CN102008900A - Method for assembling multilayer composite separation membrane based on coordination effect - Google Patents
Method for assembling multilayer composite separation membrane based on coordination effect Download PDFInfo
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Abstract
The invention discloses a method for assembling a multilayer compound separation membrane based on coordination effect, belonging to the technical field of membrane separation. The method comprises the steps of: preprocessing a supporting body to ensure that the surface of the supporting body has functional groups which can have the coordination effect with transition metal ions; filtering the transition metal ions/polyelectrolyte mixed liquor through static adsorption or dynamic filtration; assembling a polymer with functional groups which can have the coordination effect with transition metals through static adsorption or dynamic filtration; and repeating over and over again to form the ultrathin multilayer composite membrane. The method can obtain the separation membrane with good performance after a plurality of layers are assembled, and overcomes the defect that the ultrathin membrane is easy to strip.
Description
Technical field
The present invention relates to a kind of assemble method, belong to the membrane separation technique field based on coordination MULTILAYER COMPOSITE diffusion barrier.
Background technology
Membrane separation technique is efficient, energy-conservation, is playing the part of important role in many industries.Composite membrane the is integrated porous permeability of support membrane and the efficient selective of separating layer is the important diffusion barrier kind of a class.In the composite membrane preparation field, ultra-thinization of selective separation layer is one of main difficult problem wherein.Utilize the polyelectrolyte membrane of layer upon layer electrostatic adsorption technology (LbL) assembling of alternating deposit to realize the nanoscale of film thickness and structure is regulated and control by the party number and other assembling condition that change polyelectrolyte.Polyelectrolyte claims polyion again, is meant the macromolecule that has many ionogenic ionic groups in main chain or side chain.The macromolecule that polyelectrolyte can be divided into polycation, polyanion and have the disassociation group of both positive and negative electric charge, i.e. Amphiphatic high polymer electrolyte.At present, constructing as the polyelectrolyte multilayer film of diffusion barrier is the film forming driving force with the electrostatic adsorption power between lotus opposite charges polyion substantially all, because a little less than layer and the electrostatic force between the layer compare chemical bond and want, therefore, during as diffusion barrier, long-time stability remain further to be improved.In addition, based on the used solvent polarity of the self-assembling technique of electrostatic adsorption power very big (being generally water), but quite a few polymer is arranged owing to do not contain charged group, water insoluble, so can not realize film forming with the Electrostatic Absorption package technique, therefore, development is constructed very necessity of multilayer film based on other driving force between polymer.
Summary of the invention
The object of the present invention is to provide a kind of new method of on porous supporting body, utilizing transition metal and polymer complex effect to construct the MULTILAYER COMPOSITE diffusion barrier.Utilize this assemble method of the present invention to construct multilayer film based on coordination MULTILAYER COMPOSITE diffusion barrier, can realize ultra-thinization of selective separation layer, improve the stability of composite membrane, effectively constituents for suppressing obtains high performance diffusion barrier to the transition swelling of membrane material.
Principle of the present invention is: at first supporter is carried out preliminary treatment, make its surface have can with the functional group of transition metal ions generation coordination, then by static absorption or dynamic filtration transition metal ions/polyelectrolyte mixed liquor, static again absorption or dynamic filtration assembling have can with the polymer of transition metal generation coordination functional group, repeated multiple times just can form ultra-thin multilayer complex films.
The invention provides a kind of assemble method, it is characterized in that, may further comprise the steps based on coordination MULTILAYER COMPOSITE diffusion barrier:
(1) ratio that equates according to positive and negative charge is dissolved in polyanion electrolyte and transition-metal cation in the deionized water, is made into the preparation liquid A of mass fraction 0.1%-2%; Can be dissolved in the solvent C with the polymer B of transition metal generation coordination, be made into mass fraction 0.1%-2% preparation liquid D; The preparation liquid standing and defoaming;
(2) organic porous films is carried out preliminary treatment (as plasma treatment, hydrolysis process, radiation treatment etc.), its surperficial precoating layer can with the polymer B of transition metal generation coordination;
(3) 0～1.0MPa pressure or-0.02～-suction function of 0.09MPa under, the preparation liquid A of step (1) is adsorbed or dynamic filtration 5s～3600s at the organic porous films surface static, make the functional group on polyelectrolyte guiding transition metal ions and film surface that coordination take place, thereby be deposited on the skin of organic porous films;
(4) organic porous films is clean with rinsed with deionized water, in 30～100 ℃ of scopes, dry;
(5) 0～1.0MPa pressure or-0.02～-suction function of 0.09MPa under, the preparation liquid D of step (1) is deposited or dynamic filtration 5s～3600s at the organic porous films surface static, make the functional group of polymer and the transition metal generation coordination on film surface, thereby be deposited on the outermost layer of organic porous films;
(6) organic porous films is clean with the solvent C rinsing, in 30～100 ℃ of scopes, dry or dry;
(7) repeat (3) to (6) just can realize multilayer complex films on organic porous supports assembling.
