CN102643449B - Method for preparing polymer porous membrane without solvent - Google Patents
Method for preparing polymer porous membrane without solvent Download PDFInfo
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- CN102643449B CN102643449B CN 201210133874 CN201210133874A CN102643449B CN 102643449 B CN102643449 B CN 102643449B CN 201210133874 CN201210133874 CN 201210133874 CN 201210133874 A CN201210133874 A CN 201210133874A CN 102643449 B CN102643449 B CN 102643449B
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Abstract
The invention discloses a method for preparing polymer porous membrane without solvent. The method includes steps of utilizing benzoyl peroxide as trigger and hexamethylene diacrylate as crosslinking agent, subjecting liquid-phase monomer methyl acrylic hydroxy ethyl ester to bulk polymerization between two glass sheets through thermal initiation, crosslinking and curing to forming a membrane; meanwhile, forming silica particles by porogen tetraethoxysilane through sol melting and gelling during membrane forming , and removing the silica particles to forming pores after membrane forming. The method for preparing polymer porous membrane has no needs of organic solvent and is environment-friendly, expense on solvent can be saved, solvent recycling process is omitted, and membrane forming cost is reduced. The surface of the membrane prepared by the method is high in hydrophilcity, low in protein adsorption and adjustable in thickness and expresses high flux, excellent separation effect and pollution-resistance performance when used for bioseparation.
Description
Technical field
The present invention relates to a kind of non-solvent preparation of polymer porous film, belong to the preparing technical field of porous-film.
Background technology
Method for preparing porous film (being mainly immersion precipitation phase inversion process, 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 polymeric film preparation process.On the one hand, solvent mixes forming the homogeneous phase film-casting liquid as dissolve medium with film-forming polymer, various additive.On the other hand, the inversion of phases Solvent is formed with vital role to the structure of film.In the immersion precipitation phase inversion process, the exchange of solvent of organic solvent and non-solvent (water commonly used) has caused the generation of inversion of phases.The film-forming polymer chain is dissolved in the continuous polymer-rich phase of formation in organic solvent, and in film-casting liquid, other add component, and for example pore-creating agent, form the polymer-poor phase that disperses.Along with the carrying out of exchange of solvent, polymer-rich phase film-forming main body, and polymer-poor phase forms fenestra.Adjust the interaction between solvent and non-solvent, will obtain having finger-like pore, the film of the Different Pore Structures such as sponge hole.In solvent evaporated method, organic solvent is under room temperature or heating condition, and organic solvent evaporates in air, and the film-forming polymer substrate concentration exceeds solubleness and constantly separates out precipitation, final film-forming.
The organic solvent that film-forming process is commonly used comprises DMF (DMF), N,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone (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 often has neural system, respiratory system, liver, renal toxicity, and skin is had hormesis, reports that even 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 specified 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 film-casting liquid is generally 60%-90%, cost is higher.The 3rd, the organic solvent recovery difficult is large.Organic solvent reclaims general adopt underpressure distillation or rectifying recovery, because masking organic solvent boiling point is high, and organic solvent concentration low (being usually less than 8%) in masking waste water, reclaim energy consumption high, reclaim less economical.Simultaneously, due to the bio-toxicity of organic solvent and relatively poor biodegradability, the processing of masking waste water is difficult also.
In sum, guaranteeing to realize under the film properties prerequisite that the preparation of film will become an important technology under the organic solvent-free condition.
Summary of the invention
The object of the present invention is to provide a kind of non-solvent preparation of polymer porous film, this preparation method's process is simple to operation, environmental protection, and prepared film has antipollution, high-throughput, highly selective characteristic.
The present invention is realized that by following technical proposals a kind of non-solvent preparation of polymer porous film is characterized in that comprising the following steps:
1) be reacted into membrane process
with organic monomer methacrylic acid hydroxyl ethyl ester (HEMA), pore-creating agent tetraethoxy (TEOS), initiator benzoyl peroxide (BPO), linking agent 1, 6-hexanediyl ester (HDODA) carries out the mixed preparing film-casting liquid in following ratio: the mass ratio 1:(0.25-4 of organic monomer methacrylic acid hydroxyl ethyl ester and pore-creating agent tetraethoxy), initiator benzoyl peroxide quality is 5% of methacrylic acid hydroxyl ethyl ester quality, linking agent 1, 6-hexanediyl ester volume is 4% of organic monomer methacrylic acid hydroxyl ethyl ester volume, under nitrogen protection, film-casting liquid is used supersound process 2-10 minute, get film-casting liquid and drop in first piece sheet one end, live film-casting liquid 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, film-casting liquid is sprawled the formation liquid film between two sheet glass sheets, 0.1-3KPa exerts pressure on two blocks of sheet glass, two sheet glass sheets are transferred in vacuum drying oven in temperature 60-90 ℃ of thermal treatment 12-36h, take out cool to room temperature,
2) pore process
With two sheet glass sheet strip ofves, it is in 1% hydrofluoric acid that the sheet glass that will adhere to solid film immerses massfraction, film is peeled off from sheet glass automatically, and to transfer to rapidly massfraction be to soak 0.5-4h in 10% hydrofluoric acid, remove silica dioxide granule, again film is transferred in ethanol and washs, be immersed at last 12-24h in deionized water, obtain polymer porous film.
