotated under 3000rmp rotating speeds afterwards, 1min is soaked in the toluene solution for placing into the sulfonic acid chloride of 0.02%1,3,6- naphthalene three, 20s is rotated under 3000rmp rotating speeds；Alternately above-mentioned steps 10 times, are made the nascent state polysulfonamide nanofiltration or anti-of 10 thickness Osmosis composite membrane, it is that 5 aqueous hydrochloric acid solutions are washed to be heat-treated at 90 DEG C after 15min with pH.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(10) embodiment 10：
After polysulfones support membrane is fully washed with 30wt% ethanol water, the 1% piperazine aqueous solution, 2% camphor are put into 2min is soaked in sulfonic acid, the mixed solution of 1% triethylamine, then 40s is rotated under 7000rmp rotating speeds, places into 0.02%1, 1min is soaked in the toluene solution of the sulfonic acid chloride of 3,6- naphthalene three, 40s is rotated under 7000rmp rotating speeds；Alternately above-mentioned steps 10 It is secondary, often complete once to assemble just with 0.5% polyvinyl alcohol water solution one side immersion treatment 1min, the nascent state that 10 thickness are made is gathered Sulfonamide nanofiltration or reverse osmosis composite membrane, it is that 5 aqueous hydrochloric acid solutions are washed to be heat-treated at 90 DEG C after 15min with pH.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(11) embodiment 11：
After polysulfones support membrane is fully washed with 30wt% ethanol water, 0.3% polyacrylic acid aqueous solution list is put into Face immersion treatment 3min, soaks 1min, so in the 0.5% piperazine aqueous solution, 2% camphorsulfonic acid, the mixed solution of 1% triethylamine 20s is rotated under 3000rmp rotating speeds afterwards, 1min is soaked in the toluene solution for placing into the sulfonic acid chloride of 0.02%1,3,6- naphthalene three, 20s is rotated under 3000rmp rotating speeds；Alternately above-mentioned steps 10 times, are made the nascent state polysulfonamide nanofiltration or anti-of 10 thickness Osmosis composite membrane, it is that 5 aqueous hydrochloric acid solutions are washed to be heat-treated at 90 DEG C after 15min with pH.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(12) embodiment 12：
After polysulfones support membrane is fully washed with 30wt% ethanol water, 0.5% polyvinyl alcohol water solution list is put into Face immersion treatment 5min, at the 0.5% piperazine aqueous solution, the 1% m-xylene diamine aqueous solution, 2% camphorsulfonic acid, 2% triethylamine 2min is soaked in reason, 0.01% nano zeolite molecule, 0.1%SDS mixed solutions, then 40s is rotated under 7000rmp rotating speeds, 1min is soaked in the toluene/hexane solution for placing into the sulfonic acid chloride of 0.02%1,3,6- naphthalene three, is rotated under 7000rmp rotating speeds 40s；Alternately above-mentioned steps 10 times, are made the nanofiltration of nascent state polysulfonamide or the reverse osmosis composite membrane of 10 thickness, at 90 DEG C Washed after lower heat treatment 15min with pH for 5 aqueous hydrochloric acid solutions.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(13) embodiment 13：
After polysulfones support membrane is fully washed with 30wt% ethanol water, 0.5% polyvinyl alcohol water solution list is put into Face immersion treatment 5min, at the 0.5% piperazine aqueous solution, the 1% m-xylene diamine aqueous solution, 2% camphorsulfonic acid, 2% triethylamine 2min is soaked in reason, 0.01% nano zeolite molecule, 0.1%SDS mixed solutions, then 40s is rotated under 7000rmp rotating speeds, Place into 0.02%1- hydroxyls -2,4, toluene/IsoparG solution of 6- benzene sulfonyl chlorides and soak 1min, under 7000rmp rotating speeds Rotate 40s；Alternately above-mentioned steps 8 times, are made the nanofiltration of nascent state polysulfonamide or the reverse osmosis composite membrane of 8 thickness, 90 It is that 5 aqueous hydrochloric acid solutions are washed to be heat-treated at DEG C after 15min with pH.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(14) embodiment 14：
