CN104248918B - A kind of method that semi-intercrossing network method prepares hydrophilic anti-pollution composite hyperfiltration membrane - Google Patents
A kind of method that semi-intercrossing network method prepares hydrophilic anti-pollution composite hyperfiltration membrane Download PDFInfo
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Abstract
The present invention relates to a kind of method that semi-intercrossing network method prepares hydrophilic anti-pollution composite hyperfiltration membrane, dried membrane material and additive are joined in organic solvent, stirring and dissolving, form mixed solution；In above-mentioned mixed solution, add lithium chloride, then add the hydrophilic macromolecule containing hydroxyl, the most swelling, dissolving, add cross-linking agent and carry out cross-linking reaction, after cross-linking reaction completes, be filtered to remove impurity, vacuumizing and defoaming obtains casting solution；Basement membrane cross-linking agent is carried out dipping pretreatment, knifing machine fixes pretreated basement membrane, casting solution is scratched membrane surface, is immersed in film forming in coagulating bath by scraping the basement membrane scribbling casting solution, make the flat plate ultrafiltration composite membrane with half interpenetrating network structure.Preparation method of the present invention, the ultrafilter membrane prepared has good hydrophilic and mechanical property, and mechanical strength is high, anti-pollution, and pure water flux is high, reduces cost of sewage disposal, and preparation method is suitable for industrialized production.
Description
Technical field
The present invention relates in material science and field of environment protection, for the manufacture method of the polymeric membrane of reusing sewage,
A kind of method that specifically semi-intercrossing network method prepares hydrophilic anti-pollution composite hyperfiltration membrane.Belong to flat plate ultrafiltration composite membrane
Technology of preparing.
Background technology
Membrane separating process is the subjects cross coupled such as material science and process engineering science, interpenetrates and produce
Frontier, Ultra filtration membrane process has easy and simple to handle, it is easy to accomplish features such as being continuously separated on a large scale and automatically control, at water
The aspects such as the regeneration of process, waste water process and water resource are widely applied, and Ultra filtration membrane process also apply be applicable to
In the industries such as petrochemical industry, biochemical industry, fine chemistry industry, food medicine, textile printing and dyeing, raw material and product separate, purify and dense
Contracting.
Polysulfones (such as polysulfones, polyether sulfone, benzodiazine polyethersulfone ketone etc.) and fluoropolymer (such as Kynoar etc.)
High comprehensive performance, industrial application ultrafiltration membrane material the most widely, have good mechanical strength and the close property of resistance to compression and
Thermostability, and the advantage such as the good He wide pH range of chemical stability, but it is dirty to there is film in ultrafiltration membrane technique application process
Dye, the problems such as mechanical strength is not enough of film, the generation of these problems wherein major reason is that membrane material itself causes, such as film material
The hydrophobicity of material causes the lyophobic dust in feed liquid to produce non-specific binding with membrane material, and absorption is on film surface and on film surface
Cause the aperture of fenestra to diminish even to block fenestra, cause fouling membrane, cause membrane flux and aquifer yield with constantly assembling in fenestra
Decline rapidly, finally damage film properties, therefore the hydrophilic modifying of material of preparing is particularly important.
The method of membrane material hydrophilic modifying mainly has Physical and chemical method, and Physical has surfactant-modified, surface
Coating modification and the blending and modifying etc. to membrane material；Chemical method has plasma modification, ultraviolet irradiation to excite and uv photo initiated grafting
Polymerization, high-energy irradiation are grafted and introduce hydrophilic functional group's (such as sulfonic group, hydroxyl etc.) by some specific method.
But the method for these membrane material hydrophilic modifyings above-mentioned, or mainly for film modifying surface, along with when running
Between the decay of increase hydrophilic serious；Or needing complex chemical reaction, modified effect is undesirable or industrialization is amplified
Difficulty.
The network structure that semi-intercrossing network is made up of two kinds of polymer, wherein having a kind of polymer is uncrosslinked line style
Molecule, it is interspersed in the another kind of polymer cross-linked, and half interpenetrating network structure can have general physical blending simultaneously, connect
Branch, the excellent properties of block polymer, the introducing of this structure is remarkably improved mechanical property and the heat stability of film.Utilize half
Interpenetrating networks method prepared high-performance proton exchange membrane (Chinese patent CN200810041474.5 and
CN200910048260.5) report, but in the hydrophilic anti-pollution Compound Ultrafiltration film preparation with pressure as drive pattern
Application but rarely has report.
Summary of the invention
For defect present in prior art, it is an object of the invention to provide one semi-intercrossing network method and prepare parent
The method of aqueous antipollution composite hyperfiltration membrane, the ultrafilter membrane using the method to prepare, there is good hydrophilic and mechanical property,
Mechanical strength is high, anti-pollution, and pure water flux is high, reduces cost of sewage disposal, and preparation method is suitable for industrialized production.
