CN104248918A - Method for preparing hydrophilic pollution-resistant composite ultrafiltration membrane by semi-interpenetrating network method - Google Patents
Method for preparing hydrophilic pollution-resistant composite ultrafiltration membrane by semi-interpenetrating network method Download PDFInfo
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Abstract
The invention relates to a method for preparing a hydrophilic pollution-resistant composite ultrafiltration membrane by a semi-interpenetrating network method; a dried membrane material and an additive are added into an organic solvent, and stirred to dissolve to form a mixed solution; lithium chloride is added into the mixed solution, a hydrophilic polymer containing hydroxyl groups is also added for full swelling and dissolving, a crosslinking agent is added for crosslinking reaction, after the crosslinking reaction is completed, impurities are removed by filtering, a membrane casting solution is obtained by vacuum deaeration; a basement membrane is soaked with the crosslinking agent for pretreatment, the pretreated basement membrane is fixed on a membrane blade, the surface of the basement membrane is coated with the membrane casting solution, the basement membrane coated with the membrane casting solution is dipped into a coagulating bath for membrane formation to obtain a flat ultrafiltration composite membrane with a semi-interpenetrating network structure. The ultrafiltration membrane prepared by the method has good hydrophilicity and mechanical properties, high mechanical strength, pollution resistance and high pure water flux, and can reduce the cost of sewage treatment, and the 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, is the method for a kind of semi-intercrossing network legal system for hydrophilic anti-pollution composite hyperfiltration membrane specifically.Belong to the technology of preparing of flat plate ultrafiltration composite membrane.
Background technology
Membrane separating process is that the subjects such as material science and process engineering science intersects and combines, interpenetrates and the frontier that produces, Ultra filtration membrane process has easy and simple to handle, be easy to realize to be continuously separated on a large scale and the feature such as control automatically, be widely applied in the regeneration etc. of water treatment, wastewater treatment and water resource, Ultra filtration membrane process also can be applicable to the industry Raws such as petrochemical industry, biochemical industry, fine chemistry industry, food medicine, textile printing and dyeing and separation of products, purification and concentrated.
Polysulfones is (as polysulfones, polyether sulfone, benzodiazine polyethersulfone ketone etc.) and fluoropolymer (as Kynoar etc.) be high comprehensive performance, industrial application ultrafiltration membrane material extremely widely, there is good mechanical strength and the close property of resistance to compression and heat resistance, and the advantage such as the good He wide pH scope of application of chemical stability, but there is fouling membrane in ultrafiltration membrane technique application process, the problems such as the mechanical strength deficiency of film, the generation of these problems wherein major reason is that membrane material itself causes, hydrophobicity as membrane material causes the lyophobic dust in feed liquid and membrane material to produce non-specific binding, be adsorbed on film surface and in film surface and fenestra constantly gathering cause the aperture of fenestra to diminish even to block fenestra, cause fouling membrane, membrane flux and aquifer yield is caused to decline rapidly, final infringement film properties, therefore the hydrophilic modifying of material of preparing is seemed particularly important.
The method of membrane material hydrophilic modifying mainly contains Physical and chemical method, and Physical has surfactant-modified, surface coating modified and to membrane material blending and modifying etc.; Chemical method has plasma modification, ultraviolet irradiation excites and UV graft polymerization, high-energy irradiation grafting and introduce hydrophilic functional group's (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 the increase hydrophily decay of running time is serious; Or needing comparatively complicated chemical reaction, modified effect is undesirable or industrialization amplification is difficult.
The network structure that semi-intercrossing network is made up of two kinds of polymer, a kind of polymer is wherein had to be uncrosslinked linear molecule, it is interspersed in crosslinked another kind of polymer, half interpenetrating network structure can have the excellent properties of general physical blending, grafting, block polymer simultaneously, and the introducing of this structure can significantly improve mechanical property and the heat endurance of film.Utilize the report of semi-intercrossing network method existing preparation high-performance proton exchange membrane (Chinese patent CN200810041474.5 and CN200910048260.5), but the application in the hydrophilic anti-pollution Compound Ultrafiltration film preparation taking pressure as drive pattern rarely has report.