In the present invention, described polymer B be have can with all possible polymer of transition metal generation coordination functional group, surfactant as modification, inorganic salts etc., as the Diphosphonate compound, the polymer that contains phosphate group, poly 4 vinyl pyridine (P4VP), polymine (PEI), polyene propyl group sal-ammoniac (PAH), diallyl dimethyl ammoniumchloride (PDDA), the polyvinyl chlorimide, shitosan (CS), polyvinylamine (PVAM), polyvinyl-4-alkyl pyridinium chloride; The characteristics of described polyanion electrolyte are to have electronegative functional group on long-chain or the side chain, as sulfonic group, carboxyl, hydroxyl, or the like, polyacrylic acid (PAA) is arranged, polyvinyl sulfuric acid salt (PVS), dextran sulfate (DEX), kayexalate (PSS), SPSF (SPSF), sulfonated polyether sulfone (SPES), sodium alginate, cellulose acetate, sulfonated cellulose, carboxymethyl cellulose, poly 4 vinyl pyridine (P4VP), polymine (PEI), polyene propyl group sal-ammoniac (PAH), diallyl dimethyl ammoniumchloride (PDDA), polyvinyl chlorimide, shitosan (CS), polyvinylamine (PVAM), polyvinyl-4-alkyl pyridinium chloride; Described transition metal is all transition metals in the periodic table of elements, as cobalt, copper, nickel, silver, zirconium, cadmium etc.; Described solvent C can be water, methyl alcohol, ethanol, propyl alcohol, butanols, N, dinethylformamide (DMF), N, N-dimethylacetylamide (DMAc), oxolane, furans etc.
In the present invention, described organic porous films is NF membrane, milipore filter or micro-filtration membrane, the membrane material of described organic porous films is organic polymer films and organic inorganic hybridization film, the kit form of described organic porous films is tubular membrane, hollow-fibre membrane, flat sheet membrane or rolled film, and the membrane aperture of described organic porous films is between 1 nanometer to 100 micron.
The invention belongs to method based on the self assembly layer by layer of coordination compound polyelectrolyte, promptly at first preliminary treatment is carried out in substrate, make its surface have can with the functional group of transition metal generation coordination, assemble polyelectrolyte and transition metal ions then in the above, again the assembling have can with the polymer of transition metal generation coordination functional group, repeated multiple times just can form ultra-thin compound polyelectrolyte multilayer film.
The principle of technical solution of the present invention is: with polyanion compound/transition metal ions and have and can alternately assemble at substrate surface with the polymer of transition metal generation coordination functional group, based on coordination, assembling becomes the polymer multi-layer film.Because the method makes that the active force between polymeric layer and the layer is a coordination power, is the good diffusion barrier of availability after assembling several layers, and has overcome the defective that ultrathin membrane is easily peeled off.
The specific embodiment
Provide instantiation below the present invention is done detailed explanation.
Embodiment 1
The employing organic porous films is polyacrylonitrile (PAN) material, and form is flat milipore filter, and molecular cut off 20,000, membrane area are 28cm
2The material that the basement membrane top layer is had with transition metal generation coordination functional group is polymine (PEI, molecular weight are 60,000), and used polyanion composite materials is kayexalate (PSS, molecular weight is 70,000), transition-metal cation is divalence cobalt (Co
2+Cobalt nitrate hexahydrate), have to be poly 4 vinyl pyridine (P4VP with the polymeric material of transition-metal cation generation coordination functional group, molecular weight is 60,000), polymine is dissolved in the deionized water, kayexalate and cobalt nitrate hexahydrate are dissolved in the deionized water, and poly 4 vinyl pyridine is dissolved in the ethanol.
Assembling condition and method:
(1) polymine is made into the solution 500ml of 0.5wt% with deionized water; With deionized water kayexalate is made into the solution 500ml of 0.62wt%, adds the 2.1815g cobalt nitrate hexahydrate again; Poly 4 vinyl pyridine is made into the solution 500ml of 0.23wt% with ethanol;
(2) for making polyacrylonitrile ultrafiltration film surface absorption polymine, earlier to the polyacrylonitrile ultrafiltration film processing that is hydrolyzed; The polypropylene screen milipore filter is immersed 30min in the 2mol/LNaOH aqueous solution, 65 ℃ of constant temperature;
(3) taking out diaphragm is 7 with rinsed with deionized water to pH value, and in the ultrafiltration cup of packing into, the polyethyleneimine: amine aqueous solution is at the film upstream side, the 0.1MPa that pressurizes, and time 30min, face dynamically adsorb PEI;
(4) take out the diaphragm rinsed with deionized water, 40 ℃ of oven dry down;
(5) diaphragm is packed in the ultrafiltration cup, the mixed aqueous solution of kayexalate and cobalt nitrate hexahydrate is at the film upstream side, pressurization 0.1MPa, and time 30min, face dynamically adsorb PSS (Co)
1/2
(6) take out the diaphragm rinsed with deionized water, 40 ℃ of oven dry down;
(7) diaphragm is packed in the ultrafiltration cup, the ethanolic solution of poly-tetrem thiazolinyl pyridine is at the film upstream side, pressurization 0.1MPa, and time 30min, face dynamically adsorb P4VP;
(8) take out diaphragm ethanol rinsing, 40 ℃ of oven dry down;
(9) repeat (5) to (8) and just can realize polymer multi-layer film (PSS (Co) on organic porous polypropylene nitrile flat sheet membrane
1/2/ P4VP)
nAssembling (n is the number of plies).
