CN105727761A - Protein-fouling-resistant zwitter-ion ultrafiltration membrane and preparation method thereof - Google Patents
Protein-fouling-resistant zwitter-ion ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN105727761A CN105727761A CN201610136103.XA CN201610136103A CN105727761A CN 105727761 A CN105727761 A CN 105727761A CN 201610136103 A CN201610136103 A CN 201610136103A CN 105727761 A CN105727761 A CN 105727761A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/74—Natural macromolecular material or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a protein-fouling-resistant zwitter-ion ultrafiltration membrane and a preparation method thereof. The zwitter-ion ultrafiltration membrane is prepared by coating gel, prepared through sol-gel reaction of zwitterionization chitosan and polyvinyl alcohol, on a supporter to form a membrane, and soaking the membrane into water for phase conversion reaction. The zwitter-ion ultrafiltration membrane prepared from the polyvinyl alcohol modified by the zwitterionization chitosan is highly resistant to water, remarkable in hydrophilicity and antifouling performance and good in antifouling selectivity and particularly achieves the ratio of removing bovine serum albumin up to 97.6%; the zwitter-ion ultrafiltration membrane capable of achieving targeted protein fouling resistance can maintain high membrane flux and high bovine serum albumin removal rate through multiple experiments and is long in service life; additionally, the zwitter-ion ultrafiltration membrane is simple in preparation technology, highly repeatable and easy to achieve scale production, requires no strict control over reaction conditions and the like.
Description
Technical field
The present invention relates to a kind of ultrafilter membrane and preparation method thereof, be specifically related to a kind of anti-protein-contamination amphion ultrafilter membrane and preparation method thereof, belong to technical field of membrane separation.
Background technology
Ultrafiltration refers under the promotion of differential static pressure, and with the process that film is easily separated for separating medium according to separated material molecular weight difference, the main separate object of ultrafilter membrane is protein, various enzyme, antibacterial, virus, latex etc..Ultrafiltration, as a kind of novel isolation technics, has some obvious advantages: process is fairly simple, operation have can seriality, good economy performance, separation is big, energy-conservation, efficiently.At present, hyperfiltration technique is widely used in the fields such as water process, medicine, biochemical technology, it is particularly due to it in protein purification, does not need substantial amounts of salt and buffer, can the activity of Protein requirement well, ultrafiltration thus have in the concentration and purification of bio-chemistry separation and biological sample and be more and more widely applied.
The main problems faced of current hyperfiltration technique is in that biomacromolecule makes the hole plug on film surface and aperture reduce in the absorption of film surface non-directional and deposition, causes serious fouling membrane, makes ultrafiltration efficiency reduce, limits hyperfiltration technique application in practice.Research surface, the hydrophilic improving ultrafiltration membrane surface can be effectively reduced the biomacromolecule non-directional absorption on film surface, thus the problem improving Pollution of Ultrafiltration Membrane.Therefore, the exploitation of hydrophilic film material and the hydrophilic modifying of hydrophobic membrane materials are the effective ways fundamentally solving fouling membrane.
Polyvinyl alcohol (PVA) is prepared through alcoholysis reaction by polyvinyl acetate, there is good hydrophilic, endurance, thermostability, biocompatibility, chemical stability and low cost, it it is a kind of membrane material having much captivation, thus the anti-fouling performance that can fundamentally improve film of ultrafiltration membrane material made by polyvinyl alcohol, reduce the protein pollution to ultrafilter membrane.Studies have found that; adopt membrane material prepared by pure polyvinyl alcohol; owing to polyvinyl alcohol molecule exists in substantial amounts of strand and interchain hydrogen bond; water-resistance is poor; hot water can be dissolved in; the formation of ultrafilter membrane is played inhibition, limits its application industrially, therefore typically require and adopt the method for hydroxyl protection that polyvinyl alcohol is modified.Chitosan (CS) has good biocidal property and film property and is widely used in the fields such as water process, biomaterial, membrane material.Therefore, there is scholar that prepared by chitosan and polyvinyl alcohol blending film forming, the addition of chitosan can destroy the hydrogen bond that polyvinyl alcohol is originally defined, the part amino of chitosan self and the hydroxyl of polyvinyl alcohol are had an effect simultaneously, form chitosan and polyvinyl alcohol molecule interchain hydrogen bond, thus improving water-resistance (Zhang Ruping, the fourth Matthew of polyvinyl alcohol film, functional material, 2007,12,2005-2007).