Summary of the invention
For the defect existed in prior art, the object of the present invention is to provide a kind of semi-intercrossing network legal system for the method for hydrophilic anti-pollution composite hyperfiltration membrane, adopt milipore filter prepared by the method, there is good hydrophily and mechanical property, mechanical strength is high, anti-pollution, and pure water flux is high, reduce cost of sewage disposal, preparation method is suitable for suitability for industrialized production.
For reaching above object, the technical scheme that the present invention takes is:
Semi-intercrossing network legal system, for a method for hydrophilic anti-pollution composite hyperfiltration membrane, is characterized in that, comprises the following steps:
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, fully swelling, dissolving,
Add crosslinking agent and carry out cross-linking reaction, after cross-linking reaction completes, cross and filter impurity, vacuumizing and defoaming obtains casting solution;
Basement membrane crosslinking agent is carried out dipping pretreatment,
Knifing machine fixes pretreated basement membrane, by casting solution blade coating to membrane surface, being immersed in film forming in coagulating bath by scraping the basement membrane scribbling casting solution, making 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 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 any with formic acid, acetic acid, propionic acid in one of any with the combination of arbitrary proportion.
On the basis of technique scheme, 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 one of any in DMA (DMAC), DMF (DMF), 1-METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO).
On the basis of technique scheme, the described hydrophilic macromolecule containing hydroxyl is shitosan, cellulose or polyvinyl alcohol.
On the basis of technique scheme, the molecular weight ranges 100,000 to 1000,000 of shitosan, deacetylation is greater than 60%; Cellulosic molecular weight ranges 150,000 to 200,000; The molecular weight ranges 100,000 to 300,000 of polyvinyl alcohol, alcoholysis degree is greater than 70%.
On the basis of technique scheme, described crosslinking agent is one of any in formaldehyde, glyoxal, glutaraldehyde, epoxychloropropane, polyethylene glycol bisglycidyl ether, polyglycerol triglycidyl ether.
By the method for semi-intercrossing network legal system for hydrophilic anti-pollution composite hyperfiltration membrane, it is characterized in that, concrete steps are as follows:
1) by mass percentage by 12 ~ 20% dried membrane materials, the additive with 5 ~ 15% joins in the organic solvent of 50 ~ 81%, stirring and dissolving at 50 ~ 70 DEG C, forms mixed solution;
2) under agitation, in above-mentioned mixed solution, add the lithium chloride of 1 ~ 10% by mass percentage, and then add the hydrophilic macromolecule containing hydroxyl of 1 ~ 5%, fully swelling, dissolving;
3) to step 2) add crosslinking agent in gained mixed solution, continue stirring and carry out cross-linking reaction 6 ~ 12 hours, after cross-linking reaction completes, cross after filtering impurity, vacuumizing and defoaming obtains casting solution, and the addition of crosslinking agent is 1 ~ 10% of the gross mass of membrane material, additive, organic solvent, lithium chloride and the hydrophilic macromolecule containing hydroxyl by mass percentage;
4) basement membrane is placed in cross-linking agent solution to soak and carry out pretreatment at least 24 hours;
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, dimensional thickness between scraper and basement membrane is 150 ~ 180 μm, by casting solution blade coating to membrane surface, film forming in coagulating bath is immersed in by scraping the basement membrane scribbling casting solution, primary membrane, after washing, protecting hole process, makes the flat plate ultrafiltration composite membrane with half interpenetrating network structure.
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 half interpenetrating network structure flat plate ultrafiltration composite membrane be kept in the glycerine water solution of 20% and soak that to protect hole stand-by.
Semi-intercrossing network legal system of the present invention is for the method for hydrophilic anti-pollution composite hyperfiltration membrane, adopt milipore filter prepared by the method, there is good hydrophily and mechanical property, mechanical strength is high, anti-pollution, pure water flux is high, reduces cost of sewage disposal, and preparation method is suitable for suitability for industrialized production.