The polymer multi-layer film of above-mentioned assembling is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: the polymer multi-layer film is 2 layers, and the material liquid ethanol content is the ethanol/water system of 95wt%, 60 ℃ of experimental temperatures, film downstream pressure 100Pa.
Recording the infiltration evaporation film properties is: permeation flux 293.27g/ (m
2H), be 99.5% through water content in the liquid, separation factor is 3781.
Embodiment 2
The employing organic porous films is polyacrylonitrile (PAN) material, and form is flat milipore filter, and molecular cut off 20,000, membrane area are 28cm
2, the material that the basement membrane top layer is had with transition metal generation coordination functional group is polymine (PEI, molecular weight are 60,000), and used polyanion composite materials is kayexalate (PSS, molecular weight are 70,000), and transition metal is cupric (Cu
2+Copper chloride dihydrate), have to be poly 4 vinyl pyridine (P4VP with the polymeric material of transition metal generation coordination functional group, molecular weight is 60,000), polymine is dissolved in the deionized water, kayexalate and copper chloride dihydrate are dissolved in the deionized water, and poly 4 vinyl pyridine is dissolved in the ethanol.
Assembling condition and method:
(1) polymine is made into the solution 500ml of 0.3wt% with deionized water; With deionized water kayexalate is made into the solution 500ml of 0.56wt%, adds the 1.1235g copper chloride dihydrate again; Poly 4 vinyl pyridine is made into the solution 500ml of 0.21wt% with ethanol;
(2) for making polyacrylonitrile ultrafiltration film surface absorption polymine, earlier polyacrylonitrile ultrafiltration film is hydrolyzed; The polypropylene screen milipore filter is immersed 30min in the 2mol/L NaOH aqueous solution, 65 ℃ of constant temperature;
(3) taking out diaphragm is 7 with rinsed with deionized water to pH value, and in the ultrafiltration cup of packing into, the polyethyleneimine: amine aqueous solution is at the film upstream side, the 0.2MPa that pressurizes, and time 30min, face dynamically adsorb PEI;
(4) take out the diaphragm rinsed with deionized water, 20 ℃ of oven dry down;
(5) diaphragm is packed in the ultrafiltration cup, the mixed aqueous solution of kayexalate and copper chloride dihydrate is at the film upstream side, pressurization 0.2MPa, and time 30min, face dynamically adsorb PSS (Cu)
1/2
(6) take out the diaphragm rinsed with deionized water, 20 ℃ of oven dry down;
(7) diaphragm is packed in the ultrafiltration cup, the ethanolic solution of poly-tetrem thiazolinyl pyridine is at the film upstream side, pressurization 0.2MPa, and time 30min, face dynamically adsorb P4VP;
(8) take out diaphragm ethanol rinsing, 20 ℃ of oven dry down;
(9) repeat (5) to (8) and just can realize polymer multi-layer film (PSS (Cu) on organic porous polypropylene nitrile flat sheet membrane
1/2/ P4VP)
nAssembling.
The polymer multi-layer film of above-mentioned assembling is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: the polymer multi-layer film is 5 layers, and the material liquid ethanol content is the ethanol/water system of 95wt%, 60 ℃ of experimental temperatures, film downstream pressure 100Pa.
Recording the infiltration evaporation film properties is: permeation flux 295.82g/ (m
2H), be 98.64% through water content in the liquid, separation factor is 1378.06.
Specific embodiment 3
Adopt to do/wetting phase transformation approach spinning uni-endodermis doughnut support membrane, polyacrylonitrile (PAN) material, internal diameter 1.1mm, molecular cut off 60000, make the doughnut endodermis have material polymine (PEI, molecular weight are 60,000) with transition metal generation coordination functional group, used polyanion composite materials is kayexalate (PSS, molecular weight is 70,000), transition metal is divalence cobalt (Co
2+Cobalt nitrate hexahydrate), have to be poly 4 vinyl pyridine (P4VP with the polymeric material of transition metal generation coordination functional group, molecular weight is 60,000), polymine is dissolved in the deionized water, kayexalate and cobalt nitrate hexahydrate are dissolved in the deionized water, and poly 4 vinyl pyridine is dissolved in the ethanol.