Although, the water-resistance of polyvinyl alcohol film can be improved after chitosan and polyvinyl alcohol blending, but after repeating this test, find that the hydrophilic of film declines to some extent, pure water flux is less than 50L m-2·h-1, hydrophilic is poor, and pollution resistance is poor simultaneously, and anti-soil selectivity is also poor, it is impossible to meets actual ultrafiltration demand, has a strong impact on its service life on the whole.
Summary of the invention
For the problems referred to above that prior art exists, it is an object of the invention to provide that a kind of good hydrophilic property, pollution resistance be good, the anti-protein-contamination amphion ultrafilter membrane of long service life and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of anti-protein-contamination amphion ultrafilter membrane, is be immersed in the water generation phase conversion reaction on supporter after film forming by the gel coating that bisexual ion purification chitosan is prepared with the reaction of polyvinyl alcohol collosol and gelization to prepare.
As a kind of preferred version, described bisexual ion purification chitosan is to be prepared by imidization chitosan and sulfonated reagent generation sulfonating reaction, described imidization chitosan is to be reacted with paradime thylaminobenzaldehyde by chitosan, then occurs reduction reaction to prepare with boron hydride (such as sodium borohydride).
As it is preferred that scheme, after the preparation of described imidization chitosan comprises the steps: to mix the acetic acid solution of chitosan with the alcoholic solution of paradime thylaminobenzaldehyde, the pH value regulating mixed solution with hydrochloric acid is 2～3, reaction being stirred at room temperature 5～7 hours, the pH value then adding sodium hydrate aqueous solution adjustment reaction solution in reaction solution is 4～6, is subsequently added into sodium borohydride solution and carries out reduction reaction, after reacting completely, precipitate out precipitation, collect precipitation, prepare imidization chitosan.
As further preferred version, the acetic acid solutions method of chitosan is: dissolves the chitosan in and is configured to the chitosan solution that mass concentration is 1.5～2.0% in the acetic acid solution that mass concentration is 1～2%, and stirs 30～60 minutes at 55～65 DEG C.
As further preferred version, the ethanol solution concentration of paradime thylaminobenzaldehyde is 0.05～0.07g/mL.
Mol ratio as further preferred version, chitosan and paradime thylaminobenzaldehyde is 1:1.5～1:2.5, and the mol ratio of chitosan and sodium borohydride is 1:3～1:5.
As further preferred version, the concentration of sodium hydrate aqueous solution is 1～3mo/L.
As further preferred version, the concentration of sodium borohydride solution is 0.5～0.8mol/L.
As it is preferred that scheme, the preparation of described bisexual ion purification chitosan comprises the steps: to be dissolved in hydrochloric acid solution by imidization chitosan, add sulfonated reagent, stirring reaction 5～6 hours at 55～65 DEG C, after reacting completely, reactant is joined in acetone and precipitate, collect precipitation, prepare bisexual ion purification chitosan.
As further preferred version, the concentration of hydrochloric acid solution is dissolving 1～2g imidization chitosan in 0.5～1.5mol/L, 100mL hydrochloric acid solution.
As further preferred version, described sulfonated reagent is selected from any one in halogenosulfonic acid salt (such as chlorosulfonic acid), sulfur trioxide complex (such as trimethyl amine sulfur trioxide), sultones (such as propane sultone).
As further preferred version, described sulfonated reagent is 1.2:1～1.6:1 with the mol ratio of amino in chitosan molecule.
The preparation method of a kind of anti-protein-contamination amphion ultrafilter membrane, comprises the steps:
A) solution blended process is adopted, bisexual ion purification chitosan solution and poly-vinyl alcohol solution are mixed into uniform solution, in solution, then add cross-linking agent, and the pH value regulating solution is 2～3, under room temperature, stirring carries out collosol and gel reaction in 10～12 hours, prepares gel；
B) by prepared gel coating film forming on polyfluortetraethylene plate, the thickness controlling thin film is 0.2～0.3mm, is immersed in by the film obtained in pure water and phase conversion reaction occurs, obtain described amphion ultrafilter membrane.By gel coating on polyfluortetraethylene plate compared to being coated on the supporter such as glass plate or non-woven fabrics, owing to politef is the material that a kind of surface can be only small, so the film surface after coating not easily adheres in its surface, the ultrafilter membrane prepared is not susceptible to the phenomenons such as hole contraction, reaming, making membrane aperture uniform, membrane flux is better.
