CN106422799B - Double solvent method preparation has the film of hierarchical porous structure - Google Patents
Double solvent method preparation has the film of hierarchical porous structure Download PDFInfo
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- CN106422799B CN106422799B CN201610857872.9A CN201610857872A CN106422799B CN 106422799 B CN106422799 B CN 106422799B CN 201610857872 A CN201610857872 A CN 201610857872A CN 106422799 B CN106422799 B CN 106422799B
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/026—Sponge structure
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
The present invention relates to the films that a kind of preparation of Double solvent method has hierarchical porous structure, it is characterized in that joined the good solvent for having excellent compatibility and solubility property with polymer in the casting film system, and property compatible with water is poor and can dissolve the low boiling point solvent of polymer again with volatility, two kinds of phase separations can occur for two kinds of different solvents in casting film liquid system；In film forming procedure by casting film drop on low boiling point solvent, and the system is formed a film at high humidity, it is regular pore structure that upper surface, which can be made, and lower surface is the hole of spongelike structure；The Double solvent method that the present invention uses, preparation method is novel, and obtained film does not have cortex, and fenestra is completely through film, and the fenestra between film upper surface, lower surface and its upper and lower surface differs in size, and has hierarchical porous structure；The film upper surface is regular pore structure, and aperture is 0.1~6 μm, and lower surface is spongy pore structure, and aperture is 0.001~0.1 μm.
Description
Technical field
The present invention relates to the films that a kind of preparation of Double solvent method has hierarchical porous structure.
Background technique
Membrane separation technique is to develop faster new and high technology in the past 30 years, in the world the forward position of generally acknowledged most development prospect
Technology has become one of hot spot and key technology of social sustainable development of various countries' research.Membrane separation technique have it is high-efficient,
Environmental protection and energy saving, it is easy to operate simple the advantages that.Core of the membrane material as film, further influences membrane separation technique.Membrane material shadow
The structure and properties of seperation film are rung, and film-forming method also determines the form and structure of film, eventually affects the separation effect of film
Energy.
Phase separation method be prepare the most common method of perforated membrane, including phase separation method, thermally induced phase separation and
Composite thermotropic phase separation method.Phase separation method is that membrane material is dissolved among solvent, forms homogeneous phase solution, striking
Film, is then immersed in coagulating bath and occurs mutually to separate, form the perforated membrane of different structure by film forming.Perforated membrane is prepared using this method
The amount of required solvent is big, and control technological parameter is more, and the stability being film-made is poor.Thermally induced phase separation is the variation by temperature
Initiation mutually separates, the method for forming perforated membrane, and pore size, porosity, the thickness of cortex of film etc. of this method preparation are easy to control
System, the parameter for needing to control is few, and the structure being film-made includes the structures such as honeycomb, spongy, dendroid, spherocrystal, but use
Diluent is mostly water-insoluble cosolvent, not soluble in water, still needs to be extracted with other extractant after film forming, pollutes environment, energy
Consumption is big.Composite thermotropic phase separation method, high polymer and diluent form homogeneous phase solution when being using high temperature, and homogeneous phase solution is same when cooling
Shi Fasheng phase separation and Thermal inactive, in film forming procedure, water is both extractant and coolant, the table of preparation liquid
Layer solvent can exchange with water and cause phase separation, and which determine cortex constructions.
In conclusion the fenestra for using phase separation method to prepare is finger-like pore, honeycomb structure, spongy hole, dendroid hole, ball
Geode etc., but it has thin epidermis, its application cannot be influenced completely through film by being formed by fenestra.Therefore, one is prepared
Film through pore structure is most important.
Summary of the invention
The purpose of the present invention is to provide the film that a kind of preparation of Double solvent method has hierarchical porous structure, the preparation method is new
Grain husk, obtained film do not have cortex, and fenestra is completely through film, and between film upper surface, lower surface and its upper and lower surface
Fenestra differs in size, and has hierarchical porous structure.