After polysulfones support membrane is fully washed with 30wt% ethanol water, 0.5% polyvinyl alcohol water solution list is put into Face immersion treatment 5min, at the 0.5% piperazine aqueous solution, the 1% m-xylene diamine aqueous solution, 2% camphorsulfonic acid, 2% triethylamine 2min is soaked in reason, 0.01% nano zeolite molecule, 0.1%SDS mixed solutions, then 40s is rotated under 7000rmp rotating speeds, Place into 0.02%1- amino -2,4, toluene/IsoparG solution of 6- benzene sulfonyl chlorides and soak 1min, under 7000rmp rotating speeds Rotate 40s；Alternately above-mentioned steps 8 times, are made the nanofiltration of nascent state polysulfonamide or the reverse osmosis composite membrane of 8 thickness, 90 It is that 5 aqueous hydrochloric acid solutions are washed to be heat-treated at DEG C after 15min with pH.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(15) embodiment 15：
After polysulfones support membrane is fully washed with 30wt% ethanol water, 0.5% polyvinyl alcohol water solution list is put into Face immersion treatment 5min, at the 0.5% piperazine aqueous solution, the 1% m-xylene diamine aqueous solution, 10% camphorsulfonic acid, 5% triethylamine 2min is soaked in reason, 5% nano zeolite molecule, 5%SDS mixed solutions, then 40s is rotated under 7000rmp rotating speeds, places into Soaked in the sulfonic acid chloride of 0.01%1,3,6- naphthalenes three, toluene/Isopar G mixed solutions of 0.01%1- amino -2,4,6- benzene sulfonyl chlorides 1min is steeped, 40s is rotated under 7000rmp rotating speeds；Alternately above-mentioned steps 8 times, the nascent state polysulfonamide that 8 thickness are made is received Filter or reverse osmosis composite membrane, it is that 5 aqueous hydrochloric acid solutions are washed to be heat-treated at 90 DEG C after 15min with pH.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(16) embodiment 16：
After polysulfones support membrane is fully washed with 30wt% ethanol water, the 1% piperazine aqueous solution and 2% 3 second are put into 2min is soaked in the mixed solution of amine, then 20s is rotated under 2000rmp rotating speeds, the sulphonyl of 0.02%1,3,6- naphthalene three is placed into Immersion 1min in the toluene solution of chlorine, 0.01% nano zeolite molecule, 0.1%SDS mixed solutions, in 2000rmp rotating speeds Lower rotation 20s；Alternately above-mentioned steps 8 times, are made the nanofiltration of nascent state polysulfonamide or the reverse osmosis composite membrane of 8 thickness, It is that 5 aqueous hydrochloric acid solutions are washed to be heat-treated at 90 DEG C after 15min with pH.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(17) embodiment 17：
After polysulfones support membrane is fully washed with 30wt% ethanol water, 0.5% polyvinyl alcohol water solution list is put into Face immersion treatment 5min, at the 0.5% piperazine aqueous solution, the 1% m-xylene diamine aqueous solution, 10% camphorsulfonic acid, 5% triethylamine 2min is soaked in reason, 5% nano zeolite molecule, 5%SDS mixed solutions, then 40s is rotated under 7000rmp rotating speeds, places into 1min is soaked in 0.02%1- amino -2,4, toluene/Isopar G solution of 6- benzene sulfonyl chlorides, is rotated under 7000rmp rotating speeds 40s；Alternately above-mentioned steps 8 times, are made the nanofiltration of nascent state polysulfonamide or the reverse osmosis composite membrane of 8 thickness, at 90 DEG C Washed after heat treatment 15min with pH for 5 aqueous hydrochloric acid solutions.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(18) embodiment 18：
After microporous silica membrane is fully washed with 30wt% ethanol water, the 0.001% piperazine aqueous solution is put into 2min is soaked with the mixed solution of 0.1% triethylamine, then 0.001%1, is soaked in the toluene solution of the sulfonic acid chloride of 3,6- naphthalene three 1min is steeped, layer assembly is carried out by reacting, 20 thickness nascent state polysulfonamide nanofiltrations or reverse osmosis composite membrane is made, at 40 DEG C Washed after lower heat treatment 10min with pH for 5 aqueous hydrochloric acid solutions.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(19) embodiment 19：
After polysulfones support membrane is fully washed with 30wt% ethanol water, be put into the 0.001% piperazine aqueous solution and 2min is soaked in the mixed solution of 0.1% triethylamine, then 0.001%1, is soaked in the toluene solution of the sulfonic acid chloride of 3,6- naphthalene three 1min, layer assembly is carried out by reacting；Repeat the above steps 50 times, the nascent state polysulfonamide nanofiltration or anti-of 50 thickness is made Osmosis composite membrane, it is that 5 aqueous hydrochloric acid solutions are washed to be heat-treated at 110 DEG C after 15min with pH.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(20) embodiment 20：