Assembling condition and method:
(1) polymine is made into the solution 500ml of 0.6wt% with deionized water; With deionized water kayexalate is made into the solution 500ml of 0.75wt%, adds the 2.345g cobalt nitrate hexahydrate again; Poly 4 vinyl pyridine is made into the solution 500ml of 0.35wt% with ethanol;
(2) for making polyacrylonitrile hollow-fibre membrane endodermis absorption polymine, earlier hollow-fibre membrane is hydrolyzed: hollow-fibre membrane is immersed 30min in the 2mol/LNaOH aqueous solution, 65 ℃ of constant temperature;
(3) taking out hollow-fibre membrane is 7 with rinsed with deionized water to pH value, 50 ℃ of oven dry down;
(4) hollow-fibre membrane is packed in the lucite tube, two ends epoxy resin end-blocking is made hollow-fiber module;
(5) utilize circulating pump that polymine solution is pumped into the hollow-fibre membrane inner chamber, apply in the fiber outside-negative pressure of 0.08MPa, aspirate 40min, make polymine be trapped and adsorb, form functional group's enriched layer at the fiber inner surface;
(6) utilize circulating pump that deionized water is pumped into the hollow-fibre membrane inner chamber, the flushing endodermis dries up under 50 ℃ then;
(7) utilize circulating pump that the mixed aqueous solution of kayexalate and cobalt nitrate hexahydrate is pumped into doughnut basement membrane inner chamber, apply in the fiber outside-negative pressure of 0.08MPa, aspirate 40min, make PSS (Co)
1/2Be deposited on skin with the PEI layer by coordination;
(8) utilize circulating pump that deionized water is pumped into doughnut basement membrane inner chamber, the flushing endodermis dries up under 50 ℃ then;
(9) ethanolic solution that utilizes circulating pump will gather tetrem thiazolinyl pyridine pumps into the hollow-fibre membrane inner chamber, applies in the fiber outside-negative pressure of 0.08MPa, aspirates 40min, makes P4VP and PSS (Co)
1/2Layer is deposited on outermost layer by coordination;
(10) utilize circulating pump that ethanol is pumped into the hollow-fibre membrane inner chamber, the flushing endodermis dries up under 50 ℃ then;
(11) repeat (7) to (10) and just can realize (the PSS (Co) of polymer multi-layer film on organic porous hollow fiber membrane
1/2/ P4VP)
nAssembling (n is the number of plies).
The doughnut polymer multi-layer film of above-mentioned assembling is carried out the infiltration evaporation performance test, and test condition is: the polymer multi-layer film is 3 layers, and the material liquid ethanol content is the ethanol/water system of 95wt%, 60 ℃ of experimental temperatures, film downstream pressure 100Pa.
Recording the infiltration evaporation film properties is: permeation flux 250.82g/ (m
2H), be 98.69% through water content in the liquid, separation factor is 1431.38.
Specific embodiment 4
The employing organic porous films is polyacrylonitrile (PAN) material, and form is flat milipore filter, and molecular cut off 20,000, membrane area are 28cm
2, the material that the basement membrane top layer is had with transition metal generation coordination functional group is polymine (PEI, molecular weight are 60,000), and used polyanion composite materials is polyacrylic acid (PAA, molecular weight are 4,000,000), and transition metal is divalence cobalt (Co
2+Cobalt nitrate hexahydrate), having can be poly dimethyl two propylene ammonium chloride (PDDA with the polymeric material of transition metal generation coordination functional group, molecular weight is 450,000), polymine is dissolved in the deionized water, polyacrylic acid and cobalt nitrate hexahydrate are dissolved in the deionized water, and poly dimethyl two propylene chloride leaches are at N, in the dinethylformamide (DMF).
Assembling condition and method:
(1) polymine is made into the solution 500ml of 0.6wt% with deionized water; With deionized water polyacrylic acid (PAA) is made into the solution 500ml of 0.7wt%, adds the 3.34g cobalt nitrate hexahydrate again; Poly dimethyl two propylene ammonium chlorides are made into the solution 500ml of 0.35wt% with DMF;
(2) for making polyacrylonitrile ultrafiltration film surface absorption polymine, earlier polyacrylonitrile ultrafiltration film is hydrolyzed: the polypropylene screen milipore filter is immersed 35min in the 2mol/LNaOH aqueous solution, 60 ℃ of constant temperature;
(3) taking out diaphragm is 7 with rinsed with deionized water to pH value, and in the ultrafiltration cup of packing into, the polyethyleneimine: amine aqueous solution is at the film upstream side, the 0.15MPa that pressurizes, and time 20min, face dynamically adsorb PEI;
(4) take out the diaphragm rinsed with deionized water, 60 ℃ of oven dry down;
(5) diaphragm is packed in the ultrafiltration cup, the mixed aqueous solution of polyacrylic acid and cobalt nitrate hexahydrate is at the film upstream side, pressurization 0.15MPa, and time 20min, face dynamically adsorb PAA (Co)
1/2
(6) take out the diaphragm rinsed with deionized water, 60 ℃ of oven dry down;
(7) diaphragm is packed in the ultrafiltration cup, the DMF solution of poly dimethyl two propylene ammonium chlorides is at the film upstream side, pressurization 0.15MPa, and time 20min, face dynamically adsorb PDDA;
(8) take out diaphragm DMF rinsing, 60 ℃ of oven dry down;
(9) repeat (5) to (8) and just can realize polymer multi-layer film (PAA (Co) on organic porous polypropylene nitrile flat sheet membrane
1/2/ PDDA)
nAssembling (n is the number of plies).