Double solvent method preparation of the invention has the film of hierarchical porous structure, successively contains following steps:
1) under 30~60 DEG C, stirring condition, polymer, additive, good solvent and low boiling point solvent is uniformly mixed, is molten
The polymeric casting film liquid that mass concentration is 1~20% is obtained after solution, filtering, deaeration；
Additive concentration in casting solution with mass percent is expressed as 0~6%；The low boiling point solvent is in casting film
Concentration is expressed as 30~60% with mass percent in liquid；Good solvent concentration in casting solution is expressed as with mass percent
14~69%；
2) the polymeric casting film drop that step 1) obtains is obtained into polymer casting on low boiling point solvent with microsyringe
Film liquid/low boiling point solvent system, and the system is formed a film at high humidity；
The temperature of the low boiling point solvent is 20~40 DEG C；
The film formation time is 30~60min；
3) film made from step 2 is impregnated into 1~12h in water, takes out and dries 6~12h at 60~90 DEG C up to the present invention
The film with hierarchical porous structure.
The polymer is polyetherimide, in polyether-ether-ketone, polystyrene, poly(aryl ether ketone), polysulfones, polybenzimidazoles
One or more of mixtures；
The additive is one of anhydrous lithium chloride, polyethylene glycol；
The good solvent is dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, one in N-Methyl pyrrolidone
Kind or several mixtures；
The low boiling point solvent is one of benzene, tetrahydrofuran, chloroform or carbon tetrachloride；
The humidity of the high humility is 50~95%.
Compared with prior art, the present invention having the advantage that
1) Double solvent method preparation of the present invention has the film of hierarchical porous structure, and the solvent that this method uses is and gathers
Close object have excellent compatibility and solubility property good solvent and property compatible with water difference and have volatility can dissolve polymerization again
Two kinds of phase separations can occur for the low boiling point solvent of object, two kinds of different solvents in casting film liquid system；
2) Double solvent method of the invention preparation has the film of hierarchical porous structure, by casting film drop low in film forming procedure
On boiling point solvent, and the system is formed a film at high humidity, the presence of low boiling point solvent enables to table in casting film liquid system
Face induces generation mutually to separate and prepare regular pore structure at high humidity, and the presence of good solvent enables to down in casting film liquid system
Surface generates phase separation in low boiling point solvent and prepares the hole of spongelike structure；
3) Double solvent method that uses of the present invention, preparation method is novel, and obtained film does not have a cortex, fenestra completely through
Film, and the fenestra between film upper surface, lower surface and its upper and lower surface differs in size, and has hierarchical porous structure；
4) film prepared using Double solvent method of the invention, the film upper surface are regular pore structure, aperture is 0.1~
6 μm, lower surface is spongy pore structure, and aperture is 0.001~0.1 μm；
5) film prepared by the present invention with hierarchical porous structure, through hole expand the application field of seperation film, together
When, the solvent pairs method used also provides new approaches for the preparation of seperation film.
Detailed description of the invention
Fig. 1 schemes for the section SEM of 1 made membrane of the embodiment of the present invention.
Specific embodiment
Embodiment 1
By 0.2g polyetherimide, 12g chloroform, 7.8g dimethylformamide, under 30 DEG C of heating, stirring uniformly mixing,
1% polyetherimide casting solution is obtained after dissolution, filtering, deaeration；Take the casting film drop of 30 μ L at 20 DEG C with microsyringe
Chloroform on, and the system is placed in 60min under 95% air humidity environment, takes out the film and impregnate 1h in deionized water, take
Dry 6h at 90 DEG C out up to the film of the present invention with hierarchical porous structure, which is honeycomb structure knot
Structure, average pore size are 6 μm, and lower surface is spongy pore structure, and average pore size is 0.1 μm.
Embodiment 2
By 4g polysulfones, 6g tetrahydrofuran, 1g anhydrous lithium chloride, 9g dimethyl acetamide, under 45 DEG C of heating, stirring uniformly
20% polysulfones casting solution is obtained after mixing, dissolution, filtering, deaeration；Take the casting film drop of 40 μ L at 25 DEG C with microsyringe
Tetrahydrofuran on, and the system is placed in 40min under 50% air humidity environment, takes out the film and impregnate in deionized water
10h takes out and dries 10h at 70 DEG C up to the film of the present invention with hierarchical porous structure, which is honeycomb
Shape pore structure, average pore size are 0.1 μm, and lower surface is spongy pore structure, and average pore size is 0.01 μm.