After polysulfones support membrane is fully washed with 30wt% ethanol water, the 15% piperazine aqueous solution and 5% 3 are put into 5min is soaked in the mixed solution of ethamine, then 5%1,3min is soaked in the toluene solution of the sulfonic acid chloride of 3,6- naphthalene three, by anti- Layer assembly should be carried out, the nanofiltration of nascent state polysulfonamide or reverse osmosis composite membrane is made, is heat-treated at 40 DEG C after 25min with use PH washs for 5 aqueous hydrochloric acid solutions.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：
(21) comparative example 21：
After polysulfones support membrane is fully washed with 30wt% ethanol water, the 15% piperazine aqueous solution and 5% 3 are put into 20s is soaked in the mixed solution of ethamine, then 5%1,1min is soaked in the toluene solution of the sulfonic acid chloride of 3,6- naphthalene three, by anti- Layer assembly should be carried out, the nanofiltration of nascent state polysulfonamide or reverse osmosis composite membrane is made, is heat-treated at 40 DEG C after 15min with use PH washs for 5 aqueous hydrochloric acid solutions.
The polysulfonamide nanofiltration obtained with the method or performance of composite antiosmosis membrane are as follows：

Claims (9)

1. a kind of polysulfonamide nanofiltration or reverse osmosis composite membrane preparation method, it is characterized in that：Comprise the following steps：
A. porous support membrane is washed for 30~50wt% alcohol/aqueous solution with alcohol content, then it is totally standby with pure water rinsing；
B. the porous support membrane of washes clean is pre-processed, the pretreatment is applied on the larger support membrane surface of hole defect Cover polymer coating；
C. by polyamine aqueous phase solution and sulfonic acid chloride organic phase solution respectively by pretreated porous support membrane at least Alternately coating reaction once, forms at least one layer of nascent state polysulfonamide nanofiltration by molecule layer assembly or counter-infiltration is compound Film；
D. at a temperature of 40~110 DEG C, 1~20min of heat treatment is carried out to the nanofiltration of nascent state polysulfonamide or reverse osmosis composite membrane, The heat treatment is carried out in an assembling process or after being completed；
E. it is 3~5 abundant washing step d gained composite film surface of hydrochloric acid or aqueous sulfuric acid with pH value, obtains film forming.
2. polysulfonamide nanofiltration according to claim 1 or reverse osmosis composite membrane preparation method, it is characterized in that：It is described porous Support membrane is high-molecular porous support membrane or inorganic porous support membrane.
3. polysulfonamide nanofiltration according to claim 2 or reverse osmosis composite membrane preparation method, it is characterized in that：The high score Sub- porous support membrane is polysulfones, polyether sulfone, polyacrylonitrile or polyimides；The inorganic porous support membrane is silicon oxide ceramics Film, titanium oxide ceramics film or zirconia ceramics film.
4. polysulfonamide nanofiltration according to claim 1 or reverse osmosis composite membrane preparation method, it is characterized in that：The sulphonyl Chlorine organic phase solution includes 0.001~5wt% sulfonic acid chloride monomer, 0~10wt% additive and 85~99.999wt% Organic phase solvent；
The sulfonic acid chloride monomer has following structure：
Wherein, A is aliphatic group, benzene, biphenyl or naphthalene, R1、R2And R3It is-SO2Cl groups ,-SO2The number of Cl groups is at least For two；
The additive includes 0~5wt% nano-particle and 0~5wt% surfactant；
The organic phase solvent is by ethyl acetate, chloroform, toluene, dimethylbenzene, Isopar series, n-hexane, heptane and positive 12 One or more of compositions in alkane；
The polynary amine monomers of the polyamine aqueous phase solution including 0.001~15wt%, 0~25wt% additive and 60~ 99.999wt% aqueous phase solvent；
The polynary amine monomers have following structure：
Wherein, R in cyclic structure monomer1And R2It is-NH- or-CH2-, substituent R3、R4And R5It is-CH3Or-NH2；B is fat The full carbon of fat or the miscellaneous linear segment of carbon, substituent R6、R7And R8For-NH2Or-CH3,-NH2Number at least two；
The additive includes 0~5wt% acid absorbent or catalyst, 0~10wt% pore-foaming agent, 0~5wt% nanometer The surfactant of particle and 0~5wt%；
The aqueous phase solvent is the mixed solvent of water or water and organic solvent, and the organic solvent is by acetone, methanol, ethanol, different One or more of compositions in propyl alcohol.