The polymer multi-layer film of above-mentioned assembling is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: the polymer multi-layer film is 4 layers, the material liquid t butanol content is the butanol/water system of 95wt%, 50 ℃ of experimental temperatures, film downstream pressure 100Pa.
Recording the infiltration evaporation film properties is: permeation flux 393.27g/ (m
2H), be 99.73% through water content in the liquid, separation factor is 3781.
Specific embodiment 5
The employing organic porous films is polysulfones (PS) material, and form is flat milipore filter, and molecular cut off 20,000, membrane area are 28cm
2, the material that the basement membrane top layer is had with transition metal generation coordination functional group is polymine (PEI, molecular weight are 60,000), and used polyanion composite materials is kayexalate (PSS, molecular weight are 70,000), and transition metal is cupric (Cu
2+Copper chloride dihydrate), have to be poly 4 vinyl pyridine (P4VP with the polymeric material of transition metal generation coordination functional group, molecular weight is 60,000), polymine is dissolved in the deionized water, kayexalate and copper chloride dihydrate are dissolved in the deionized water, and poly 4 vinyl pyridine is dissolved in the ethanol.
Assembling condition and method:
(1) polymine is made into the solution 500ml of 0.5wt% with deionized water; With deionized water kayexalate is made into the solution 500ml of 0.62wt%, adds the 1.2786g copper chloride dihydrate again; Poly 4 vinyl pyridine is made into the solution 500ml of 0.23wt% with ethanol;
(2) polysulphone super-filter membrane is carried out plasma treatment, the surface is electronegative, makes polysulphone super-filter membrane surface absorption polymine;
(3) with in the membrane excess of imports filter bowl on chip, the polyethyleneimine: amine aqueous solution is at the film upstream side, pressurization 0.5MPa, and time 40min, face dynamically adsorb PEI;
(4) take out the diaphragm rinsed with deionized water, 70 ℃ of oven dry down;
(5) diaphragm is packed in the ultrafiltration cup, the mixed aqueous solution of kayexalate and copper chloride dihydrate is at the film upstream side, pressurization 0.5MPa, and time 40min, face dynamically adsorb PSS (Cu)
1/2
(6) take out the diaphragm rinsed with deionized water, 70 ℃ of oven dry down;
(7) diaphragm is packed in the ultrafiltration cup, the ethanolic solution of poly 4 vinyl pyridine is at the film upstream side, pressurization 0.5MPa, and time 40min, face dynamically adsorb P4VP;
(8) take out diaphragm ethanol rinsing, 70 ℃ of oven dry down;
(9) repeat (5) to (8) and just can realize polymer multi-layer film (PSS (Cu) on organic porous polysulfones flat sheet membrane
1/2/ P4VP)
nAssembling.
The polymer multi-layer film of above-mentioned assembling is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: the polymer multi-layer film is 6 layers, the material liquid isopropanol content is the isopropanol system of 95wt%, 60 ℃ of experimental temperatures, film downstream pressure 100Pa.
Recording the infiltration evaporation film properties is: permeation flux 350.82g/ (m
2H), be 99.86% through water content in the liquid, separation factor is 13552.43.
Specific embodiment 6
The employing organic porous films is polyacrylonitrile (PAN) material, and form is flat milipore filter, and molecular cut off 20,000, membrane area are 28cm
2, the material that the basement membrane top layer is had with transition metal generation coordination functional group is polymine (PEI, molecular weight are 60,000), and used polyanion composite materials is kayexalate (PSS, molecular weight are 70,000), and transition metal is divalence cobalt (Co
2+Cobalt nitrate hexahydrate), have to be poly 4 vinyl pyridine (P4VP with the polymeric material of transition metal generation coordination functional group, molecular weight is 60,000), polymine is dissolved in the deionized water, kayexalate and cobalt nitrate hexahydrate are dissolved in the deionized water, and poly 4 vinyl pyridine is dissolved in the oxolane.
