CN102908913A - Solvent-free preparation method for pH value sensitive type separation membrane - Google Patents
Solvent-free preparation method for pH value sensitive type separation membrane Download PDFInfo
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- CN102908913A CN102908913A CN2012103682516A CN201210368251A CN102908913A CN 102908913 A CN102908913 A CN 102908913A CN 2012103682516 A CN2012103682516 A CN 2012103682516A CN 201210368251 A CN201210368251 A CN 201210368251A CN 102908913 A CN102908913 A CN 102908913A
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Abstract
The invention discloses a solvent-free preparation method for a pH value sensitive type separation membrane. The method comprises the following steps: taking 1-hydroxy cyclohexyl phenyl ketone as an initiator; taking hexanediol diacrylate as a cross-linking agent; initiating polymerization, cross-linking, curing and membrane-forming of membrane-forming monomer methacrylic acid hydroxybutyrate and charging monomer methacrylic acid between two glass sheets through ultraviolet; and forming pores by removing silica particles which are formed by porogen tetraethoxysilane. The preparation method is free from solvent, and environment-friendly; and expense of the solvent is saved, and the process of recovering the solvent is not required. The prepared membrane has good responsiveness to environment pH value; under an acid condition, the aperture of the membrane is enlarged, the flux is increased and the interception rate is reduced; the pH response performance is reverse and stable; and the membrane can be recycled.
Description
Technical field
The present invention relates to a kind of non-solvent preparation of pH value sensitive type diffusion barrier, belong to the membrane separation technique field.
Background technology
Membrane preparation method (mainly being immersion precipitation phase inversion, solvent evaporated method etc.) commonly used all need use a large amount of organic solvents, effect aspect two below organic solvent mainly plays in the polymer film preparation process.On the one hand, solvent mixes formation homogeneous phase casting solution as dissolve medium with film forming polymer, various additive.On the other hand, the inversion of phases Solvent is formed with important function to the structure of film.In the immersion precipitation phase inversion, the exchange of solvent of organic solvent and non-solvent (water commonly used) has caused the generation of inversion of phases.The organic solvent that film-forming process is commonly used comprises DMF (DMF), DMA (DMAc), 1-METHYLPYRROLIDONE (NMP) etc.Film-forming process with an organic solvent has following shortcoming in a large number.At first, organic solvent is harmful to human body and environment.For example, DMF is often toxic to nervous system, respiratory system, liver and kidney, and skin is had spread effect, even reports that DMF can cause cancer and chromosome aberration.DMAc will cause the infringement of liver, causes toxic hepatitis.Occupational health standard (GBZ2-2002) the workplace harmful factors Exposed limit value stipulated time weighted average allowable concentration 20mg/m of country of the People's Republic of China (PRC)
3Secondly, cost with an organic solvent is higher.Because organic solvent shared mass ratio in casting solution is generally 60%-90%, cost is higher.The 3rd, the organic solvent recovery difficult is large.Organic solvent reclaims general adopt decompression distillation or rectifying recovery, because masking organic solvent boiling point is high, and organic solvent concentration low (being usually less than 8%) in the masking waste water, reclaim energy consumption high, reclaim less economical.Simultaneously, because the bio-toxicity of organic solvent and relatively poor biodegradability, the processing of masking waste water is difficult also.
In recent years, polymer film traditional, function singleness can not satisfy people's needs far away, and polymer film novel high-performance, multi-functional arises at the historic moment." intelligence " polymer film of can be according to the variation of external environmental condition and automatically the separating behavior of himself being made suitable adjustment has caused scientist's interest and concern.The characteristics of this class smart membrane are that it not only can the perception environment, and can accord with one's environment.The environment-responsive of smart membrane be since in the polymer film variation of macromolecular conformation and state of aggregation have invertibity, thereby so that infiltration, diffusion and the transmission of certain material in film can change with the variation of environmental stimulus signal.The pH response film to external world pH value of environment has the film of stimuli responsive, and fenestra can reversibly shrink or expand with extraneous pH variation, has strengthened the operating flexibility of film, has expanded the range of application of film.In theory, pH response film can be by changing environment pH value, realize that film is to the Selective Separation of ionic mixture, on using, the separating-purifying that can be used for ionic drug and biological products, the controllable release of medicine, the exploitation of medical equipment (such as hemodialysis membrane) and water body purifying (such as the recovery of electrophoretic paint, electrically charged bacterium, toxin removes etc. in liquid, the pure water).The preparation method of at present pH response film is grafted to charged material or zwitterionic materials in film surface or the fenestra.