For reaching object above, the present invention adopts the technical scheme that:
A kind of method that semi-intercrossing network method prepares hydrophilic anti-pollution composite hyperfiltration membrane, it is characterised in that include with
Lower step:
Using the one in polysulfones or fluoropolymer as membrane material,
Dried membrane material and additive are joined in organic solvent, stirring and dissolving, form mixed solution；
In above-mentioned mixed solution, add lithium chloride, then add the hydrophilic macromolecule containing hydroxyl, the most swelling, molten
Solve,
Adding cross-linking agent and carry out cross-linking reaction, after cross-linking reaction completes, be filtered to remove impurity, vacuumizing and defoaming obtains casting film
Liquid；
Basement membrane cross-linking agent is carried out dipping pretreatment,
Knifing machine fixes pretreated basement membrane, casting solution is scratched membrane surface, will scrape and scribble casting solution
Basement membrane be immersed in film forming in coagulating bath, make the flat plate ultrafiltration composite membrane with half interpenetrating network structure.
On the basis of technique scheme, described polysulfones is polysulfones, polyether sulfone or benzodiazine polyethersulfone ketone；
Described fluoropolymer is Kynoar；
Described basement membrane is polyester non-woven fabric.
On the basis of technique scheme, described additive is water soluble polymer polyvinylpyrrolidone (PVP), gathers
Any one in ethylene glycol (PEG), or described additive is water soluble polymer polyvinylpyrrolidone (PVP), poly-second two
In alcohol (PEG) one of arbitrarily with formic acid, acetic acid, propanoic acid in one of arbitrarily with the combination of arbitrary proportion.
On the basis of technique scheme, described polyvinylpyrrolidone mean molecule quantity is 15,000 to 40,000,
Polyethylene Glycol mean molecule quantity is 6,000 to 20,000.
On the basis of technique scheme, described organic solvent is N,N-dimethylacetamide (DMAC), N, N-diformazan
In base Methanamide (DMF), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide one of arbitrarily.
On the basis of technique scheme, the described hydrophilic macromolecule containing hydroxyl is chitosan, cellulose or poly-
Vinyl alcohol.
On the basis of technique scheme, the molecular weight ranges 100 of chitosan, 000 to 1000,000, deacetylation is big
In 60%；The molecular weight ranges 150,000 to 200,000 of cellulose；The molecular weight ranges 100,000 to 300 of polyvinyl alcohol,
000, alcoholysis degree is more than 70%.
On the basis of technique scheme, described cross-linking agent is formaldehyde, Biformyl, glutaraldehyde, epoxychloropropane, poly-second
In glycol bisglycidyl ether, polyglycerol triglycidyl ether one of arbitrarily.
The method preparing hydrophilic anti-pollution composite hyperfiltration membrane by semi-intercrossing network method, it is characterised in that concrete steps are such as
Under:
1) by mass percentage by dried to 12～20% membrane material, 50～81% are joined with the additive of 5～15%
In organic solvent, stirring and dissolving at 50～70 DEG C, form mixed solution；
2) under agitation, interpolation 1～the lithium chloride of 10% in above-mentioned mixed solution by mass percentage, the most again
Interpolation 1～the hydrophilic macromolecule containing hydroxyl of 5%, the most swelling, dissolving；
3) to step 2) add cross-linking agent in gained mixed solution, continue stirring and carry out cross-linking reaction 6～12 hours, crosslinking
After having reacted, after being filtered to remove impurity, vacuumizing and defoaming obtains casting solution, and the addition of cross-linking agent is film by mass percentage
The 1～10% of the gross mass of material, additive, organic solvent, lithium chloride and the hydrophilic macromolecule containing hydroxyl；
4) it is placed in basement membrane in cross-linking agent solution to soak at least 24 hours and carries out pretreatment；
5) on knifing machine, pretreated basement membrane is fixed, by following parameter adjustment knifing machine: basement membrane walks cloth speed 1.2
～1.5m/s, the dimensional thickness between scraper and basement membrane is 150～180 μm, casting solution is scratched membrane surface, will scrape and scribble
The basement membrane of casting solution is immersed in film forming in coagulating bath, and primary membrane, after washing, protecting hole process, is made and had half interpenetrating network structure
Flat plate ultrafiltration composite membrane.
On the basis of technique scheme, the body lotion that described coagulating bath uses is deionized water.
On the basis of technique scheme, described in there is the flat plate ultrafiltration composite membrane of half interpenetrating network structure be saved in
The glycerine water solution of 20% soaks guarantor hole stand-by.