As a kind of preferred version, the mass ratio of polyvinyl alcohol and bisexual ion purification chitosan is 10:1～1:1.
As a kind of preferred version, described cross-linking agent selects tetraethyl orthosilicate or epoxychloropropane.
As a kind of preferred version, the quality of the cross-linking agent of addition is the 5～10% of polyvinyl alcohol and bisexual ion purification chitosan mass sum.
As a kind of preferred version, the compound method of bisexual ion purification chitosan solution is: is dissolved in the deionized water of 40～60mL by 1g bisexual ion purification chitosan and prepares.
As a kind of preferred version, the compound method of poly-vinyl alcohol solution is: is dissolved in the deionized water of 5～20mL by 1g polyvinyl alcohol and prepares.
Compared with prior art, the present invention has following significance beneficial effect:
The present invention adopts the amphion ultrafilter membrane that the chitin modified polyvinyl alcohol of bisexual ion purification prepares, and (pure water flux is up to 75L m to have significant hydrophilic while having good water-resistance-2·h-1) and pollution resistance (protein and lysozyme are all had good pollution resistance), and there is good anti-soil selectivity, especially to the removal efficiency of bovine serum albumin up to 97.6%, anti-protein-contamination that can be pointed, this ultrafilter membrane still keeps higher membrane flux and the removal efficiency to bovine serum albumin, long service life after test of many times；Also find that the ultrafilter membrane better heat stability of preparation extends the service life of this ultrafilter membrane further simultaneously；It addition, the ultrafilter membrane of the present invention also has preparation technology simple, it is not necessary to strictly control reaction condition, reproducible, it is easy to accomplish the advantages such as scale.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of chitosan (a), imidization chitosan (b), bisexual ion purification chitosan (c) in the embodiment of the present invention 1；
Fig. 2 is the thermogravimetric curve figure of chitosan (a) in the embodiment of the present invention 1, imidization chitosan (b), bisexual ion purification chitosan (c)；
Fig. 3 is the infrared spectrogram of PVA+TEOS blend (a) and ultrafilter membrane (b) in the embodiment of the present invention 1；
Fig. 4 is the scanning electron microscope (SEM) photograph of the ultrafilter membrane prepared in the embodiment of the present invention 1；
Fig. 5 is different content bisexual ion purification chitosan ultrafiltration membrane (Z-0, Z-1, Z-2 in the embodiment of the present invention 2～5, Z-4 represents the amount ratio of amphoterisation ion polysaccharide respectively 0%, 10%, 20%, 40%) to pure water, protein, lysozyme water flux block diagram；
Fig. 6 is the recovery rate block diagram of the different content bisexual ion purification chitosan ultrafiltration membrane prepared in the embodiment of the present invention 2～5.
Detailed description of the invention
The present invention is expanded on further below in conjunction with specific embodiment.Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally conventionally condition or according to manufacturer it is proposed that condition.
Embodiment 1
One, the preparation of imidization chitosan: be the chitosan solution of 2% by the acetic acid solutions mass concentration that mass concentration is 2%, and stir 60 minutes at 60 DEG C, containing 2g chitosan in the solution of configuration；Weigh 4g paradime thylaminobenzaldehyde and be dissolved in the dehydrated alcohol of 70mL to be configured to the alcoholic solution of paradime thylaminobenzaldehyde；Regulate pH value with the hydrochloric acid solution of 1mol/L after the two kinds of solution mixing that will be configured to and be about 3, reaction 6 hour is stirred at room temperature, the pH value of the sodium hydroxide solution adjustment reaction solution then adding 3mL, 2mol/L in reaction solution is about 5, then the sodium borohydride solution adding 80 μ L, 0.63mol/L in reaction solution carries out reduction reaction, after reacting completely, the sodium hydroxide solution adding 15mL, 3mol/L rapidly precipitates out precipitation, collect precipitation and respectively wash three times with acetone and ethanol successively, namely preparing imidization chitosan after drying.
Two, the preparation of bisexual ion purification chitosan: 3g imidization chitosan is dissolved in the hydrochloric acid solution that 200mL concentration is 1mol/L, it is subsequently adding 1.5mL propane sultone, stirring reaction 6 hours at 50 DEG C, after reacting completely, reactant is joined in acetone and precipitate, collect precipitation, prepare bisexual ion purification chitosan.