The present invention, on the basis keeping original membrane material premium properties, adopts cheap polyester non-woven fabric to do basement membrane, and introduce the mechanical strength that half interpenetrating network structure strengthens composite membrane, the composite membrane of preparation shows stronger hydrophily, and antifouling property significantly improves.
Detailed description of the invention
Semi-intercrossing network legal system of the present invention, for the method for hydrophilic anti-pollution composite hyperfiltration membrane, comprises the following steps:
Using the one in polysulfones (as polysulfones, polyether sulfone, benzodiazine polyethersulfone ketone etc.) or fluoropolymer (as Kynoar etc.) 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, fully swelling, dissolving,
Add crosslinking agent and carry out cross-linking reaction, after cross-linking reaction completes, cross and filter impurity, vacuumizing and defoaming obtains casting solution;
Using polyester non-woven fabric as basement membrane, basement membrane crosslinking agent carries out dipping pretreatment,
Knifing machine fixes pretreated basement membrane, by casting solution blade coating to membrane surface, being immersed in film forming in coagulating bath by scraping the basement membrane scribbling casting solution, making the flat plate ultrafiltration composite membrane with half interpenetrating network structure.
In the present invention, by the blended hydrophilic macromolecule (such as shitosan etc. refer to following) added containing hydroxyl, semi-intercrossing network method is utilized to make membrane material and hydrophilic macromolecule form half interpenetrating network structure; The introducing of half interpenetrating network structure fundamentally can change the hydrophily of milipore filter, and the interpolation of the masking composition such as hydrophilic macromolecule containing hydroxyl can improve the anti-microbial property of milipore filter, thus improves the antifouling property of composite membrane from many aspects.In addition, for increasing compound film strength, improving the fastness of coating film forming, the present invention uses crosslinking agent to carry out pretreatment to the basement membrane (polyester non-woven fabric) playing supporting layer effect.
Each component proportion (mass percent) is listed as follows:
Each component every increasing or decreasing 1% in span all can be used as a selectable specific embodiment.
On the basis of technique scheme, concrete steps are as follows:
1) by mass percentage by 12 ~ 20% dried membrane materials, additive with 5 ~ 15% joins in the organic solvent of 50 ~ 81%, stirring and dissolving at 50 ~ 70 DEG C, in span, every increasing or decreasing 1 DEG C all can be used as a selectable specific embodiment, forms mixed solution;
2) under agitation, in above-mentioned mixed solution, add the lithium chloride of 1 ~ 10% by mass percentage, and then add the hydrophilic macromolecule containing hydroxyl of 1 ~ 5%, fully swelling, dissolving;
3) to step 2) add crosslinking agent in gained mixed solution, continue stirring and carry out cross-linking reaction 6 ~ 12 hours, in span, every increasing or decreasing 1h all can be used as a selectable specific embodiment, after cross-linking reaction completes, cross after filtering impurity, vacuumizing and defoaming obtains casting solution, and by mass percentage, the addition of crosslinking agent is 1 ~ 10% of the gross mass of membrane material, additive, organic solvent, lithium chloride and the hydrophilic macromolecule containing hydroxyl;
4) basement membrane is placed in cross-linking agent solution to soak and carry out pretreatment at least 24 hours;
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 be used as a selectable specific embodiment, dimensional thickness between scraper and basement membrane is 150 ~ 180 μm, in span, every increasing or decreasing 1 μm all can be used as a selectable specific embodiment, by casting solution blade coating to membrane surface, film forming in coagulating bath is immersed in by scraping the basement membrane scribbling casting solution, primary membrane is through washing, after protecting hole process, make the flat plate ultrafiltration composite membrane with half interpenetrating network structure.
In said ratio, the cumulative of mass percent of membrane material, additive, organic solvent, lithium chloride, hydrophilic macromolecule containing hydroxyl should be 100%, the gross mass metering of the mixed solution that the addition of crosslinking agent is then formed by aforementioned component.
