CN103599708B - A kind of composite membrane and preparation method thereof - Google Patents
A kind of composite membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of composite membrane and preparation method thereof. This composite membrane includes porous support membrane, be coated on porous support membrane intermediate layer and coating on the intermediate layer there is the stratum disjunctum selecting separating property, it is characterized in that, the material in described intermediate layer includes hydroxy silicon oil and silicon-containing polymer, and the aperture of described porous support membrane is 10-2000nm. The composite membrane of the present invention adopts hydroxy silicon oil and silicon-containing polymer intermingling material as intermediate layer. The addition of hydrophilic hydroxy group silicone oil makes intermediate layer cortex form uniform hydrophilic points, adds and the affinity of hydrophilic stratum disjunctum, makes composite membrane not only have higher infiltration and select separating property, and intensity height is not easily stripped. The preparation method of the composite membrane of the present invention is simple, easily controllable, suitable in gas separation, reverse osmosis, Nano filtering composite membrane preparation, be with a wide range of applications.
Description
Technical field
The present invention relates to membrane material technology, particularly relate to a kind of multilayer complex films and preparation method thereof.
Background technology
Membrane technology is a kind of emerging new and high technology, compared with conventional separation techniques, have that energy consumption is low, equipment simple, can the advantages such as normal-temperature operation, strong adaptability, reliability be high, be widely used to food, medicine, biology, environmental protection, chemical industry, metallurgy, the energy, oil, water process, electronics, the field such as bionical. Membrane material is the basis of a successful membrane separating process, and its permeance property and selection separating property directly govern whole membrane separating process, and therefore high performance membrane material and advanced masking technique have become the emphasis of various countries' membrane science research.
Composite membrane is prepared by porous support membrane to form the ultra-thin dense layer surface with centrifugation, and method includes dip coating, interfacial polymerization, plasma polymerization etc. Dip coating (dip-coating) is to immerse porous counterdie to have in high selective polymer separation materials solution, makes separation material be coated in the method on counterdie, can be used for the preparation of gas separation, reverse osmosis, Nano filtering composite membrane. The casting solution that composite membrane counterdie is usually formed by the organic solvent solution of membrane material and additive is prepared from through inversion of phases, but the porous film surface roughness being prepared from practical operation is higher, hardly results in uniform and smooth cortex. In this case being directly coated with separation layer materials on counterdie, if coating solution concentration is relatively low, easily occur hole to ooze, coating solution directly penetrates into hole, and stratum disjunctum surface can form defect, reduces the selection separating property of composite membrane;If coating solution concentration is higher, stratum disjunctum is thicker, then can affect the permeance property of composite membrane.
In order to make up the defective hole of counterdie cortex, the silicon-containing polymer material that research staff's selected area update strategy performance is excellent, if polydimethylsiloxane (PDMS) is as intermediate layer, then coating separation layer materials prepares sandwich diaphragm thereon. " plug-hole " effect is played in silicon-containing polymer intermediate layer, and coating solution just can form very thin densification and uniform stratum disjunctum on its surface, thus obtaining permeability and the composite membrane selecting separation property all good. But due to separation layer materials such as polyether co-polyamide (PEBA) shows as hydrophilic, and intermediate layer PDMS etc. are perfect hydrophobic materials, therefore there is the phenomenon that intermediate layer is easily peeled in conjunction with poor effect with stratum disjunctum.
Summary of the invention
It is an object of the invention to overcome the deficiency of existing technology of composite film preparation, it is provided that a kind of novel sandwich diaphragm and preparation method thereof. The technological core of the present invention is in that interlayer surfaces forms uniform hydrophilic points, increases the affinity of itself and hydrophilic stratum disjunctum using blended as intermediate layer to hydrophilic hydroxy silicon oil and silicon-containing polymer. The composite membrane of the present invention has higher selective penetrated property, and stratum disjunctum is not easily stripped.
Adopt the following technical scheme that to realize the purpose of the present invention:
A kind of composite membrane, including porous support membrane, the intermediate layer being coated on porous support membrane and coating on the intermediate layer have select separating property stratum disjunctum, it is characterized in that, the material in described intermediate layer includes hydroxy silicon oil and silicon-containing polymer, and the aperture of described porous support membrane is 10-2000nm.