In sum, the technology of preparation pH value sensitive type diffusion barrier under the organic solvent-free condition is proposed, tool most important theories meaning and using value.
Summary of the invention
The object of the present invention is to provide a kind of non-solvent preparation of pH value sensitive type diffusion barrier, this preparation method's process is simple to operation, environmental protection, and prepared film has pH value response characteristic.
The present invention realized by following technical proposals, and a kind of non-solvent preparation of pH value sensitive type diffusion barrier is characterized in that may further comprise the steps:
1) is reacted into membrane process
With monomer methacrylic acid hydroxyl ethyl ester (HEMA), pore-foaming agent ethyl orthosilicate (TEOS), crosslinking agent 1,6-hexanediyl ester (HDODA), charged monomer methacrylic acid (MAA) and initator 1-hydroxy-cyclohexyl phenyl ketone (HCPK) be 1:1:0.08:(0.02-0.20 in mass ratio): (0.0102-0.0120) mix the formation casting solution, under nitrogen protection to the ultrasonic processing of casting solution 2-10 minute, get casting solution and drop in first piece sheet one end, live casting solution on first block of sheet glass with an end cap of second block of sheet glass, second block of sheet glass of translation overlaps two sheet glass sheets, casting solution is sprawled the formation liquid film between two sheet glass sheets, two sheet glass sheets are placed ultraviolet lighting processing 1-3min under the 200W high-pressure sodium lamp;
2) pore process
With two sheet glass sheet strip ofves, it is in 1% the hydrofluoric acid that the sheet glass that will adhere to solid film immerses mass fraction, solid film is peeled off from sheet glass automatically, and it is transferred to mass fraction is to soak 0.5-4h in 10% the hydrofluoric acid, again solid film is transferred in the ethanol and washs, be immersed at last 12-24h in the deionized water, obtain having pH value sensitive type diffusion barrier.
The invention has the advantages that: with respect to conventional method, the method preparation process need not organic solvent, green non-pollution; Can save solvent cost, therefore can reduce the masking cost; Need not simultaneously the solvent recovery process, reduce equipment investment and energy consumption.Monomer material is cheap and easy to get, and the film preparation process is simple, and mild condition is easy to amplify.Film has good response to environment pH value, and film aperture under acid condition increases, and flux increases and the rejection reduction.The pH response performance is reversible and stable, can repeatedly recycle.
Description of drawings
Fig. 1 is that the flux of the made pH value sensitive type diffusion barrier of the embodiment of the invention 1 is with pH value change curve.
Fig. 2 is that the flux of the made pH value sensitive type diffusion barrier of the embodiment of the invention 2 is with pH phase change curve on weekly duty.
Fig. 3 is that the flux of commercialization CAM of Comparative Examples 1 of the present invention is with pH value change curve.
The specific embodiment
Take by weighing monomer methacrylic acid hydroxyl ethyl ester 1.0g; pore-foaming agent ethyl orthosilicate 1.0g, crosslinking agent 1; 6-hexanediyl ester 80mg, charged monomer methacrylic acid 50mg and initator 1-hydroxy-cyclohexyl phenyl ketone 10.5mg; the mixed preparing casting solution, under nitrogen protection to the ultrasonic processing of casting solution 5min.The casting solution that measures volume and be 50 μ L drops in first piece sheet (75mm*25mm) end, live casting solution on first block of sheet glass with an end cap of second block of sheet glass (75mm*25mm), and second block of sheet glass of translation overlap two sheet glass sheets, and casting solution is sprawled the formation liquid film between two sheet glass sheets.The two sheet glass sheets that accompany liquid film are placed ultraviolet lighting 1min under the 200W high-pressure sodium lamp, take out cool to room temperature.With two sheet glass sheets separately, it is that solid film is peeled off from sheet glass automatically in 1% the hydrofluoric acid that the sheet glass that has adhered to solid film immerses mass fraction, and places that to transfer to mass fraction be that 10% hydrofluoric acid soaks 1h.Again solid film is transferred in the ethanol and washs three times, be immersed at last 24h in the deionized water, obtain poly (HEMA/MAA) film 1.