5. polysulfonamide nanofiltration according to claim 4 or reverse osmosis composite membrane preparation method, it is characterized in that：Sulfonic acid chloride list Body is 1 substitutive derivative of the sulfonic acid chloride of 1,3,6- naphthalenes three, the sulfonic acid chloride of 2,4,6- benzene three or the sulfonic acid chloride of 2,4,6- benzene three；It is polynary Amine monomers are ethylenediamine, piperazine, trien, m-xylene diamine, 2,5- lupetazins or N, N`- diaminopiperazine.
6. polysulfonamide nanofiltration according to claim 4 or reverse osmosis composite membrane preparation method, it is characterized in that：The nanometer Particle is the inorganic or organic nano level particle for having hole or non-porous, ring-type or non-annularity pattern；Described surfactant includes Anion surfactant, cationic surfactant, zwitterionic surfactant and polyoxyethylene-type surfactant；Institute The acid absorbent or catalyst stated are lutidines, triethylamine, sodium hydroxide or sodium carbonate；Described pore-foaming agent is camphor sulphur Acid or its triethylamine salt.
7. polysulfonamide nanofiltration according to claim 1 or reverse osmosis composite membrane preparation method, it is characterized in that：In step b The polymer coating of coating is polyvinyl alcohol, polyethyleneimine, PLA, polyacrylic acid or poly- (2- alkyl -2- oxazolines).
8. polysulfonamide nanofiltration according to claim 1 or reverse osmosis composite membrane preparation method, it is characterized in that：It is described layer by layer It is assembled with following several ways：
By porous support membrane alternate immersion in sulfonic acid chloride organic phase solution and polyamine aqueous phase solution；
Uniform alternating spray sulfonic acid chloride organic phase solution and polyamine aqueous phase solution on porous support membrane surface；
Replace spin coating sulfonic acid chloride organic phase solution and polyamine aqueous phase solution in open support film surface using spin coating spin-coating method.
9. polysulfonamide nanofiltration prepared by polysulfonamide nanofiltration according to claim 1 or reverse osmosis composite membrane preparation method Or reverse osmosis composite membrane, the number of plies of the nanofiltration or reverse osmosis composite membrane is 1-50 layers.
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CN111437734B (en) * 2020-05-09 2022-04-19 中国乐凯集团有限公司 Super-hydrophobic solvent-resistant composite nanofiltration membrane and preparation method thereof
CN114432903A (en) * 2020-11-06 2022-05-06 中国石油化工股份有限公司 Composite membrane with acid resistance and preparation method and application thereof
CN112642305A (en) * 2021-01-12 2021-04-13 天津工业大学 Acid-resistant composite nanofiltration membrane and preparation method thereof
CN113856501A (en) * 2021-09-29 2021-12-31 中国科学院过程工程研究所 Composite nanofiltration membrane and preparation method and application thereof
CN115253699A (en) * 2022-07-18 2022-11-01 浙江工业大学 Preparation method of high-permeability reverse osmosis membrane
CN115253699B (en) * 2022-07-18 2024-05-03 浙江工业大学 Preparation method of high-permeability reverse osmosis membrane
CN117654288A (en) * 2024-02-01 2024-03-08 蓝星（杭州）膜工业有限公司 Composite membrane and preparation method and application thereof
CN117654288B (en) * 2024-02-01 2024-04-19 蓝星（杭州）膜工业有限公司 Composite membrane and preparation method and application thereof

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