On the basis of technique scheme, 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 any with formic acid, acetic acid, propionic acid in one of any 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 one of any in DMA (DMAC), DMF (DMF), 1-METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO).
On the basis of technique scheme, the described hydrophilic macromolecule containing hydroxyl is shitosan, cellulose or polyvinyl alcohol, the molecular weight ranges 100,000 to 1000,000 of shitosan, and deacetylation is greater than 60%; Cellulosic molecular weight ranges 150,000 to 200,000; The molecular weight ranges 100,000 to 300,000 of polyvinyl alcohol, alcoholysis degree is greater than 70%.
On the basis of technique scheme, described crosslinking agent is one of any in formaldehyde, glyoxal, glutaraldehyde, epoxychloropropane, polyethylene glycol bisglycidyl ether, polyglycerol triglycidyl ether.
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 half interpenetrating network structure flat plate ultrafiltration composite membrane be kept in the glycerine water solution of 20% and soak that to protect hole stand-by.
The present invention's beneficial effect is compared with prior art:
(1) half interpenetrating network structure that the polymeric film material after the hydrophilic macromolecule containing hydroxyl in the present invention and crosslinking agent react and in casting solution is formed, prepared ultrafiltration composite membrane is made to have good mechanical strength and chemical stability, the more important thing is that composite membrane prepared by the present invention strengthens the antifouling property of film from hydrophily, anti-microbial property aspect, extend the service life of film;
(2) crosslinking agent is used to carry out pretreatment to the basement membrane playing supporting layer effect in the preparation method of ultrafiltration composite membrane of the present invention, reduce the surface energy of basement membrane, coating is carried out with crosslinked simultaneously, add the binding strength between the basement membrane of supporting layer effect and casting solution coating material, made the firm difficult drop-off of composite bed;
(3) the present invention adopts polyether sulfone, polysulfones, benzodiazine polyethersulfone ketone and Kynoar one of them with containing hydroxyl hydrophilic macromolecule (polyvinyl alcohol, cellulose or shitosan) blended as material of preparing, keep original polyether sulfone on the one hand, polysulfones, the premium properties of the materials such as benzodiazine polyethersulfone ketone and Kynoar, on the other hand due to the hydrophily containing hydroxyl hydrophilic macromolecular material, prepared film is not only had high temperature resistant, chemical-resistant reagent and the feature such as nontoxic, also there is good biocompatibility, effluent quality is good, flux is large, and preparation method's simple process of the present invention, easy to operate, chemical industry can be widely used in, medicine, food, the water treatment procedures such as environmental protection.
Be below specific embodiment, described embodiment only in order to explain the present invention, is not construed as limiting the invention, and 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, the pure water flux by experiment outer press filtering device of the homemade dead end in room measures, be about to scrape after the composite membrane made dries naturally and be cut into circular film, put into ultrafiltration cup first precompressed 30min under 0.15Mpa, until water flux is basicly stable, and then under 0.1MPa, measure the pure water flux of film; Film cutoff performance measures using the bovine serum albumin of 1g/L (BSA) solution as medium; With three-stage distillation water with lie drip method DSA100 contact angle instrument (
gmbH, Germany) on measure contact angle; By surface and the fracture morphology of being observed film after the direct metal spraying of dry film by XL-30 field emission scanning electron microscope (FEI, USA); The mechanical strength of film is measured by burst pressure testing arrangement, namely slowly increases the pressure be applied on milipore filter, until film is only broked into, and record burst pressure; Fouling membrane degree is to characterize the adsorbance of bovine serum albumin (BSA).
Embodiment 1
By dried 18g polyether sulfone, 9g polyvinylpyrrolidone, be dissolved in 61gN-methyl pyrrolidone organic solvent, stir under 70 DEG C of conditions, dissolve completely to polymer,
Continue under agitation to add 7g lithium chloride and 5g cellulose to mixed solution, make its abundant swelling dissolving,
Add 7g glutaraldehyde cross-linking and react 12 hours, left standstill after filtering impurity, vacuumizing and defoaming obtains casting solution.