Three, the preparation of amphion ultrafilter membrane: 10g polyvinyl alcohol is dissolved in the deionized water of 100mL at 50 DEG C and is configured to poly-vinyl alcohol solution；1g bisexual ion purification chitosan is dissolved in the deionized water of 50mL and is configured to bisexual ion purification chitosan solution；Adopt solution blended process, the bisexual ion purification chitosan solution configured and poly-vinyl alcohol solution being stirred 8 hours at 30 DEG C makes it be mixed into uniform solution, then in solution, add 0.96g tetraethyl orthosilicate (TEOS), and the pH value regulating solution is 2, under room temperature, stirring carries out collosol and gel reaction for 12 hours (TEOS carries out cross-linking reaction with polyvinyl alcohol and bisexual ion purification chitosan respectively, thus realizing polyvinyl alcohol and bisexual ion purification chitosan blend), prepare gel；By prepared gel coating film forming on polyfluortetraethylene plate, the thickness controlling thin film is 0.2～0.3mm, is immersed in by the film obtained in pure water and phase conversion reaction occurs, obtain described amphion ultrafilter membrane.
Fig. 1 be chitosan (a) used in embodiment 1 and imidization chitosan (b) prepared, bisexual ion purification chitosan (c) infrared spectrum as shown in Figure 1, by different characteristic peak in Fig. 1 it can be seen that the change of chitosan in preparation process, 1654cm in (a)-1And 1594cm-1Respectively C=O and-NH in chitosan2Vibration absorption peak, 1611cm in (b)-1For the vibration absorption peak of-NH-,-the NH of chitosan is described2Replaced by-NH-, chitosan and paradime thylaminobenzaldehyde react successfully, 1637cm in (c)-1For-N+(CH3)3The vibration absorption peak of middle N-C, and 1148cm-1And 1033cm-1For the vibration absorption peak of sulfonic acid group, chitosan by self with amino react with the aldehyde radical in paradime thylaminobenzaldehyde, after the subsequent treatment such as a series of reduction, thus preparing bisexual ion purification chitosan ,-N in bisexual ion purification chitosan+(CH3)3And SO3 -The existence of hydrophilic ionic improves its hydrophilic, thus the hydrophilic further increasing the amphion ultrafilter membrane of final preparation (shows as the pure water flux of film by conventional 50L m-2·h-1Left and right is increased to 75L m-2·h-1Left and right).
Fig. 2 is chitosan (a) used in embodiment 1 and the thermogravimetric curve such as figure of imidization chitosan (b) prepared, bisexual ion purification chitosan (c), as seen from Figure 2: bisexual ion purification chitosan is compared with chitosan and imidization chitosan, its weightless ratio is less, heat stability is better, and the heat stability that ultrafilter membrane for finally preparing is good provides good theory support.
Fig. 3 is the infrared spectrogram of the ultrafilter membrane (b) of PVA (polyvinyl alcohol)+TEOS (tetraethyl orthosilicate) blend (a) used in embodiment 1 and preparation, the difference of ultrafilter membrane and PVA+TEOS blend can be drawn by the change of the characteristic peak in Fig. 3, simultaneously as-N in bisexual ion purification chitosan+(CH3)3And SO3 -The existence of hydrophilic ionic improves the hydrophilic of ultrafilter membrane, and in crosslinking, the ultrafilter membrane of amphoterisation ionizing chitosan component can be significantly improved in hydrophilic than PVA+TEOS blend.
Fig. 4 is the Electronic Speculum figure of the ultrafilter membrane prepared in embodiment 1, from fig. 4, it can be seen that the ultrafilter membrane uniform pore diameter prepared, atresia shrinkage phenomenon, the membrane flux good for it and pollution resistance lay the foundation.
After tested, ultrafilter membrane prepared by the present embodiment is soaked in distilled water 24 hours, has no dissolving, lamination, has water-resistance well, good hydrophilic property, and pure water flux is 75L m-2·h-1, simultaneously the removal efficiency of bovine serum albumin is 97.6% by it, has obvious antifouling effect, and after test of many times, this ultrafilter membrane still keeps higher flux and the removal efficiency to bovine serum albumin, simultaneously Heat stability is good, the long service life of most telolemma.