Prepared poly (HEMA/MAA) film 1 is 2.0 o'clock in the pH value, and water flux is 1925L/ (m
2H), the saccharomycete rejection is 78.4%.Be 6.0 o'clock in the pH value, water flux is 1252L/ (m
2H), the saccharomycete rejection is 96.2%.Be 10.0 o'clock in the pH value, water flux is 1016L/ (m
2H), the saccharomycete rejection is 97.2%.Film shows the response to low pH value, and the aperture increases under the acid condition, and flux increases and the rejection reduction.
Take by weighing monomer methacrylic acid hydroxyl ethyl ester 1.0g; pore-foaming agent ethyl orthosilicate TEOS1.0g, crosslinking agent 1; 6-hexanediyl ester 80mg, charged monomer methacrylic acid 100mg and initator 1-hydroxy-cyclohexyl phenyl ketone 11.0mg; the mixed preparing casting solution, under nitrogen protection to the ultrasonic processing of casting solution 5min.The casting solution that measures volume and be 50 μ L drops in first piece sheet (75mm*25mm) end, live casting solution on first block of sheet glass with an end cap of second block of sheet glass (75mm*25mm), second block of sheet glass of translation overlaps two sheet glass sheets, and casting solution is sprawled the formation liquid film between two sheet glass sheets.The two sheet glass sheets that accompany liquid film are placed ultraviolet lighting 1min under the 200W high-pressure sodium lamp, take out cool to room temperature.With two sheet glass sheets separately, it is that solid film is peeled off from sheet glass automatically in 1% the hydrofluoric acid that the sheet glass that has adhered to solid film immerses mass fraction, and to transfer to rapidly mass fraction be to soak 1h in 10% the hydrofluoric acid.Again solid film is transferred in the ethanol and washs three times, be immersed at last 24h in the deionized water, obtain poly (HEMA/MAA) film 2.
Prepared poly (HEMA/MAA) film 2 is 2.0 o'clock in the pH value, and water flux is 1244L/ (m
2H), the saccharomycete rejection is 64.2%.Be 6.0 o'clock in the pH value, water flux is 831L/ (m
2H), the saccharomycete rejection is 95.4%.Be 10.0 o'clock in the pH value, water flux is 734L/ (m
2H), the saccharomycete rejection is 96.7%.Film shows the response to low pH value, and the aperture increases under the acid condition, and flux increases and the rejection reduction.
Take by weighing monomer methacrylic acid hydroxyl ethyl ester 1.0g; pore-foaming agent ethyl orthosilicate 1.0g, crosslinking agent 1; 6-hexanediyl ester 80mg, charged monomer methacrylic acid 150mg and initator 1-hydroxy-cyclohexyl phenyl ketone 11.5mg; the mixed preparing casting solution, under nitrogen protection to the ultrasonic processing of casting solution 5min.The casting solution that measures volume and be 50 μ L drops in first piece sheet (75mm*25mm) end, live casting solution on first block of sheet glass with an end cap of second block of sheet glass (75mm*25mm), second block of sheet glass of translation overlaps two sheet glass sheets, and casting solution is sprawled the formation liquid film between two sheet glass sheets.The two sheet glass sheets that accompany liquid film are placed ultraviolet lighting 1min under the 200W high-pressure sodium lamp, take out cool to room temperature.With two sheet glass sheets separately, it is that solid film is peeled off from sheet glass automatically in 1% the hydrofluoric acid that the sheet glass that has adhered to solid film immerses mass fraction, and it is transferred to mass fraction is to soak 1h in 10% the hydrofluoric acid.Again solid film is transferred in the ethanol and washs three times, be immersed at last 24h in the deionized water, obtain poly (HEMA/MAA) film 3.
Prepared poly (HEMA/MAA) film 3 is 2.0 o'clock in the pH value, and water flux is 812L/ (m
2H), the saccharomycete rejection is 56.3%.Be 6.0 o'clock in the pH value, water flux is 596L/ (m
2H), the saccharomycete rejection is 96.9%.Be 10.0 o'clock in the pH value, water flux is 562L/ (m
2H), the saccharomycete rejection is 97.0%.Film shows the response to low pH value, and the aperture increases under the acid condition, and flux increases and the rejection reduction.