Basement membrane non-woven polyester is arranged in glutaraldehyde solution to soak and carries out pretreatment at least 24 hours,
The polyester non-woven fabric dried after pretreatment is installed on knifing machine, cloth speed 1.2m/s walked by adjustment non-woven fabrics, dimensional thickness between scraper and basement membrane is 160 μm and carries out knifing, after nascent composite membrane runs in atmosphere, be immersed in 25 DEG C solidify film forming in bath water, to scrape after the composite membrane made soaks at least 24 hours in deionized water, the glycerine water solution with 20% soaks that to protect hole for subsequent use.The performance parameter of made composite membrane is in table 1.
Embodiment 2
Dried 12g polysulfones, 8g polyethylene glycol, 2g formic acid are dissolved into 74gN, in N-dimethylacetylamide organic solvent, stir under 60 DEG C of conditions, dissolve completely to polymer,
Continue under agitation to add 1g lithium chloride and 3g polyvinyl alcohol to mixed solution, make its abundant swelling dissolving,
Add 1g polyethylene glycol bisglycidyl ether cross-linking reaction 6 hours, left standstill after filtering impurity, vacuumizing and defoaming obtains casting solution.
Basement membrane non-woven polyester is arranged in polyethylene glycol bisglycidyl ethereal solution to soak and carries out pretreatment at least 24 hours,
The polyester non-woven fabric dried after pretreatment is installed on knifing machine, cloth speed 1.5m/s walked by adjustment non-woven fabrics, dimensional thickness between scraper and basement membrane is 150 μm and carries out knifing, after nascent composite membrane runs in atmosphere, be immersed in 28 DEG C solidify film forming in bath water, to scrape after the composite membrane made soaks at least 24 hours in deionized water, the glycerine water solution with 20% soaks that to protect hole for subsequent use.The performance parameter of made composite membrane is in table 1.
Embodiment 3
By dried 15g benzodiazine polyethersulfone ketone, 5g polyethylene glycol, be dissolved into 67gN, in dinethylformamide organic solvent, stir under 50 DEG C of conditions, dissolve completely to polymer,
Continue under agitation to add 8g lithium chloride and 5g cellulose to mixed solution, make its abundant swelling dissolving,
Add 10g glutaraldehyde cross-linking and react 12 hours, left standstill after filtering impurity, vacuumizing and defoaming obtains casting solution.
Basement membrane non-woven polyester is arranged in glutaraldehyde solution to soak and carries out pretreatment at least 24 hours,
Pretreated polyester non-woven fabric is installed on knifing machine, cloth speed 1.3m/s walked by adjustment non-woven fabrics, dimensional thickness between scraper and basement membrane is 160 μm and carries out knifing, after nascent composite membrane runs in atmosphere, be immersed in 28 DEG C solidify film forming in bath water, to scrape after the composite membrane made soaks at least 24 hours in deionized water, the glycerine water solution with 20% soaks that to protect hole for subsequent use.The performance parameter of made composite membrane is in table 1.
Embodiment 4
Dried 20g Kynoar, 9g polyvinylpyrrolidone, 3g propionic acid are dissolved in 57gN-methyl pyrrolidone (NMP) organic solvent, stir under 70 DEG C of conditions, dissolve completely to polymer,
Continue under agitation to add 6g lithium chloride and 5g cellulose to mixed solution, make its abundant swelling dissolving,
Add 5g epoxychloropropane cross-linking reaction 12 hours, left standstill after filtering impurity, vacuumizing and defoaming obtains casting solution.
Basement membrane non-woven polyester is arranged in epoxychloropropane solution to soak and carries out pretreatment at least 24 hours,
Pretreated polyester non-woven fabric is installed on knifing machine, cloth speed 1.2m/s walked by adjustment non-woven fabrics, dimensional thickness between scraper and basement membrane is 180 μm and carries out knifing, after nascent composite membrane runs in atmosphere, be immersed in 27 DEG C solidify film forming in bath water, to scrape after the composite membrane made soaks at least 24 hours in deionized water, the glycerine water solution with 20% soaks that to protect hole for subsequent use.The performance parameter of made composite membrane is in table 1.