The stratum disjunctum with selection separating property of the present invention refers to for, in gas separation, reverse osmosis, nanofiltration separation process, component having the selectivity hydrophilic thin layer through function.
The aperture of described porous support membrane is preferably 10-100nm, more preferably 10-30nm.
In technique scheme, described hydroxy silicon oil and silicon-containing polymer are configured to after the hydroxy silicon oil-silicon-containing polymer blend solution of 1-15wt% for preparing intermediate layer, in blend solution, hydroxy silicon oil is 1:1-9:1 with the mass ratio of silicon-containing polymer, it is preferable that 6:4-8:2. in a specific embodiment, the hydroxy silicon oil weighed in proportion and silicon-containing polymer are dissolved in organic solvent, preparation solute concentration be the preferred 5-10wt% of 1-15wt%() hydroxy silicon oil-silicon-containing polymer blend solution, be coated on described porous support membrane forming thickness is the intermediate layer of 0.5-5 ��m, described organic solvent can adopt normal hexane, isobutyltrimethylmethane., normal heptane, gasoline, one or more mixed solvent in petroleum ether, but it is not limited to this, in the scope realizing technical solution of the present invention, commonly used in the art have volatile organic solvent and all can adopt.
In technique scheme, described Hydroxyl Content in Hydroxysilicone fluid is preferably 0.5-3%, more preferably 1-2.5%; Hydroxy silicon oil viscosity is preferably 25-100000cs, more preferably 5000-50000cs.
In technique scheme, the thickness in described intermediate layer is preferably 0.5-5 ��m, more preferably 0.5-2 ��m.
The present invention is not particularly limited for silicon-containing polymer, and in the scope realizing technical solution of the present invention, silicon-containing polymer commonly used in the art all can adopt, and present invention preferably employs the one in polydimethylsiloxane, poly-trimethyl silicane propine.
In technique scheme, the thickness of described porous support membrane is 50-200 ��m, and the thickness of described stratum disjunctum is 0.05-5 ��m, more preferably 0.1-2 ��m.
The present invention is not particularly limited for the kind of porous support membrane, in the scope realizing technical solution of the present invention, porous support membrane commonly used in the art all can adopt, and the membrane material of currently preferred porous support membrane is one or more in polysulfones (PS), polyether sulfone (PES), polyacrylonitrile (PAN), Polyetherimide (PEI), Kynoar (PVDF).
In technique scheme, described separating layer membrane materials is preferably the one in polyether co-polyamide (PEBA), polyvinyl alcohol (PVA), polyamide (PA).
The preparation method of composite membrane of the present invention, comprises the steps:
(1) 1:1-9:1 in mass ratio, hydroxy silicon oil and silicon-containing polymer are dissolved in solvent orange 2 A, it is configured to hydroxy silicon oil-silicon-containing polymer blend solution that concentration is 1-15wt%, it is coated in after standing and defoaming on porous support membrane, at 60-90 DEG C of dry 5-15min desolvation, obtain the composite membrane in porous counterdie/hydroxy silicon oil-silicon-containing polymer intermediate layer;
(2) separation layer materials is dissolved in the stratum disjunctum solution being configured to 0.5-10wt% in solvent B, after standing and defoaming at 40-60 DEG C dip-coating on the composite membrane in porous counterdie/hydroxy silicon oil-silicon-containing polymer intermediate layer, at 60-90 DEG C of dry 5-15min desolvation, obtain the sandwich diaphragm of porous counterdie/hydroxy silicon oil-silicon-containing polymer intermediate layer/stratum disjunctum;
Wherein: solvent orange 2 A described in step (1) is one or more the mixed solvent in normal hexane, isobutyltrimethylmethane., normal heptane, gasoline, petroleum ether; Solvent B described in step (2) is the one in ethanol/butanol/water, propanol/butanol, butanol, ethanol/water; The thickness in described hydroxy silicon oil-silicon-containing polymer intermediate layer is 0.5-5 ��m, and the thickness of described stratum disjunctum is 0.05-5 ��m.