The method that semi-intercrossing network method of the present invention prepares hydrophilic anti-pollution composite hyperfiltration membrane, uses the method
The ultrafilter membrane of preparation, has good hydrophilic and mechanical property, and mechanical strength is high, anti-pollution, and pure water flux is high, reduces dirt
Cost of water treatment, preparation method is suitable for industrialized production.
The present invention, on the basis of keeping original membrane material premium properties, uses cheap polyester non-woven fabric to do basement membrane, draws
Entering half interpenetrating network structure and strengthen the mechanical strength of composite membrane, the composite membrane of preparation shows stronger hydrophilic, resistance tocrocking
Can significantly improve.
Detailed description of the invention
The method that semi-intercrossing network method of the present invention prepares hydrophilic anti-pollution composite hyperfiltration membrane, including following step
Rapid:
By polysulfones (such as polysulfones, polyether sulfone, benzodiazine polyethersulfone ketone etc.) or fluoropolymer (such as Kynoar
Deng) in one as membrane material,
Dried membrane material and additive are joined in organic solvent, stirring and dissolving, form mixed solution；
In above-mentioned mixed solution, add lithium chloride, then add the hydrophilic macromolecule containing hydroxyl, the most swelling, molten
Solve,
Adding cross-linking agent and carry out cross-linking reaction, after cross-linking reaction completes, be filtered to remove impurity, vacuumizing and defoaming obtains casting film
Liquid；
Polyester non-woven fabric is carried out dipping pretreatment as basement membrane, basement membrane cross-linking agent,
Knifing machine fixes pretreated basement membrane, casting solution is scratched membrane surface, will scrape and scribble casting solution
Basement membrane be immersed in film forming in coagulating bath, make the flat plate ultrafiltration composite membrane with half interpenetrating network structure.
In the present invention, contained the hydrophilic macromolecule (such as chitosan etc., as described below) of hydroxyl by blended addition, profit
Membrane material is made to form half interpenetrating network structure with hydrophilic macromolecule by semi-intercrossing network method；The introducing of half interpenetrating network structure can
Fundamentally change the hydrophilic of ultrafilter membrane, and the interpolation of the masking compositions such as the hydrophilic macromolecule containing hydroxyl can improve super
The anti-microbial property of filter membrane, thus improve the antifouling property of composite membrane from many aspects.It addition, for increasing compound film strength, carrying
The fastness of high coating film forming, the present invention uses cross-linking agent that the basement membrane (polyester non-woven fabric) playing supporting layer effect is carried out pre-place
Reason.
Each component proportion (mass percent) is listed as follows:
Every increasing or decreasing 1% all can be as a selectable specific embodiment in span for each component.
On the basis of technique scheme, specifically comprise the following steps that
1) by mass percentage by dried to 12～20% membrane material, 50～81% are joined with the additive of 5～15%
In organic solvent, stirring and dissolving at 50～70 DEG C, in span, every increasing or decreasing 1 DEG C all can may select as one
Specific embodiment, formed mixed solution；
2) under agitation, interpolation 1～the lithium chloride of 10% in above-mentioned mixed solution by mass percentage, the most again
Interpolation 1～the hydrophilic macromolecule containing hydroxyl of 5%, the most swelling, dissolving；
3) to step 2) add cross-linking agent in gained mixed solution, continue stirring and carry out cross-linking reaction 6～12 hours, taking
In the range of value, every increasing or decreasing 1h all, can be filtered to remove after cross-linking reaction completes as a selectable specific embodiment
After impurity, vacuumizing and defoaming obtains casting solution, and by mass percentage, the addition of cross-linking agent is membrane material, additive, You Jirong
The 1～10% of the gross mass of agent, lithium chloride and the hydrophilic macromolecule containing hydroxyl；
4) it is placed in basement membrane in cross-linking agent solution to soak at least 24 hours and carries out pretreatment；
5) on knifing machine, pretreated basement membrane is fixed, by following parameter adjustment knifing machine: basement membrane walks cloth speed 1.2
～1.5m/s, in span every increasing or decreasing 0.1m/s all can as a selectable specific embodiment, scraper with
Dimensional thickness between basement membrane is 150～180 μm, and in span, every increasing or decreasing 1 μm all can may select as one
Specific embodiment, casting solution is scratched membrane surface, is immersed in film forming in coagulating bath, just by scraping the basement membrane scribbling casting solution
Filming, after washing, protecting hole process, makes the flat plate ultrafiltration composite membrane with half interpenetrating network structure.
In said ratio, membrane material, additive, organic solvent, lithium chloride, the quality of hydrophilic macromolecule containing hydroxyl
The cumulative of percentage ratio should be 100%, the gross mass metering of the mixed solution that the addition of cross-linking agent is then formed by aforementioned component.