Embodiment 5
By dried 16g polyether sulfone, 9g polyvinylpyrrolidone, 6g acetic acid in 56gN-methyl pyrrolidone (NMP) organic solvent, stir under 60 DEG C of conditions, dissolve completely to polymer,
Continue under agitation to add 10g lithium chloride and 3g shitosan to mixed solution, make its abundant swelling dissolving,
Add 7g formaldehyde crosslinking and react 10 hours, left standstill after filtering impurity, vacuumizing and defoaming obtains casting solution.
Basement membrane non-woven polyester is arranged in formalin to soak and carries out pretreatment at least 24 hours,
Pretreated polyester non-woven fabric is installed on knifing machine, cloth speed 1.2m/s walked by adjustment non-woven fabrics, dimensional thickness between scraper and basement membrane is 160 μm and carries out knifing, after nascent composite membrane runs in atmosphere, be immersed in 28 DEG C solidify film forming in bath water, to scrape after the composite membrane made soaks at least 24 hours in deionized water, the glycerine water solution with 20% soaks that to protect hole for subsequent use.The performance parameter of made composite membrane is in table 1.
Embodiment 6
By dried 13g benzodiazine polyethersulfone ketone, 4g polyvinylpyrrolidone, 3g acetic acid, be dissolved into 74gN, in N-dimethylacetylamide organic solvent, stir under 60 DEG C of conditions, dissolve completely to polymer,
Continue under agitation to add 5g lithium chloride and 1g shitosan to mixed solution, make its abundant swelling dissolving,
Add 3g formaldehyde crosslinking and react 8 hours, left standstill after filtering impurity, vacuumizing and defoaming obtains casting solution.
Basement membrane non-woven polyester is arranged in formalin to soak and carries out pretreatment at least 24 hours,
Pretreated polyester non-woven fabric is installed on knifing machine, cloth speed 1.3m/s walked by adjustment non-woven fabrics, dimensional thickness between scraper and basement membrane is 160 μm and carries out knifing, after nascent composite membrane runs in atmosphere, be immersed in 28 DEG C solidify film forming in bath water, to scrape after the composite membrane made soaks at least 24 hours in deionized water, the glycerine water solution with 20% soaks that to protect hole for subsequent use.The performance parameter of made composite membrane is in table 1.
Embodiment 7
By dried 17g polysulfones, 8g polyethylene glycol, be dissolved in 68g dimethyl sulfoxide (DMSO) organic solvent, stir under 60 DEG C of conditions, dissolve completely to polymer,
Continue under agitation to add 2g lithium chloride 5g polyvinyl alcohol to mixed solution, make its abundant swelling dissolving,
Add 5g glyoxal cross-linking reaction 12 hours, left standstill after filtering impurity, vacuumizing and defoaming obtains casting solution.
Basement membrane non-woven polyester is arranged in glyoxal solution to soak and carries out pretreatment at least 24 hours,
The polyester non-woven fabric dried after pretreatment is installed on knifing machine, cloth speed 1.5m/s walked by adjustment non-woven fabrics, dimensional thickness between scraper and basement membrane is 160 μm and carries out knifing, after nascent composite membrane runs in atmosphere, be immersed in 28 DEG C solidify film forming in bath water, to scrape after the composite membrane made soaks at least 24 hours in deionized water, the glycerine water solution with 20% soaks that to protect hole for subsequent use.The performance parameter of made composite membrane is in table 1.
Embodiment 8
By dried 14g Kynoar, 12g polyethylene glycol, be dissolved in 63gN-methyl pyrrolidone (NMP) organic solvent, stir under 70 DEG C of conditions, dissolve completely to polymer,
Continue under agitation to add 8g lithium chloride and 3 celluloses to mixed solution, make its abundant swelling dissolving,
Add 6g polyglycerol triglycidyl ether cross-linking reaction 12 hours, left standstill after filtering impurity, vacuumizing and defoaming obtains casting solution.