Assembling condition and method:
(1) polymine is made into the solution 500ml of 0.5wt% with deionized water; With deionized water kayexalate is made into the solution 500ml of 0.62wt%, adds the 2.1815g cobalt nitrate hexahydrate again; Poly 4 vinyl pyridine is made into the solution 500ml of 0.23wt% with ethanol;
(2) for making polyacrylonitrile ultrafiltration film surface absorption polymine, earlier to polyacrylonitrile ultrafiltration film processings that be hydrolyzed, with 30min in the polypropylene screen milipore filter immersion 2mol/L NaOH aqueous solution, 65 ℃ of constant temperature;
(3) taking out diaphragm is 7 with rinsed with deionized water to pH value, and in the ultrafiltration cup of packing into, the polyethyleneimine: amine aqueous solution is at the film upstream side, the 0.1MPa that pressurizes, and time 30min, face dynamically adsorb PEI;
(4) take out the diaphragm rinsed with deionized water, 40 ℃ of oven dry down;
(5) diaphragm is packed in the ultrafiltration cup, the mixed aqueous solution of kayexalate and cobalt nitrate hexahydrate is at the film upstream side, pressurization 0.1MPa, and time 30min, face dynamically adsorb PSS (Co)
1/2
(6) take out the diaphragm rinsed with deionized water, 40 ℃ of oven dry down;
(7) diaphragm is packed in the ultrafiltration cup, the tetrahydrofuran solution of poly-tetrem thiazolinyl pyridine is at the film upstream side, pressurization 0.1MPa, and time 30min, face dynamically adsorb P4VP;
(8) take out diaphragm oxolane rinsing, 40 ℃ of oven dry down;
(9) repeat (5) to (8) and just can realize polymer multi-layer film (PSS (Co) on organic porous polypropylene nitrile flat sheet membrane
1/2/ P4VP)
nAssembling (n is the number of plies).
The polymer multi-layer film of above-mentioned assembling is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: the polymer multi-layer film is 5 layers, and material liquid benzene content is the benzene/cyclohexane system of 50wt%, 60 ℃ of experimental temperatures, film downstream pressure 100Pa.
Recording the infiltration evaporation film properties is: permeation flux 293.27g/ (m
2H), be 79% through benzene content in the liquid, separation factor is 3.76.
Specific embodiment 7
The employing organic porous films is polyacrylonitrile (PAN) material, and form is flat milipore filter, and molecular cut off 20,000, membrane area are 28cm
2, the material that the basement membrane top layer is had with transition metal generation coordination functional group is polymine (PEI, molecular weight are 60,000), and used polyanion composite materials is kayexalate (PSS, molecular weight are 70,000), and transition metal is divalence cobalt (Co
2+Cobalt nitrate hexahydrate), have to be poly 4 vinyl pyridine (P4VP with the polymeric material of transition metal generation coordination functional group, molecular weight is 60,000), polymine is dissolved in the deionized water, kayexalate and cobalt nitrate hexahydrate are dissolved in the deionized water, and poly 4 vinyl pyridine is dissolved in the ethanol.
Assembling condition and method:
(1) polymine is made into the solution 500ml of 0.5wt% with deionized water; With deionized water kayexalate is made into the solution 500ml of 0.62wt%, adds the 2.1815g cobalt nitrate hexahydrate again; Poly 4 vinyl pyridine is made into the solution 500ml of 0.23wt% with ethanol;
(2) for making polyacrylonitrile ultrafiltration film surface absorption polymine, earlier polyacrylonitrile ultrafiltration film is hydrolyzed, the polypropylene screen milipore filter is immersed 30min in the 2mol/L NaOH aqueous solution, 65 ℃ of constant temperature;
(3) taking out diaphragm is 7 with rinsed with deionized water to pH value, and in the ultrafiltration cup of packing into, the polyethyleneimine: amine aqueous solution is at the film upstream side, the 0.1MPa that pressurizes, and time 30min, face dynamically adsorb PEI;
(4) take out the diaphragm rinsed with deionized water, 40 ℃ of oven dry down;
(5) diaphragm is packed in the ultrafiltration cup, the mixed aqueous solution of kayexalate and cobalt nitrate hexahydrate is at the film upstream side, pressurization 0.1MPa, and time 30min, face dynamically adsorb PSS (Co)
1/2
(6) take out the diaphragm rinsed with deionized water, 40 ℃ of oven dry down;
(7) diaphragm is packed in the ultrafiltration cup, the ethanolic solution of poly-tetrem thiazolinyl pyridine is at the film upstream side, pressurization 0.1MPa, and time 30min, face dynamically adsorb P4VP;
(8) take out diaphragm ethanol rinsing, 40 ℃ of oven dry down;
(9) repeat (5) to (8) and just can realize polymer multi-layer film (PSS (Co) on organic porous polypropylene nitrile flat sheet membrane
1/2/ P4VP)
nAssembling (n is the number of plies).
The polymer multi-layer film of above-mentioned assembling is carried out the ion isolation test in the nanofiltration membrane cisterna, test condition is: the polymer multi-layer film is 2 layers, contain sodium ion, magnesium ion, chlorion and sulfate ion in the material liquid, experimental temperature is a room temperature, and face pressure is 0.6MPa.
Recording separating property is: to the rejection of sodium ion 35%, to the rejection of chlorion 40%, to the rejection of magnesium ion 95%, to the rejection of sulfate ion 96%.