On the basis of technique scheme, described additive is water soluble polymer polyvinylpyrrolidone (PVP), gathers
Any one in ethylene glycol (PEG), or described additive is water soluble polymer polyvinylpyrrolidone (PVP), poly-second two
In alcohol (PEG) one of arbitrarily with formic acid, acetic acid, propanoic acid in one of arbitrarily with the combination of arbitrary proportion；
Described polyvinylpyrrolidone mean molecule quantity is 15,000 to 40,000, and Polyethylene Glycol mean molecule quantity is 6,
000 to 20,000.
On the basis of technique scheme, described organic solvent is N,N-dimethylacetamide (DMAC), N, N-diformazan
In base Methanamide (DMF), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide one of arbitrarily.
On the basis of technique scheme, the described hydrophilic macromolecule containing hydroxyl is chitosan, cellulose or poly-
Vinyl alcohol, the molecular weight ranges 100 of chitosan, 000 to 1000,000, deacetylation is more than 60%；The molecular weight ranges of cellulose
150,000 to 200,000；The molecular weight ranges 100 of polyvinyl alcohol, 000 to 300,000, alcoholysis degree is more than 70%.
On the basis of technique scheme, described cross-linking agent is formaldehyde, Biformyl, glutaraldehyde, epoxychloropropane, poly-second
In glycol bisglycidyl ether, polyglycerol triglycidyl ether one of arbitrarily.
On the basis of technique scheme, the body lotion that described coagulating bath uses is deionized water.
On the basis of technique scheme, described in there is the flat plate ultrafiltration composite membrane of half interpenetrating network structure be saved in
The glycerine water solution of 20% soaks guarantor hole stand-by.
The present invention compared with prior art provides the benefit that:
(1) with the polymeric film material in casting solution after the hydrophilic macromolecule containing hydroxyl in the present invention reacts with cross-linking agent
The half interpenetrating network structure that material is formed, makes prepared ultrafiltration composite membrane have good mechanical strength and chemical stability, more
It is important that the antifouling property of reinforcing membrane in terms of hydrophilic, anti-microbial property of the composite membrane prepared by the present invention, extend film
Service life；
(2) preparation method of ultrafiltration composite membrane of the present invention use cross-linking agent the basement membrane playing supporting layer effect is carried out pre-place
Reason, reduces the surface energy of basement membrane, makes coating carry out with crosslinking simultaneously, and the basement membrane having added supporting layer effect is coated with casting solution
Cover the binding strength between material, make the firm difficult drop-off of composite bed；
(3) present invention use polyether sulfone, polysulfones, benzodiazine polyethersulfone ketone and Kynoar one of them with contain
Hydroxyl hydrophilic macromolecule (polyvinyl alcohol, cellulose or chitosan) is blended as material of preparing, on the one hand keeps original polyethers
The premium properties of the materials such as sulfone, polysulfones, benzodiazine polyethersulfone ketone and Kynoar, on the other hand due to hydrophilic containing hydroxyl
The hydrophilic of property macromolecular material, makes prepared film not only have high temperature resistant, chemical-resistant reagent and the feature such as nontoxic, also has
Having good biocompatibility, effluent quality is good, and flux is big, and the preparation method simple process of the present invention, easily operate, can be wide
General it is applied to the water treatment procedures such as chemical industry, medicine, food, environmental protection.
Being below specific embodiment, described embodiment only in order to explain the present invention, is not intended that limitation of the present invention,
The person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
In performance measurement of the present invention, the strainability of film is measured by pure water flux and rejection, and pure water leads to
Measure and be measured by the outer press filtering device of the homemade dead end of laboratory, will scrape after the composite membrane made dries naturally and be cut into circle
Shape diaphragm, puts into first precompressed 30min under 0.15Mpa in ultrafiltration cup, until water flux is basicly stable, the most again under 0.1MPa
Measure the pure water flux of film；Film cutoff performance is measured using bovine serum albumin (BSA) solution of 1g/L as medium；With three grades
Distilled water with lie dripping method DSA100 contact angle instrument (GmbH, Germany) on measure contact angle；Direct by dry film
Observed surface and the fracture morphology of film by XL-30 field emission scanning electron microscope (FEI, USA) after metal spraying；The mechanical strength of film passes through
Burst pressure force test device is measured, and is i.e. slowly increased the pressure being applied on ultrafilter membrane, until film is only broked into, records explosion
Pressure；Fouling membrane degree characterizes with the adsorbance to bovine serum albumin (BSA).