The invention has the advantages that: with respect to traditional 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 recuperation process, reduce facility 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.Prepared polyHEMA film surface hydrophilicity is strong, and physical strength is higher, and protein adsorption quantity is low, and film thickness is controlled, has showed high-throughput when being used for bioseparation and (has reached as high as 8549L/ (m
2H)), higher cell retention rate (reaching 98%) and good contamination resistance (washing flux recovery rate reaches as high as 97%).
Description of drawings
Fig. 1 is the surface scan Electronic Speculum figure of the embodiment of the present invention 2 prepared polymer porous films.
Fig. 2 is the bottom surface scanning electron microscope (SEM) photograph of the embodiment of the present invention 2 prepared polymer porous films.
Fig. 3 is the section face scanning electron microscope (SEM) photograph of the embodiment of the present invention 5 prepared polymer porous films.
Embodiment
Take organic monomer methacrylic acid hydroxyl ethyl ester HEMA2g, initiator B PO0.1g, pore-creating agent TEOS0.5g measures 80 μ L linking agent HDODA, mixed preparing film-casting liquid, supersound process 5min under nitrogen protection.The film-casting liquid that measures volume and be 20 μ L drops in first piece sheet (75mm*25mm) end, live film-casting liquid 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 film-casting liquid is sprawled the formation liquid film between two sheet glass sheets.The two sheet glass sheets that accompany the film-casting liquid liquid film are transferred in vacuum drying oven thermal treatment 24h under 80 ℃ of normal pressures, take out cool to room temperature.It is that in 1% hydrofluoric acid HF, film is peeled off from sheet glass automatically that the sheet glass that will adhere to solid film immerses the 100mL massfraction, and to transfer to rapidly the 100mL massfraction be to soak 1h in 10% hydrofluoric acid HF, removes silica dioxide granule.Again film is transferred in ethanol and washs three times, be immersed at last 24h in deionized water, obtain the polymethyl acrylic acid hydroxy methacrylate polyHEMA film 1 of solventless method preparation.
Prepared polyHEMA film is through scanning electron microscope analysis, and fenestra is evenly distributed, and pore size distribution 0.4-2.3 μ m, film thickness are 11.8 μ m.The static state hydrolysis feeler of film is only 20.8 °, and wetting ability is strong.The static protein adsorption amount of film is only 3.2 μ g/cm
2, have excellent anti-protein adsorptive power.For separating of 1g/L yeast and 1g/L bovine serum albumin mixed solution, flux stabilized is at 316L/ (m
2H), separation selectivity is good, and the yeast rejection is 98.4%, and the bovine serum albumin rejection is 3.1%.Antifouling property is excellent, and after washing, the flux recovery rate reaches 93.0%.
Embodiment 2
Take organic monomer methacrylic acid hydroxyl ethyl ester HEMA2g, initiator B PO0.1g, pore-creating agent TEOS2g measures 80 μ L linking agent HDODA, mixed preparing film-casting liquid, supersound process 5min under nitrogen protection.The film-casting liquid that measures volume and be 20 μ L drops in first piece sheet (75mm*25mm) end, live film-casting liquid 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 film-casting liquid is sprawled the formation liquid film between two sheet glass sheets.The two sheet glass sheets that accompany the film-casting liquid liquid film are transferred in vacuum drying oven thermal treatment 24h under 80 ℃ of normal pressures, take out cool to room temperature.It is that in 1% hydrofluoric acid HF, film is peeled off from sheet glass automatically that the sheet glass that will adhere to solid film immerses the 100mL massfraction, and to transfer to rapidly the 100mL massfraction be to soak 1h in 10% hydrofluoric acid HF, removes silica dioxide granule.Again film is transferred in ethanol and washs three times, be immersed at last 24h in deionized water, obtain the polymethyl acrylic acid hydroxy methacrylate polyHEMA film 2 of solventless method preparation.