Embodiment 8
The employing organic porous films is polyacrylonitrile (PAN) material, and form is flat milipore filter, and molecular cut off 20,000, membrane area are 28cm
2, the material that the basement membrane top layer is had with transition metal generation coordination functional group is polymine (PEI, molecular weight are 60,000), and used polyanion composite materials is kayexalate (PSS, molecular weight are 70,000), and transition metal is divalence cobalt (Co
2+Cobalt nitrate hexahydrate), have to be poly 4 vinyl pyridine (P4VP with the polymeric material of transition metal generation coordination functional group, molecular weight is 60,000), polymine is dissolved in the deionized water, kayexalate and cobalt nitrate hexahydrate are dissolved in the deionized water, and poly 4 vinyl pyridine is dissolved in the ethanol.
Assembling condition and method:
(1) polymine is made into the solution 500ml of 0.5wt% with deionized water; With deionized water kayexalate is made into the solution 500ml of 0.62wt%, adds the 2.1815g cobalt nitrate hexahydrate again; Poly 4 vinyl pyridine is made into the solution 500ml of 0.23wt% with ethanol;
(2) for making polyacrylonitrile ultrafiltration film surface absorption polymine, earlier polyacrylonitrile ultrafiltration film is hydrolyzed, the polypropylene screen milipore filter is immersed 30min in the 2mol/LNaOH aqueous solution, 65 ℃ of constant temperature;
(3) taking out diaphragm is 7 with rinsed with deionized water to pH value, and in the ultrafiltration cup of packing into, the polyethyleneimine: amine aqueous solution is at the film upstream side, the 0.7MPa that pressurizes, and time 50min, face dynamically adsorb PEI;
(4) take out the diaphragm rinsed with deionized water, 80 ℃ of oven dry down;
(5) diaphragm is packed in the ultrafiltration cup, the mixed aqueous solution of kayexalate and cobalt nitrate hexahydrate is at the film upstream side, pressurization 0.7MPa, and time 50min, face dynamically adsorb PSS (Co)
1/2
(6) take out the diaphragm rinsed with deionized water, 80 ℃ of oven dry down;
(7) diaphragm is packed in the ultrafiltration cup, the ethanolic solution of poly-tetrem thiazolinyl pyridine is at the film upstream side, pressurization 0.7MPa, and time 50min, face dynamically adsorb P4VP;
(8) take out diaphragm ethanol rinsing, 80 ℃ of oven dry down;
(9) repeat (5) to (8) and just can realize polymer multi-layer film (PSS (Co) on organic porous polypropylene nitrile flat sheet membrane
1/2/ P4VP)
nAssembling (n is the number of plies).
The polymer multi-layer film of above-mentioned assembling is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: the polymer multi-layer film is 6 layers, and the material liquid ethanol content is the ethanol/water system of 95wt%, 60 ℃ of experimental temperatures, film downstream pressure 100Pa.
Recording the infiltration evaporation film properties is: permeation flux 293.27g/ (m
2H), be 99.5% through water content in the liquid, separation factor is 3781.
Embodiment 9
The employing organic porous films is polyether sulfone (PES) material, and form is flat milipore filter, and molecular cut off 20,000, membrane area are 28cm
2, the material that the basement membrane top layer is had with transition metal generation coordination functional group is poly diallyldimethylammonium chloride (PAH, molecular weight are 5.6 ten thousand), and used polyanion composite materials is SPSF (SPSF, molecular weight are 70,000), and transition metal is divalence cobalt (Co
2+Cobalt nitrate hexahydrate), have to be polyvinylamine (PVAM with the polymeric material of transition metal generation coordination functional group, molecular weight is 60,000), poly diallyldimethylammonium chloride is dissolved in the deionized water, SPSF and cobalt nitrate hexahydrate are dissolved in the deionized water, and polyvinylamine is dissolved among the DMF.
Assembling condition and method:
(1) poly diallyldimethylammonium chloride is made into the solution 500ml of 0.5wt% with deionized water; With deionized water SPSF is made into the solution 500ml of 0.62wt%, adds the 2.1815g cobalt nitrate hexahydrate again; Polyvinylamine is made into the solution 500ml of 0.23wt% with DMF;
(2) for making polyether sulfone surface absorption poly diallyldimethylammonium chloride, earlier poly (ether-sulfone) ultrafiltration membrane is carried out plasma treatment, electronegative;
(3) diaphragm is packed in the ultrafiltration cup, the poly diallyldimethylammonium chloride aqueous solution is at the film upstream side, pressurization 0.1MPa, and time 30min, face dynamically adsorb PAH;
(4) take out the diaphragm rinsed with deionized water, 50 ℃ of oven dry down;
(5) diaphragm is packed in the ultrafiltration cup, the mixed aqueous solution of SPSF and cobalt nitrate hexahydrate is at the film upstream side, pressurization 0.3MPa, and time 20min, face dynamically adsorb SPSF (Co);
(6) take out the diaphragm rinsed with deionized water, 50 ℃ of oven dry down;
(7) diaphragm is packed in the ultrafiltration cup, the DMF solution of polyvinylamine is at the film upstream side, pressurization 0.1MPa, and time 30min, face dynamically adsorb PVAM;
(8) take out diaphragm DMF rinsing, 50 ℃ of oven dry down;
(9) repeat (5) to (8) and just can realize polymer multi-layer film (SPSF (Co)/PVAM) on organic porous polyether sulfone flat sheet membrane
nAssembling (n is the number of plies).