Basement membrane non-woven polyester is arranged in polyglycerol triglycidyl ether to soak and carries out pretreatment at least 24 hours,
Pretreated polyester non-woven fabric is installed on knifing machine, cloth speed 1.2m/s walked by adjustment non-woven fabrics, dimensional thickness between scraper and basement membrane is 170 μm and carries out knifing, after nascent composite membrane runs in atmosphere, be immersed in 28 DEG C solidify film forming in bath water, to scrape after the composite membrane made soaks at least 24 hours in deionized water, the glycerine water solution with 20% soaks that to protect hole for subsequent use.The performance parameter of made composite membrane is in table 1.
Comparative example 1
By dried 16g polyether sulfone, 9g polyvinylpyrrolidone, 6g acetic acid in 69gN-methyl pyrrolidone (NMP) organic solvent, stir under 60 DEG C of conditions, dissolve completely to polymer, left standstill after filtering impurity, vacuumizing and defoaming obtains casting solution.Basement membrane polyester non-woven fabric installs on knifing machine, cloth speed 1.2m/s walked by adjustment non-woven fabrics, dimensional thickness between scraper and basement membrane is 160 μm and carries out knifing, after nascent composite membrane runs in atmosphere, be immersed in 28 DEG C solidify film forming in bath water, to scrape after the composite membrane made soaks at least 24 hours in deionized water, the glycerine water solution with 20% soaks that to protect hole for subsequent use.The performance parameter of made composite membrane is in table 1.
Comparative example 2
Dried 20g Kynoar, 9g polyvinylpyrrolidone, 3g propionic acid are dissolved in 68gN-methyl pyrrolidone (NMP) organic solvent, stir under 60 DEG C of conditions, dissolve completely to polymer, left standstill after filtering impurity, vacuumizing and defoaming obtains casting solution.Basement membrane polyester non-woven fabric installs on knifing machine, cloth speed 1.2m/s walked by adjustment non-woven fabrics, dimensional thickness between scraper and basement membrane is 180 μm and carries out knifing, after nascent composite membrane runs in atmosphere, be immersed in 27 DEG C solidify film forming in bath water, to scrape after the composite membrane made soaks at least 24 hours in deionized water, the glycerine water solution with 20% soaks that to protect hole for subsequent use.The performance parameter of made composite membrane is in table 1.
The performance parameter of table 1 composite membrane
As can be seen from the table, the hydrophilicity of the plate compounding milipore filter that the semi-intercrossing network legal system utilizing the present invention to use is standby significantly improves, the mechanical strength of film improves, contamination resistance has enhancing by a relatively large margin, and the inventive method preparation technology is easy, easily carry out industrial operation and amplification.
The content be not described in detail in this description belongs to the known prior art of professional and technical personnel in the field.
Claims (11)
1., by the method for semi-intercrossing network legal system for hydrophilic anti-pollution composite hyperfiltration membrane, it is characterized in that, comprise the following steps:
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, fully swelling, dissolving,
Add crosslinking agent and carry out cross-linking reaction, after cross-linking reaction completes, cross and filter impurity, vacuumizing and defoaming obtains casting solution;
Basement membrane crosslinking agent is carried out dipping pretreatment,
Knifing machine fixes pretreated basement membrane, by casting solution blade coating to membrane surface, being immersed in film forming in coagulating bath by scraping the basement membrane scribbling casting solution, making the flat plate ultrafiltration composite membrane with half interpenetrating network structure.
2. semi-intercrossing network legal system of using as claimed in claim 1 is for the method for hydrophilic anti-pollution composite hyperfiltration membrane, it is characterized in that: described polysulfones is polysulfones, polyether sulfone or benzodiazine polyethersulfone ketone;
Described fluoropolymer is Kynoar;
Described basement membrane is polyester non-woven fabric.