Prepared polyHEMA film is through scanning electron microscope analysis, and fenestra is evenly distributed, and pore size distribution 0.4-2.3 μ m, film thickness are 12.1 μ m.The static state hydrolysis feeler of film is only 18.9 °, and wetting ability is strong.The static protein adsorption amount of film is only 4.1 μ g/cm
2, have excellent anti-protein adsorptive power.For separating of 1g/L yeast and 1g/L bovine serum albumin mixed solution, flux stabilized is at 2250L/ (m
2H), separation selectivity is good, and the yeast rejection is 95.8%, and the bovine serum albumin rejection is 1.1%.Antifouling property is excellent, and after washing, the flux recovery rate reaches 95.1%.
Embodiment 3
Take organic monomer methacrylic acid hydroxyl ethyl ester HEMA2g, initiator B PO0.1g, pore-creating agent TEOS6g measures 80 μ L linking agent HDODA, mixed preparing film-casting liquid, supersound process 5min under nitrogen protection.The film-casting liquid that measures volume and be 20 μ L drops in first piece sheet (75mm*25mm) end, live film-casting liquid 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 film-casting liquid is sprawled the formation liquid film between two sheet glass sheets.The two sheet glass sheets that accompany the film-casting liquid liquid film are transferred in vacuum drying oven thermal treatment 24h under 80 ℃ of normal pressures, take out cool to room temperature.It is that in 1% hydrofluoric acid HF, film is peeled off from sheet glass automatically that the sheet glass that will adhere to solid film immerses the 100mL massfraction, and to transfer to rapidly the 100mL massfraction be to soak 1h in 10% hydrofluoric acid HF, removes silica dioxide granule.Again film is transferred in ethanol and washs three times, be immersed at last 24h in deionized water, obtain the polymethyl acrylic acid hydroxy methacrylate polyHEMA film 3 of solventless method preparation.
Prepared polyHEMA film is through scanning electron microscope analysis, and fenestra is evenly distributed, and pore size distribution 0.5-2.3 μ m, film thickness are 11.6 μ m.The static state hydrolysis feeler of film is only 26.1 °, and wetting ability is strong.The static protein adsorption amount of film is only 5.0 μ g/cm
2, have excellent anti-protein adsorptive power.For separating of 1g/L yeast and 1g/L bovine serum albumin mixed solution, flux stabilized is at 8549L/ (m
2H), separation selectivity is good, and the yeast rejection is 96.1%, and the bovine serum albumin rejection is 2.2%.Antifouling property is excellent, and after washing, the flux recovery rate reaches 90.2%.
Embodiment 4
Take organic monomer methacrylic acid hydroxyl ethyl ester HEMA2g, initiator B PO0.1g, pore-creating agent TEOS2g measures 80 μ L linking agent HDODA, mixed preparing film-casting liquid, supersound process 5min under nitrogen protection.The film-casting liquid that measures volume and be 20 μ L drops in first piece sheet (75mm*25mm) end, live film-casting liquid 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 film-casting liquid is sprawled the formation liquid film between two sheet glass sheets.The 1.3KPa that exerts pressure on two blocks of sheet glass, and two sheet glass sheets are transferred in vacuum drying oven thermal treatment 24h under 80 ℃ of normal pressures, take out cool to room temperature.It is that in 1% hydrofluoric acid HF, film is peeled off from sheet glass automatically that the sheet glass that will adhere to solid film immerses the 100mL massfraction, and to transfer to rapidly the 100mL massfraction be to soak 1h in 10% hydrofluoric acid HF, removes silica dioxide granule.Again film is transferred in ethanol and washs three times, be immersed at last 24h in deionized water, obtain the polymethyl acrylic acid hydroxy methacrylate polyHEMA film 4 of solventless method preparation.
Prepared polyHEMA film is through scanning electron microscope analysis, and fenestra is evenly distributed, and pore size distribution 0.4-2.3 μ m, film thickness are 5.7 μ m.The static state hydrolysis feeler of film is only 19.4 °, and wetting ability is strong.The static protein adsorption amount of film is only 3.9 μ g/cm
2, have excellent anti-protein adsorptive power.For separating of 1g/L yeast and 1g/L bovine serum albumin mixed solution, flux stabilized is at 4703L/ (m
2H), separation selectivity is good, and the yeast rejection is 96.8%, and the bovine serum albumin rejection is 1.0%.Antifouling property is excellent, and after washing, the flux recovery rate reaches 94.8%.