Embodiment 1
By dried 18g polyether sulfone, 9g polyvinylpyrrolidone, it is dissolved into 61gN-methyl pyrrolidone organic solvent
In, stir under the conditions of 70 DEG C, be completely dissolved to polymer,
Continue under agitation to add 7g lithium chloride and 5g cellulose to mixed solution so that it is abundant swelling dissolving,
Adding 7g glutaraldehyde cross-linking to react 12 hours, stand after being filtered to remove impurity, vacuumizing and defoaming prepares casting solution.
Basement membrane non-woven polyester is arranged in glutaraldehyde solution to soak at least 24 hours and carries out pretreatment,
The polyester non-woven fabric dried after pretreatment is installed on knifing machine, adjusts non-woven fabrics and walk cloth speed 1.2m/s, scrape
Dimensional thickness between cutter and basement membrane is that 160 μm carry out knifing, after nascent composite membrane runs in atmosphere, is immersed in 25 DEG C solidifying
Gu film forming in bath water, will scrape after the composite membrane made soaks at least 24 hours in deionized water, the glycerine water solution with 20% soaks
It is standby that bubble protects hole.The performance parameter of made composite membrane is shown in Table 1.
Embodiment 2
Dried 12g polysulfones, 8g Polyethylene Glycol, 2g formic acid are dissolved into 74gN, N-dimethyl acetylamide organic solvent
In, stir under the conditions of 60 DEG C, be completely dissolved to polymer,
Continue under agitation to add 1g lithium chloride and 3g polyvinyl alcohol to mixed solution so that it is abundant swelling dissolving,
Add 1g Polyethylene Glycol bisglycidyl ether cross-linking reaction 6 hours, stand after being filtered to remove impurity, vacuumizing and defoaming
Prepare casting solution.
Basement membrane non-woven polyester is arranged in Polyethylene Glycol bisglycidyl ethereal solution to soak at least 24 hours and carries out pretreatment,
The polyester non-woven fabric dried after pretreatment is installed on knifing machine, adjusts non-woven fabrics and walk cloth speed 1.5m/s, scrape
Dimensional thickness between cutter and basement membrane is that 150 μm carry out knifing, after nascent composite membrane runs in atmosphere, is immersed in 28 DEG C solidifying
Gu film forming in bath water, will scrape after the composite membrane made soaks at least 24 hours in deionized water, the glycerine water solution with 20% soaks
It is standby that bubble protects hole.The performance parameter of made composite membrane is shown in Table 1.
Embodiment 3
By dried 15g benzodiazine polyethersulfone ketone, 5g Polyethylene Glycol, being dissolved into 67gN, dinethylformamide has
In machine solvent, stir under the conditions of 50 DEG C, be completely dissolved to polymer,
Continue under agitation to add 8g lithium chloride and 5g cellulose to mixed solution so that it is abundant swelling dissolving,
Adding 10g glutaraldehyde cross-linking to react 12 hours, stand after being filtered to remove impurity, vacuumizing and defoaming prepares casting solution.
Basement membrane non-woven polyester is arranged in glutaraldehyde solution to soak at least 24 hours and carries out pretreatment,
Pretreated polyester non-woven fabric is installed on knifing machine, adjusts non-woven fabrics and walk cloth speed 1.3m/s, scraper with
Dimensional thickness between basement membrane is that 160 μm carry out knifing, after nascent composite membrane runs in atmosphere, is immersed in the coagulating bath of 28 DEG C
Film forming in water, will scrape after the composite membrane made soaks at least 24 hours in deionized water, and the glycerine water solution with 20% soaks to be protected
Hole is standby.The performance parameter of made composite membrane is shown in Table 1.
Embodiment 4
Dried 20g Kynoar, 9g polyvinylpyrrolidone, 3g propanoic acid are dissolved into 57gN-crassitude
In ketone (NMP) organic solvent, stir under the conditions of 70 DEG C, be completely dissolved to polymer,
Continue under agitation to add 6g lithium chloride and 5g cellulose to mixed solution so that it is abundant swelling dissolving,
Adding 5g epoxychloropropane cross-linking reaction 12 hours, stand after being filtered to remove impurity, vacuumizing and defoaming prepares casting film
Liquid.
Basement membrane non-woven polyester is arranged in epoxychloropropane solution to soak at least 24 hours and carries out pretreatment,
Pretreated polyester non-woven fabric is installed on knifing machine, adjusts non-woven fabrics and walk cloth speed 1.2m/s, scraper with
Dimensional thickness between basement membrane is that 180 μm carry out knifing, after nascent composite membrane runs in atmosphere, is immersed in the coagulating bath of 27 DEG C
Film forming in water, will scrape after the composite membrane made soaks at least 24 hours in deionized water, and the glycerine water solution with 20% soaks to be protected
Hole is standby.The performance parameter of made composite membrane is shown in Table 1.