Embodiment 2-5
Same steps by embodiment 1, change the proportion shared by bisexual ion purification chitosan component in solution, the operational approach that other steps are identical with embodiment 1, prepares ultrafilter membrane and its water absorption, porosity, exchange capacity is tested, and test result is as shown in table 1:
Table 1: the ultrafilter membrane performance test data prepared in embodiment 2～5
Table 1 is the corresponding data of the amphoterisation ion chitosan ultrafiltration membrane of the different content prepared in the present embodiment 2～5, it can be seen that along with the increase of amphoterisation ion shell glycan content, its porosity, water absorption and exchange capacity increase accordingly.
Fig. 5 is the different content bisexual ion purification chitosan ultrafiltration membrane (Z-0 of preparation in embodiment 2～5, Z-1, Z-2, Z-4 represents the amount ratio of amphoterisation ion polysaccharide respectively 0%, 10%, 20%, 40%) to pure water, protein, the water flux block diagram of lysozyme, as seen from the figure: the membrane flux of the ultrafilter membrane containing bisexual ion purification chitosan is greater than the ultrafilter membrane without bisexual ion purification chitosan, and the increase of the content along with amphoterisation ion polysaccharide, amount of flux is at pure water, protein, lysozyme all increases accordingly, this also illustrates, the addition of amphoterisation ion polysaccharide makes the hydrophilic of PVA ultrafilter membrane and pollution resistance significantly improve.
Fig. 6 is the ultrafilter membrane recovery rate block diagram prepared in embodiment 2～5, as seen from the figure: the recovery rate of the ultrafilter membrane containing bisexual ion purification chitosan is greater than the ultrafilter membrane without bisexual ion purification chitosan, and the increase (Z-0 along with amphoterisation chitosan constituent content, Z-1, Z-2, Z-4 represents the amount ratio of bisexual ion purification chitosan respectively 0%, 10%, 20%, 40%), the recovery rate of ultrafilter membrane is significantly improved, and this also illustrates, the addition of amphoterisation ion polysaccharide makes PVA ultrafilter membrane better to reuse, longer service life.
Further, since when adopting epoxychloropropane as cross-linking agent, obtained ultrafilter membrane behavior pattern is similar to above-described embodiment gained ultrafilter membrane, just no longer carefully chats one by one in present specification.
Summary each comparative example can be seen that, the difference of each raw material difference bisexual ion purification chitosan in the present invention, flux still has a greater change, so the determination to raw material dosage each in the present invention is a process constantly groped and test, takes the substantial amounts of time and efforts of inventor.
In sum: chitosan will be modified preparing bisexual ion purification chitosan by the present invention, then under the effect of cross-linking agent, bisexual ion purification chitosan and polyvinyl alcohol are carried out blending reaction film forming, the ultrafilter membrane prepared is while having good water-resistance, there is hydrophilic well, protein and lysozyme all had pollution resistance well, pollution resistance is good, and also there is good anti-soil selectivity, especially bovine serum albumin is had good anti-soil selectivity, Heat stability is good, long service life, preparation technology is simple, it is easily achieved the advantages such as scale, in terms of existing technologies, achieve significance progress and unexpected effect.
Finally need it is pointed out here that: be only the part preferred embodiment of the present invention above; it is not intended that limiting the scope of the invention, some nonessential improvement and adjustment that those skilled in the art makes according to the foregoing of the present invention belong to protection scope of the present invention.
Claims (10)
1. an anti-protein-contamination amphion ultrafilter membrane, it is characterised in that: it is on supporter, after film forming, be immersed in the water generation phase conversion reaction by the gel coating that bisexual ion purification chitosan is prepared with the reaction of polyvinyl alcohol collosol and gelization to prepare.
2. anti-protein-contamination amphion ultrafilter membrane according to claim 1, it is characterized in that: described bisexual ion purification chitosan is to be prepared by imidization chitosan and sulfonated reagent generation sulfonating reaction, described imidization chitosan is to be reacted with paradime thylaminobenzaldehyde by chitosan, then prepares with boron hydride generation reduction reaction.