Embodiment 5
Take organic monomer methacrylic acid hydroxyl ethyl ester HEMA2g, initiator B PO0.1g, pore-creating agent TEOS2g measures 80 μ L linking agent HDODA, mixed preparing film-casting liquid, supersound process 5min under nitrogen protection.The film-casting liquid that measures volume and be 20 μ L drops in first piece sheet (75mm*25mm) end, live film-casting liquid 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 film-casting liquid is sprawled the formation liquid film between two sheet glass sheets.The 2.6KPa that exerts pressure on two blocks of sheet glass, and two sheet glass sheets are transferred in vacuum drying oven thermal treatment 24h under 80 ℃ of normal pressures, take out cool to room temperature.It is that in 1% hydrofluoric acid HF, film is peeled off from sheet glass automatically that the sheet glass that will adhere to solid film immerses the 100mL massfraction, and to transfer to rapidly the 100mL massfraction be to soak 1h in 10% hydrofluoric acid HF, removes silica dioxide granule.Again film is transferred in ethanol and washs three times, be immersed at last 24h in deionized water, obtain the polymethyl acrylic acid hydroxy methacrylate polyHEMA film 5 of solventless method preparation.
Prepared polyHEMA film is through scanning electron microscope analysis, and fenestra is evenly distributed, and pore size distribution 0.4-2.3 μ m, film thickness are 2.8 μ m.The static state hydrolysis feeler of film is only 18.5 °, and wetting ability is strong.The static protein adsorption amount of film is only 4.2 μ g/cm
2, have excellent anti-protein adsorptive power.For separating of 1g/L yeast and 1g/L bovine serum albumin mixed solution, flux stabilized is at 7688L/ (m
2H), separation selectivity is good, and the yeast rejection is 95.2%, and the bovine serum albumin rejection is 1.3%.Antifouling property is excellent, and after washing, the flux recovery rate reaches 95.0%.
Embodiment 6
Take organic monomer methacrylic acid hydroxyl ethyl ester HEMA2g, initiator B PO0.1g, pore-creating agent TEOS0.5g measures 80 μ L linking agent HDODA, mixed preparing film-casting liquid, supersound process 5min under nitrogen protection.The film-casting liquid that measures volume and be 10 μ L drops in first piece sheet (75mm*25mm) end, live film-casting liquid 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 film-casting liquid is sprawled the formation liquid film between two sheet glass sheets.The two sheet glass sheets that accompany the film-casting liquid liquid film are transferred in vacuum drying oven thermal treatment 24h under 80 ℃ of normal pressures, take out cool to room temperature.It is that in 1% hydrofluoric acid HF, film is peeled off from sheet glass automatically that the sheet glass that will adhere to solid film immerses the 100mL massfraction, and to transfer to rapidly the 100mL massfraction be to soak 1h in 10% hydrofluoric acid HF, removes silica dioxide granule.Again film is transferred in ethanol and washs three times, be immersed at last 24h in deionized water, obtain the polymethyl acrylic acid hydroxy methacrylate polyHEMA film 6 of solventless method preparation.
Prepared polyHEMA film is through scanning electron microscope analysis, and fenestra is evenly distributed, and pore size distribution 0.4-2.3 μ m, film thickness are 5.8 μ m.The static state hydrolysis feeler of film is only 22.6 °, and wetting ability is strong.The static protein adsorption amount of film is only 4.8 μ g/cm
2, have excellent anti-protein adsorptive power.For separating of 1g/L yeast and 1g/L bovine serum albumin mixed solution, flux stabilized is at 4568L/ (m
2H), separation selectivity is good, and the yeast rejection is 96.0%, and the bovine serum albumin rejection is 1.6%.Antifouling property is excellent, and after washing, the flux recovery rate reaches 94.0%.
Embodiment 7
Take organic monomer methacrylic acid hydroxyl ethyl ester HEMA2g, initiator B PO0.1g, pore-creating agent TEOS0.5g measures 80 μ L linking agent HDODA, mixed preparing film-casting liquid, supersound process 5min under nitrogen protection.The film-casting liquid that measures volume and be 40 μ L drops in first piece sheet (75mm*25mm) end, live film-casting liquid 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 film-casting liquid is sprawled the formation liquid film between two sheet glass sheets.The two sheet glass sheets that accompany the film-casting liquid liquid film are transferred in vacuum drying oven thermal treatment 24h under 80 ℃ of normal pressures, take out cool to room temperature.It is that in 1% hydrofluoric acid HF, film is peeled off from sheet glass automatically that the sheet glass that will adhere to solid film immerses the 100mL massfraction, and to transfer to rapidly the 100mL massfraction be to soak 1h in 10% hydrofluoric acid HF, removes silica dioxide granule.Again film is transferred in ethanol and washs three times, be immersed at last 24h in deionized water, obtain the polymethyl acrylic acid hydroxy methacrylate polyHEMA film 7 of solventless method preparation.