The polymer multi-layer film of above-mentioned assembling is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: the polymer multi-layer film is 3 layers, and the material liquid ethanol content is the ethanol/water system of 95wt%, 60 ℃ of experimental temperatures, film downstream pressure 100Pa.
Recording the infiltration evaporation film properties is: permeation flux 293.27g/ (m
2H), be 99.5% through water content in the liquid, separation factor is 3781.
Claims (7)
1. the assemble method based on coordination MULTILAYER COMPOSITE diffusion barrier is characterized in that, may further comprise the steps:
(1) ratio that equates according to positive and negative charge is dissolved in polyanion electrolyte and transition-metal cation in the deionized water, is made into the preparation liquid A of mass fraction 0.1%-2%; Can be dissolved in the solvent C with the polymer B of transition metal generation coordination, be made into mass fraction 0.1%-2% preparation liquid D; The preparation liquid standing and defoaming;
(2) organic porous films is carried out preliminary treatment, its surperficial precoating layer can with the polymer B of transition metal generation coordination;
(3) 0～1.0MPa pressure or-0.02～-suction function of 0.09MPa under, the preparation liquid A of step (1) is adsorbed or dynamic filtration 5s～3600s at the organic porous films surface static, make the functional group on polyelectrolyte guiding transition metal ions and film surface that coordination take place, thereby be deposited on the skin of organic porous films;
(4) organic porous films is clean with rinsed with deionized water, in 30～100 ℃ of scopes, dry;
(5) 0～1.0MPa pressure or-0.02～-suction function of 0.09MPa under, the preparation liquid D of step (1) is deposited or dynamic filtration 5s～3600s at the organic porous films surface static, make the functional group of polymer and the transition metal generation coordination on film surface, thereby be deposited on the outermost layer of organic porous films;
(6) organic porous films is clean with the solvent C rinsing, in 30～100 ℃ of scopes, dry or dry;
(7) repeat (3) to (6) just can realize multilayer complex films on organic porous supports assembling.
2. according to the described a kind of assemble method of claim 1 based on coordination MULTILAYER COMPOSITE diffusion barrier, it is characterized in that, described solvent C can be water, methyl alcohol, ethanol, propyl alcohol, butanols, N, dinethylformamide (DMF), N, N-dimethylacetylamide (DMAc), oxolane, furans.
3. according to the described a kind of assemble method of claim 1 based on coordination MULTILAYER COMPOSITE diffusion barrier, it is characterized in that, described organic porous films is NF membrane, milipore filter or micro-filtration membrane, the membrane material of organic porous films is organic polymer films or organic inorganic hybridization film, the kit form of organic porous films is tubular membrane, hollow-fibre membrane, flat sheet membrane or rolled film, and the membrane aperture of organic porous films is between 1 nanometer to 100 micron.
4. according to the described a kind of assemble method of claim 1, it is characterized in that based on coordination MULTILAYER COMPOSITE diffusion barrier, polymer B for have can with transition metal generation coordination functional polymer.
5. according to the described a kind of assemble method of claim 1, it is characterized in that described polyanion electrolyte is to have electronegative functional group on long-chain or the side chain based on coordination MULTILAYER COMPOSITE diffusion barrier.
6. according to the described a kind of assemble method of claim 4 based on coordination MULTILAYER COMPOSITE diffusion barrier, it is characterized in that polymer B is the Diphosphonate compound, contain the polymer of phosphate group, poly 4 vinyl pyridine (P4VP), polymine (PEI), polyene propyl group sal-ammoniac (PAH), diallyl dimethyl ammoniumchloride (PDDA), the polyvinyl chlorimide, shitosan (CS), polyvinylamine (PVAM), polyvinyl-4-alkyl pyridinium chloride.
7. according to the described a kind of assemble method of claim 5 based on coordination MULTILAYER COMPOSITE diffusion barrier, it is characterized in that, described polyanion electrolyte is polyacrylic acid (PAA), polyvinyl sulfuric acid salt (PVS), dextran sulfate (DEX), kayexalate (PSS), SPSF (SPSF), sulfonated polyether sulfone (SPES), sodium alginate, cellulose acetate, sulfonated cellulose, carboxymethyl cellulose, poly 4 vinyl pyridine (P4VP), polymine (PEI), polyene propyl group sal-ammoniac (PAH), diallyl dimethyl ammoniumchloride (PDDA), the polyvinyl chlorimide, shitosan (CS), polyvinylamine (PVAM), polyvinyl-4-alkyl pyridinium chloride.
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