3. as claimed in claim 1 by the method for semi-intercrossing network legal system for hydrophilic anti-pollution composite hyperfiltration membrane, it is characterized in that: 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 any with formic acid, acetic acid, propionic acid in one of any with the combination of arbitrary proportion.
4. semi-intercrossing network legal system of using as claimed in claim 3 is for the method for hydrophilic anti-pollution composite hyperfiltration membrane, and it is characterized in that: described polyvinylpyrrolidone mean molecule quantity is 15,000 to 40,000, polyethylene glycol mean molecule quantity is 6,000 to 20,000.
5. as claimed in claim 1 by the method for semi-intercrossing network legal system for hydrophilic anti-pollution composite hyperfiltration membrane, it is characterized in that: described organic solvent is N, one of any in N-dimethylacetylamide DMAC, DMF DMF, 1-METHYLPYRROLIDONE NMP, dimethyl sulfoxide (DMSO).
6. semi-intercrossing network legal system of using as claimed in claim 1 is for the method for hydrophilic anti-pollution composite hyperfiltration membrane, it is characterized in that: the described hydrophilic macromolecule containing hydroxyl is shitosan, cellulose or polyvinyl alcohol.
7. semi-intercrossing network legal system of using as claimed in claim 6 is for the method for hydrophilic anti-pollution composite hyperfiltration membrane, and it is characterized in that: the molecular weight ranges 100,000 to 1000,000 of shitosan, deacetylation is greater than 60%; Cellulosic molecular weight ranges 150,000 to 200,000; The molecular weight ranges 100,000 to 300,000 of polyvinyl alcohol, alcoholysis degree is greater than 70%.
8. as claimed in claim 1 by semi-intercrossing network legal system for the method for hydrophilic anti-pollution composite hyperfiltration membrane, it is characterized in that: described crosslinking agent is one of any in formaldehyde, glyoxal, glutaraldehyde, epoxychloropropane, polyethylene glycol bisglycidyl ether, polyglycerol triglycidyl ether.
9. as described in one of as any in claim 1 ~ 8 by semi-intercrossing network legal system for the method for hydrophilic anti-pollution composite hyperfiltration membrane, it is characterized in that, concrete steps are as follows:
1) by mass percentage by 12 ~ 20% dried membrane materials, the additive with 5 ~ 15% joins in the organic solvent of 50 ~ 81%, stirring and dissolving at 50 ~ 70 DEG C, forms mixed solution;
2) under agitation, in above-mentioned mixed solution, add the lithium chloride of 1 ~ 10% by mass percentage, and then add the hydrophilic macromolecule containing hydroxyl of 1 ~ 5%, fully swelling, dissolving;
3) to step 2) add crosslinking agent in gained mixed solution, continue stirring and carry out cross-linking reaction 6 ~ 12 hours, after cross-linking reaction completes, cross after filtering impurity, vacuumizing and defoaming obtains casting solution, and the addition of crosslinking agent is 1 ~ 10% of the gross mass of membrane material, additive, organic solvent, lithium chloride and the hydrophilic macromolecule containing hydroxyl by mass percentage;
4) basement membrane is placed in cross-linking agent solution to soak and carry out pretreatment at least 24 hours;
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, dimensional thickness between scraper and basement membrane is 150 ~ 180 μm, by casting solution blade coating to membrane surface, film forming in coagulating bath is immersed in by scraping the basement membrane scribbling casting solution, primary membrane, after washing, protecting hole process, makes the flat plate ultrafiltration composite membrane with half interpenetrating network structure.
10. semi-intercrossing network legal system of using as claimed in claim 9 is for the method for hydrophilic anti-pollution composite hyperfiltration membrane, it is characterized in that: the body lotion that described coagulating bath uses is deionized water.
11. as claimed in claim 9 by semi-intercrossing network legal systems for the method for hydrophilic anti-pollution composite hyperfiltration membrane, it is characterized in that: described in there is half interpenetrating network structure flat plate ultrafiltration composite membrane be kept in the glycerine water solution of 20% and soak that to protect hole stand-by.
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