Embodiment 3
By 1g polybenzimidazoles, 10g benzene, 1.2g polyethylene glycol (molecular weight 400), 7.8g dimethyl sulfoxide, at 50 DEG C plus
5% polybenzimidazoles casting solution is obtained after heat, the lower uniformly mixing of stirring, dissolution, filtering, deaeration；20 μ L are taken with microsyringe
The casting film drop on 40 DEG C of benzene, and the system is placed in 30min under 80% air humidity environment, takes out the film and going
6h is impregnated in ionized water, is taken out and is dried 8h at 80 DEG C up to the film of the present invention with hierarchical porous structure, on the film
Surface is honeycomb structure, and average pore size is 3.5 μm, and lower surface is spongy pore structure, and average pore size is 0.48 μm.
Embodiment 4
By 2g polystyrene, 8g carbon tetrachloride, 10gN- methyl pyrrolidone, under 40 DEG C of heating, stirring uniformly mixing,
10% polystyrene casting solution is obtained after dissolution, filtering, deaeration；Take the casting film drop of 30 μ L at 30 DEG C with microsyringe
Carbon tetrachloride on, and the system is placed in 50min under 65% air humidity environment, takes out the film and impregnate in deionized water
12h takes out and dries 12h at 60 DEG C up to the film of the present invention with hierarchical porous structure, which is honeycomb
Shape pore structure, average pore size are 1.2 μm, and lower surface is spongy pore structure, and average pore size is 0.05 μm.
Claims (10)
1. Double solvent method preparation have hierarchical porous structure film, which is characterized in that the preparation method of the film successively contain with
Lower step:
1) under 30~60 DEG C, stirring condition, polymer, additive, good solvent and low boiling point solvent are uniformly mixed, dissolved,
The polymeric casting film liquid that mass concentration is 1~20% is obtained after filtering, deaeration；
2) with microsyringe by the polymeric casting film drop that step 1) obtains obtained on low boiling point solvent polymeric casting film liquid/
Low boiling point solvent system, and the system is formed a film at high humidity；
The low boiling point solvent is one of benzene, tetrahydrofuran, chloroform or carbon tetrachloride；
3) film made from step 2) is impregnated into 1~12h in water, take out 6~12h of baking at 60~90 DEG C has up to described
The film of hierarchical porous structure.
2. film according to claim 1, which is characterized in that the polymer in the step 1) is polyetherimide, gathers
The mixture of one or more of ether ether ketone, polystyrene, poly(aryl ether ketone), polysulfones, polybenzimidazoles.
3. film according to claim 1, which is characterized in that the additive in the step 1) is anhydrous lithium chloride, gathers
One of ethylene glycol.
4. film according to claim 1, which is characterized in that additive in the step 1) concentration in casting solution is used
Mass percent is expressed as 0~6%, does not include 0%.
5. film according to claim 1, which is characterized in that the low boiling point solvent in the step 1) is dense in casting solution
Degree is expressed as 30~60% with mass percent.
6. film according to claim 1, which is characterized in that good solvent in the step 1) be dimethylformamide,
The mixture of one or more of dimethyl acetamide, dimethyl sulfoxide, N-Methyl pyrrolidone.
7. film according to claim 1, which is characterized in that good solvent in the step 1) concentration in casting solution is used
Mass percent is expressed as 14~69%.
8. film according to claim 1, which is characterized in that the temperature of the low boiling point solvent in the step 2) be 20~
40℃。
9. film according to claim 1, which is characterized in that the humidity of the high humility in the step 2) be 50~
95%.
10. film according to claim 1, which is characterized in that high humility film formation time in the step 2) is 30~
60min。
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| CN107522882B (en) * | 2017-10-19 | 2020-02-18 | 四川斯派恩新材料有限公司 | Polysulfone insulating film and preparation method thereof |
| CN107983169A (en) * | 2017-12-18 | 2018-05-04 | 安徽普朗膜技术有限公司 | Blended ultrafiltration membrane and preparation method thereof |
| CN111253596B (en) * | 2019-11-05 | 2023-03-10 | 浙江理工大学 | Preparation method of polyetherimide micro-nano particles with controllable particle sizes |
| CN111389245B (en) * | 2020-04-17 | 2021-04-13 | 天津工业大学 | Single-side super-hydrophobic polymer fiber membrane and preparation method and application thereof |
| CN114797484B (en) * | 2021-01-19 | 2023-02-28 | 中国石油化工股份有限公司 | Porous separation membrane with adsorption performance and preparation method and application thereof |
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