Embodiment 5
By dried 16g polyether sulfone, 9g polyvinylpyrrolidone, 6g acetic acid to 56gN-methyl pyrrolidone
(NMP), in organic solvent, stir under the conditions of 60 DEG C, be completely dissolved to polymer,
Continue under agitation to add 10g lithium chloride and 3g chitosan to mixed solution so that it is abundant swelling dissolving,
Adding 7g formaldehyde crosslinking to react 10 hours, stand after being filtered to remove impurity, vacuumizing and defoaming prepares casting solution.
Basement membrane non-woven polyester is arranged in formalin to soak at least 24 hours and carries out pretreatment,
Pretreated polyester non-woven fabric is installed on knifing machine, adjusts non-woven fabrics and walk cloth speed 1.2m/s, scraper with
Dimensional thickness between basement membrane is that 160 μm carry out knifing, after nascent composite membrane runs in atmosphere, is immersed in the coagulating bath of 28 DEG C
Film forming in water, will scrape after the composite membrane made soaks at least 24 hours in deionized water, and the glycerine water solution with 20% soaks to be protected
Hole is standby.The performance parameter of made composite membrane is shown in Table 1.
Embodiment 6
By dried 13g benzodiazine polyethersulfone ketone, 4g polyvinylpyrrolidone, 3g acetic acid, it is dissolved into 74gN, N-bis-
In methylacetamide organic solvent, stir under the conditions of 60 DEG C, be completely dissolved to polymer,
Continue under agitation to add 5g lithium chloride and 1g chitosan to mixed solution so that it is abundant swelling dissolving,
Adding 3g formaldehyde crosslinking to react 8 hours, stand after being filtered to remove impurity, vacuumizing and defoaming prepares casting solution.
Basement membrane non-woven polyester is arranged in formalin to soak at least 24 hours and carries out pretreatment,
Pretreated polyester non-woven fabric is installed on knifing machine, adjusts non-woven fabrics and walk cloth speed 1.3m/s, scraper with
Dimensional thickness between basement membrane is that 160 μm carry out knifing, after nascent composite membrane runs in atmosphere, is immersed in the coagulating bath of 28 DEG C
Film forming in water, will scrape after the composite membrane made soaks at least 24 hours in deionized water, and the glycerine water solution with 20% soaks to be protected
Hole is standby.The performance parameter of made composite membrane is shown in Table 1.
Embodiment 7
By dried 17g polysulfones, 8g Polyethylene Glycol, it is dissolved in 68g dimethyl sulfoxide organic solvent, 60 DEG C of conditions
Lower stirring, is completely dissolved to polymer,
Continue under agitation to add 2g lithium chloride 5g polyvinyl alcohol to mixed solution so that it is abundant swelling dissolving,
Adding 5g Biformyl cross-linking reaction 12 hours, stand after being filtered to remove impurity, vacuumizing and defoaming prepares casting solution.
Basement membrane non-woven polyester is arranged in glyoxal solution to soak at least 24 hours and carries out pretreatment,
The polyester non-woven fabric dried after pretreatment is installed on knifing machine, adjusts non-woven fabrics and walk cloth speed 1.5m/s, scrape
Dimensional thickness between cutter and basement membrane is that 160 μm carry out knifing, after nascent composite membrane runs in atmosphere, is immersed in 28 DEG C solidifying
Gu film forming in bath water, will scrape after the composite membrane made soaks at least 24 hours in deionized water, the glycerine water solution with 20% soaks
It is standby that bubble protects hole.The performance parameter of made composite membrane is shown in Table 1.
Embodiment 8
By dried 14g Kynoar, 12g Polyethylene Glycol, to be dissolved into 63gN-methyl pyrrolidone (NMP) organic
In solvent, stir under the conditions of 70 DEG C, be completely dissolved to polymer,
Continue under agitation to add 8g lithium chloride and 3 celluloses to mixed solution so that it is abundant swelling dissolving,
Adding 6g polyglycerol triglycidyl ether cross-linking reaction 12 hours, stand after being filtered to remove impurity, evacuation takes off
Brewed casting solution.
Basement membrane non-woven polyester is arranged in polyglycerol triglycidyl ether to soak at least 24 hours and carries out pretreatment,
Pretreated polyester non-woven fabric is installed on knifing machine, adjusts non-woven fabrics and walk cloth speed 1.2m/s, scraper with
Dimensional thickness between basement membrane is that 170 μm carry out knifing, after nascent composite membrane runs in atmosphere, is immersed in the coagulating bath of 28 DEG C
Film forming in water, will scrape after the composite membrane made soaks at least 24 hours in deionized water, and the glycerine water solution with 20% soaks to be protected
Hole is standby.The performance parameter of made composite membrane is shown in Table 1.