Prepared polyHEMA film is through scanning electron microscope analysis, and fenestra is evenly distributed, and pore size distribution 0.4-2.3 μ m, film thickness are 18.3 μ m.The static state hydrolysis feeler of film is only 20.4 °, and wetting ability is strong.The static protein adsorption amount of film is only 4.6 μ g/cm
2, have excellent anti-protein adsorptive power.For separating of 1g/L yeast and 1g/L bovine serum albumin mixed solution, flux stabilized is at 986L/ (m
2H), separation selectivity is good, and the yeast rejection is 95.8%, and the bovine serum albumin rejection is 1.4%.Antifouling property is excellent, and after washing, the flux recovery rate reaches 93.8%.
The Performance Ratio of the super strong type series filter membrane of the close granulosa isolation technique of the performance of the prepared polymer porous film of the embodiment of the present invention and existing Shanghai company limited is classified table 1 as.The filter membrane material of Shanghai close granulosa isolation technique company limited is made from mixed materials, and main component is cellulose acetate, and the aperture is 0.22 μ m, and diameter is 50mm.
Table 1
Claims (1)
1. the non-solvent preparation of a polymer porous film is characterized in that comprising the following steps:
1) be reacted into membrane process
with organic monomer methacrylic acid hydroxyl ethyl ester, the pore-creating agent tetraethoxy, the initiator benzoyl peroxide, linking agent 1, the 6-hexanediyl ester carries out the mixed preparing film-casting liquid in following ratio: the mass ratio 1:(0.25-4 of organic monomer methacrylic acid hydroxyl ethyl ester and pore-creating agent tetraethoxy), initiator benzoyl peroxide quality is 5% of methacrylic acid hydroxyl ethyl ester quality, linking agent 1, 6-hexanediyl ester volume is 4% of organic monomer methacrylic acid hydroxyl ethyl ester volume, under nitrogen protection, film-casting liquid is used supersound process 2-10 minute, get film-casting liquid and drop in first piece sheet one end, live film-casting liquid 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, film-casting liquid is sprawled the formation liquid film between two sheet glass sheets, 0.1-3KPa exerts pressure on two blocks of sheet glass, two sheet glass sheets are transferred in vacuum drying oven in temperature 60-90 ℃ of thermal treatment 12-36h, take out cool to room temperature,
2) pore process
With two sheet glass sheet strip ofves, it is in 1% hydrofluoric acid that the sheet glass that will adhere to solid film immerses massfraction, film is peeled off from sheet glass automatically, and to transfer to rapidly massfraction be to soak 0.5-4h in 10% hydrofluoric acid, remove silica dioxide granule, again film is transferred in ethanol and washs, be immersed at last 12-24h in deionized water, obtain polymer porous film.
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| CN102886211A (en) * | 2012-09-28 | 2013-01-23 | 天津大学 | Solvent-free preparation method of aperture controllable porous film |
| CN102886210A (en) * | 2012-09-28 | 2013-01-23 | 天津大学 | Solvent-free preparation method of anti-pollution self-cleaning oil-water separation film |
| CN103007770A (en) * | 2012-09-28 | 2013-04-03 | 天津大学 | Solvent-free preparation method of temperature-sensitive separation film |
| CN102908913A (en) * | 2012-09-28 | 2013-02-06 | 天津大学 | Solvent-free preparation method for pH value sensitive type separation membrane |
| CN103611424B (en) * | 2013-11-08 | 2016-06-01 | 江南大学 | A kind of method without supporter porousness polymeric membrane for separation anionic finishing of thermofixation |
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| CN102193213A (en) * | 2011-05-19 | 2011-09-21 | 东南大学 | Brightly colorful contact lens and preparation method thereof |
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| 陈鹏.PHEMASiO_2n-HA凝胶膜的制备和生物相容性研究.《中国博士学位论文全文数据库医药卫生科技辑（月刊）》.2010,(第10期),E080-15. * |
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