3. anti-protein-contamination amphion ultrafilter membrane according to claim 2, it is characterized in that: after the preparation of described imidization chitosan comprises the steps: to mix the acetic acid solution of chitosan with the alcoholic solution of paradime thylaminobenzaldehyde, the pH value regulating mixed solution with hydrochloric acid is 2～3, reaction is stirred at room temperature 5～7 hours, then the pH value adding sodium hydrate aqueous solution adjustment reaction solution in reaction solution is 4～6, it is subsequently added into sodium borohydride solution and carries out reduction reaction, after reacting completely, precipitate out precipitation, collect precipitation, prepare imidization chitosan.
4. anti-protein-contamination amphion ultrafilter membrane according to claim 3, it is characterized in that: the preparation of described bisexual ion purification chitosan comprises the steps: to be dissolved in hydrochloric acid solution by imidization chitosan, add sulfonated reagent, stirring reaction 5～6 hours at 55～65 DEG C, after reacting completely, reactant is joined in acetone and precipitate, collect precipitation, prepare bisexual ion purification chitosan.
5. anti-protein-contamination amphion ultrafilter membrane according to claim 4, it is characterised in that: described sulfonated reagent is selected from any one in halogenosulfonic acid salt, sulfur trioxide complex, sultones.
6. anti-protein-contamination amphion ultrafilter membrane according to claim 4, it is characterised in that: described sulfonated reagent is 1.2:1～1.6:1 with the mol ratio of amino in chitosan molecule.
7. the preparation method of the anti-protein-contamination amphion ultrafilter membrane described in a claim 1, it is characterised in that: comprise the steps:
A) solution blended process is adopted, bisexual ion purification chitosan solution and poly-vinyl alcohol solution are mixed into uniform solution, in solution, then add cross-linking agent, and the pH value regulating solution is 2～3, under room temperature, stirring carries out collosol and gel reaction in 10～12 hours, prepares gel；
B) by prepared gel coating film forming on polyfluortetraethylene plate, the thickness controlling thin film is 0.2～0.3mm, is immersed in by the film obtained in pure water and phase conversion reaction occurs, obtain described amphion ultrafilter membrane.
8. preparation method according to claim 7, it is characterised in that: the mass ratio of polyvinyl alcohol and bisexual ion purification chitosan is 10:1～1:1.
9. preparation method according to claim 7, it is characterised in that: described cross-linking agent selects tetraethyl orthosilicate or epoxychloropropane.
10. preparation method according to claim 7, it is characterised in that: the quality of the cross-linking agent of addition is the 5～10% of polyvinyl alcohol and bisexual ion purification chitosan mass sum.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480288A (en) * | 2020-11-23 | 2021-03-12 | 浙江工商大学 | Ionized chitosan and preparation method and application thereof |
| CN114288880A (en) * | 2021-12-17 | 2022-04-08 | 沃顿科技股份有限公司 | Antibacterial hydrophilic ultrafiltration membrane and preparation method thereof |
| CN114685695A (en) * | 2022-05-09 | 2022-07-01 | 河北科技师范学院 | Modified chitosan and preparation method thereof |
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| CN101007243A (en) * | 2006-01-26 | 2007-08-01 | 中国科学院大连化学物理研究所 | Preparation method of polyvinyl chitosan mixed film |
| CN102728241A (en) * | 2012-07-18 | 2012-10-17 | 天津工业大学 | Anti-pollution separation membrane and preparation method |
| CN103316599A (en) * | 2013-06-26 | 2013-09-25 | 浙江大学 | Preparation method of glycine betaine colloid nano particle modified chitosan nanofiltration membrane |
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| CN101007243A (en) * | 2006-01-26 | 2007-08-01 | 中国科学院大连化学物理研究所 | Preparation method of polyvinyl chitosan mixed film |
| CN102728241A (en) * | 2012-07-18 | 2012-10-17 | 天津工业大学 | Anti-pollution separation membrane and preparation method |
| CN103316599A (en) * | 2013-06-26 | 2013-09-25 | 浙江大学 | Preparation method of glycine betaine colloid nano particle modified chitosan nanofiltration membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112480288A (en) * | 2020-11-23 | 2021-03-12 | 浙江工商大学 | Ionized chitosan and preparation method and application thereof |
| CN114288880A (en) * | 2021-12-17 | 2022-04-08 | 沃顿科技股份有限公司 | Antibacterial hydrophilic ultrafiltration membrane and preparation method thereof |
| CN114685695A (en) * | 2022-05-09 | 2022-07-01 | 河北科技师范学院 | Modified chitosan and preparation method thereof |
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