Comparative example 1
By dried 16g polyether sulfone, 9g polyvinylpyrrolidone, 6g acetic acid to 69gN-methyl pyrrolidone
(NMP), in organic solvent, stir under the conditions of 60 DEG C, be completely dissolved to polymer, stand after being filtered to remove impurity, evacuation
Deaeration prepares casting solution.Basement membrane polyester non-woven fabric installs on knifing machine, adjusts non-woven fabrics and walks cloth speed 1.2m/s, scraper and base
Dimensional thickness between film is that 160 μm carry out knifing, after nascent composite membrane runs in atmosphere, is immersed in the solidification bath water of 28 DEG C
Middle film forming, will scrape after the composite membrane made soaks at least 24 hours in deionized water, and the glycerine water solution with 20% soaks protects hole
Standby.The performance parameter of made composite membrane is shown in Table 1.
Comparative example 2
Dried 20g Kynoar, 9g polyvinylpyrrolidone, 3g propanoic acid are dissolved into 68gN-crassitude
In ketone (NMP) organic solvent, stir under the conditions of 60 DEG C, be completely dissolved to polymer, stand after being filtered to remove impurity, evacuation
Deaeration prepares casting solution.Basement membrane polyester non-woven fabric installs on knifing machine, adjusts non-woven fabrics and walks cloth speed 1.2m/s, scraper and base
Dimensional thickness between film is that 180 μm carry out knifing, after nascent composite membrane runs in atmosphere, is immersed in the solidification bath water of 27 DEG C
Middle film forming, will scrape after the composite membrane made soaks at least 24 hours in deionized water, and the glycerine water solution with 20% soaks protects hole
Standby.The performance parameter of made composite membrane is shown in Table 1.
The performance parameter of table 1 composite membrane
As can be seen from the table, plate compounding ultrafilter membrane prepared by the semi-intercrossing network method utilizing the present invention to use hydrophilic
Performance significantly improves, and the mechanical strength of film is improved, and contamination resistance has an enhancing by a relatively large margin, and the inventive method system
Standby simple process, easily carries out industrial operation and amplification.
The content not being described in detail in this specification belongs to prior art known to professional and technical personnel in the field.
Claims (11)
1. the method preparing hydrophilic anti-pollution composite hyperfiltration membrane by semi-intercrossing network method, it is characterised in that include following
Step:
Using the one in polysulfones or fluoropolymer as membrane material,
Dried membrane material and additive are joined in organic solvent, stirring and dissolving, form mixed solution；
In above-mentioned mixed solution, add lithium chloride, then add the hydrophilic macromolecule containing hydroxyl, the most swelling, dissolving,
Adding cross-linking agent and carry out cross-linking reaction, after cross-linking reaction completes, be filtered to remove impurity, vacuumizing and defoaming obtains casting solution；
Basement membrane cross-linking agent is carried out dipping pretreatment,
Knifing machine fixes pretreated basement membrane, casting solution is scratched membrane surface, the base scribbling casting solution will be scraped
Film is immersed in film forming in coagulating bath, makes the flat plate ultrafiltration composite membrane with half interpenetrating network structure；
Described basement membrane is polyester non-woven fabric.
2. the method preparing hydrophilic anti-pollution composite hyperfiltration membrane by semi-intercrossing network method as claimed in claim 1, its feature
It is: described polysulfones is polysulfones, polyether sulfone or benzodiazine polyethersulfone ketone；
Described fluoropolymer is Kynoar.
3. the method preparing hydrophilic anti-pollution composite hyperfiltration membrane by semi-intercrossing network method as claimed in claim 1, its feature
It is: described additive is any one in water soluble polymer polyvinylpyrrolidone PVP, Polyethylene Glycol PEG, or described
Additive be in water soluble polymer polyvinylpyrrolidone PVP, Polyethylene Glycol PEG one of arbitrarily with in formic acid, acetic acid, propanoic acid
One of arbitrarily with the combination of arbitrary proportion.
4. the method preparing hydrophilic anti-pollution composite hyperfiltration membrane by semi-intercrossing network method as claimed in claim 3, its feature
Being: described polyvinylpyrrolidone mean molecule quantity is 15,000 to 40,000, Polyethylene Glycol mean molecule quantity is 6,000 to arrive
20,000。
5. the method preparing hydrophilic anti-pollution composite hyperfiltration membrane by semi-intercrossing network method as claimed in claim 1, its feature
It is: described organic solvent is DMAC N,N' dimethyl acetamide DMAC, N,N-dimethylformamide DMF, N-Methyl pyrrolidone
In NMP, dimethyl sulfoxide one of arbitrarily.
6. the method preparing hydrophilic anti-pollution composite hyperfiltration membrane by semi-intercrossing network method as claimed in claim 1, its feature
It is: the described hydrophilic macromolecule containing hydroxyl is chitosan, cellulose or polyvinyl alcohol.