Comparative Examples 1
The comparative film 1 that the present invention selects is the super strong type series filter membrane of Shanghai close granulosa isolation technics Co., Ltd, and its material is made from mixed materials, and main component is cellulose acetate, and the aperture is 0.22 μ m, and diameter is 50mm.Comparative film 1 is 2.0 o'clock in the pH value, and water flux is 1244L/ (m
2H), the saccharomycete rejection is 98.6%.Be 6.0 o'clock in the pH value, water flux is 1258L/ (m
2H), the saccharomycete rejection is 99.4%.Be 10.0 o'clock in the pH value, water flux is 1226L/ (m
2H), the saccharomycete rejection is 99.1%.1 couple of pH of comparative film does not have response.
Comparative Examples 2
The comparative film 2 that the present invention selects is the super strong type series filter membrane of Shanghai close granulosa isolation technics Co., Ltd, and its material is made from mixed materials, and main component is cellulose acetate, and the aperture is 0.8 μ m, and diameter is 50mm.Comparative film 2 is 2.0 o'clock in the pH value, and water flux is 2839L/ (m
2H), the saccharomycete rejection is 51.5%.Be 6.0 o'clock in the pH value, water flux is 2748L/ (m
2H), the saccharomycete rejection is 53.4%.Be 10.0 o'clock in the pH value, water flux is 2868L/ (m
2H), the saccharomycete rejection is 52.1%.2 couples of pH of comparative film do not have response.
The performance of the prepared pH value sensitive type of embodiment of the invention diffusion barrier and the Performance Ratio of comparative film are classified table 1 as.
Table 1
Claims (1)
1. the non-solvent preparation of a pH value sensitive type diffusion barrier is characterized in that may further comprise the steps:
1) is reacted into membrane process
With monomer methacrylic acid hydroxyl ethyl ester, the pore-foaming agent ethyl orthosilicate, crosslinking agent 1, the 6-hexanediyl ester, charged monomer methacrylic acid and initator 1-hydroxy-cyclohexyl phenyl ketone be 1:1:0.08:(0.02-0.20 in mass ratio): (0.0102-0.0120) mix the formation casting solution, under nitrogen protection to the ultrasonic processing of casting solution 2-10 minute, get casting solution and drop in first piece sheet one end, live casting solution on first block of sheet glass with an end cap of second block of sheet glass, second block of sheet glass of translation overlaps two sheet glass sheets, casting solution is sprawled the formation liquid film between two sheet glass sheets, two sheet glass sheets are placed ultraviolet lighting processing 1-3min under the 200W high-pressure sodium lamp;
2) pore process
With two sheet glass sheet strip ofves, it is in 1% the hydrofluoric acid that the sheet glass that will adhere to solid film immerses mass fraction, solid film is peeled off from sheet glass automatically, and it is transferred to mass fraction is to soak 0.5-4h in 10% the hydrofluoric acid, again solid film is transferred in the ethanol and washs, be immersed at last 12-24h in the deionized water, obtain having pH value sensitive type diffusion barrier.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111001310A (en) * | 2019-12-23 | 2020-04-14 | 天津膜天膜科技股份有限公司 | Preparation method of environment-friendly nanofiltration membrane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497004A (en) * | 2009-01-21 | 2009-08-05 | 四川大学 | Polyethersulfone hollow fiber intelligent membrane with pH sensitivity as well as preparation method and application thereof |
| CN102068921A (en) * | 2010-11-30 | 2011-05-25 | 天津工业大学 | PH sensitive polyvinylidene fluoride gel film and preparation method thereof |
| CN102643449A (en) * | 2012-05-03 | 2012-08-22 | 天津大学 | Method for preparing polymer porous membrane without solvent |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497004A (en) * | 2009-01-21 | 2009-08-05 | 四川大学 | Polyethersulfone hollow fiber intelligent membrane with pH sensitivity as well as preparation method and application thereof |
| CN102068921A (en) * | 2010-11-30 | 2011-05-25 | 天津工业大学 | PH sensitive polyvinylidene fluoride gel film and preparation method thereof |
| CN102643449A (en) * | 2012-05-03 | 2012-08-22 | 天津大学 | Method for preparing polymer porous membrane without solvent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111001310A (en) * | 2019-12-23 | 2020-04-14 | 天津膜天膜科技股份有限公司 | Preparation method of environment-friendly nanofiltration membrane |
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Application publication date: 20130206 |