7. the method preparing hydrophilic anti-pollution composite hyperfiltration membrane by semi-intercrossing network method as claimed in claim 6, its feature
Being: the molecular weight ranges 100 of chitosan, 000 to 1000,000, deacetylation is more than 60%；The molecular weight ranges of cellulose
150,000 to 200,000；The molecular weight ranges 100 of polyvinyl alcohol, 000 to 300,000, alcoholysis degree is more than 70%.
8. the method preparing hydrophilic anti-pollution composite hyperfiltration membrane by semi-intercrossing network method as claimed in claim 1, its feature
It is: described cross-linking agent is formaldehyde, Biformyl, glutaraldehyde, epoxychloropropane, Polyethylene Glycol bisglycidyl ether, polyglycerol
In triglycidyl ether one of arbitrarily.
9. claim 1～8 one of arbitrarily as described in prepare hydrophilic anti-pollution composite hyperfiltration membrane by semi-intercrossing network method
Method, it is characterised in that specifically comprise the following steps that
1) by mass percentage by dried to 12～20% membrane material, 50～81% are joined with the additive of 5～15%
In organic solvent, stirring and dissolving at 50～70 DEG C, form mixed solution；
2) under agitation, interpolation 1～the lithium chloride of 10% in above-mentioned mixed solution, add the most again by mass percentage
1～the hydrophilic macromolecule containing hydroxyl of 5%, the most swelling, dissolve；
3) to step 2) add cross-linking agent in gained mixed solution, continue stirring and carry out cross-linking reaction 6～12 hours, cross-linking reaction
After completing, after being filtered to remove impurity, vacuumizing and defoaming obtains casting solution, and the addition of cross-linking agent is film material by mass percentage
The 1～10% of the gross mass of material, additive, organic solvent, lithium chloride and the hydrophilic macromolecule containing hydroxyl；
4) it is placed in basement membrane in cross-linking agent solution to soak at least 24 hours and carries out pretreatment；
5) on knifing machine, fix pretreated basement membrane, by following parameter adjustment knifing machine: basement membrane walk cloth speed 1.2～
1.5m/s, the dimensional thickness between scraper and basement membrane is 150～180 μm, casting solution is scratched membrane surface, will scrape and scribble casting
The basement membrane of film liquid is immersed in film forming in coagulating bath, and primary membrane, after washing, protecting hole process, is made and had half interpenetrating network structure
Flat plate ultrafiltration composite membrane.
10. the method preparing hydrophilic anti-pollution composite hyperfiltration membrane by semi-intercrossing network method as claimed in claim 9, its feature
It is: the body lotion that described coagulating bath uses is deionized water.
11. methods preparing hydrophilic anti-pollution composite hyperfiltration membrane by semi-intercrossing network method as claimed in claim 9, its feature
Be: described in there is the flat plate ultrafiltration composite membrane of half interpenetrating network structure be saved in the glycerine water solution of 20% immersion and protect hole and treat
With.
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| CN106492659B (en) * | 2015-09-08 | 2019-06-11 | 天津工业大学 | A kind of temperature and pH double-bang firecracker answer PVDF semi-interpenetrating network polymer film and preparation method thereof |
| CN106492660B (en) * | 2015-09-08 | 2020-01-03 | 天津工业大学 | Temperature response PVDF semi-interpenetrating network polymer film and preparation method thereof |
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| CN109092086B (en) * | 2018-08-21 | 2022-04-26 | 南京工业大学 | Polyvinyl alcohol catalytic composite membrane and preparation method thereof |
| CN110158324A (en) * | 2019-05-31 | 2019-08-23 | 南通东屹高新纤维科技有限公司 | Super-hydrophobic linen-cotton textile fabric |
| CN110080006A (en) * | 2019-05-31 | 2019-08-02 | 南通东屹高新纤维科技有限公司 | The preparation method of waterproof composite fabric |
| CN110444795B (en) * | 2019-08-27 | 2020-12-29 | 中国科学院化学研究所 | Preparation method of porous proton exchange composite membrane with nano-sheet structure |
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| CN112237843A (en) * | 2020-09-25 | 2021-01-19 | 淄博蓝景膜环保科技有限公司 | Preparation method of ultrafiltration flat membrane |
| CN113877441B (en) * | 2021-11-12 | 2024-02-23 | 江苏巨之澜科技有限公司 | Composite hollow fiber woven tube filter membrane for fuel cell and preparation method and application thereof |
| CN115010214B (en) * | 2022-06-30 | 2024-03-29 | 成都美富特膜环保科技有限公司 | Sewage treatment membrane, preparation method of sewage treatment membrane and membrane separation equipment |
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