The composite membrane of the present invention may be used for gas separation, reverse osmosis, nanofiltration process.
Compared with prior art, the invention have the benefit that
1, the intermediate layer material that the present invention adopts can form smooth flawless cortex on porous counterdie, effectively make up the defect of porous counterdie, stratum disjunctum solution uniformly can be sprawled in interlayer surfaces, forms relatively thin stratum disjunctum, improves the selection separating property of composite membrane.
2, the composite membrane of the present invention adopts hydroxy silicon oil and silicon-containing polymer intermingling material as intermediate layer. The intermediate layer cortex that is added in of hydrophilic hydroxy group silicone oil forms uniform hydrophilic points, adds and the adhesion of hydrophilic stratum disjunctum, makes the peel strength of composite membrane be improved.
3, the preparation method of the composite membrane of the present invention simple, easily controllable, suitable in gas separation, reverse osmosis, Nano filtering composite membrane preparation, be with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the structural representation of the composite membrane of the present invention
Fig. 2 is the gas recombination membrane permeation prepared of embodiment and separating property test device schematic diagram
Drawing reference numeral: 1, porous support membrane, 2, intermediate layer, 3, stratum disjunctum, 4, N2Gas cylinder, 5, CO2Gas cylinder, 6, air relief valve, 7, Pressure gauge, 8, film evaluate pond, 9, stop valve; 10, soap bubble flowmeter.
Detailed description of the invention
Following non-limiting example can make those of ordinary skill in the art more fully understand the present invention, but does not limit the present invention in any way.In following embodiment, if no special instructions, the experimental technique used is conventional method, and agents useful for same etc. all can chemically Reagent Company be bought. Chemical reagent used is analytical pure.
The infiltration of composite membrane prepared by the embodiment of the present invention and separating property adopt pure CO2And N2Infiltration rate J and CO2/N2Gas selectivity ��CO2/N2Characterize. Test device is as shown in Figure 2.
The circular film cut is put into film and evaluates in pond 8, fit sealing. Open N2Gas cylinder 4 passes into N2, open stop valve 9 simultaneously and film feed side carried out N2Purge. Close stop valve 9 after 2min, regulate air relief valve 6, make the registration of Pressure gauge 7 be shown as 6atm. The soap bubble of soap bubble flowmeter 10 being connected with membrane permeation side with stopwatch test after system stability 1h is passed by time used by 5ml record. Open CO2Gas cylinder 5, carries out composite membrane to CO2Infiltration and separating property test, the same N of method of testing2��
CO2And N2Infiltration rate J calculated by following formula and obtain:
In formula:
The flux of gas, cm is permeated under V test condition3
The t testing time, s
A effective film area, cm2
�� p permeable membrane pressure reduction, cmHg
T0,p0Temperature and pressure under test condition, K, cmHg
CO2With N2Gas selectivity ��CO2/N2It is the infiltration rate J of two kinds of gasesCO2And JN2Ratio:
The raw material information related in following embodiment:
PAN counterdie: carrier film thickness is 150 ��m, average pore size is 30nm.
Polyether co-polyamide (PEBA): Arkema company, product type is
Embodiment 1
(1) polyether co-polyamide (PEBA) is dissolved in the PEBA solution being configured to 1wt% in ethanol/water (ethanol: water=7:3) mixed solvent, places 24h deaeration;
(2) PAN counterdie is laid on glass plate after deionized water cleans, after wiping the moisture on film surface, 50 DEG C of PEBA solution of step (1) are poured on film surface, rocking glass makes film surface vertically dry in the shade after all touching solution 10min, obtains PAN/PEBA(1wt% in an oven after 70 DEG C of dry 10min desolvations) composite membrane.
Test compound film is to pure CO in aforementioned manners2And N2Permeance property and separating property, result is table 1 such as.
Embodiment 2
Prepare the PEBA solution of 50 DEG C according to the method for embodiment 1, wherein PEBA concentration in the solution is 3wt%.
PAN counterdie is laid on glass plate after deionized water cleans, after wiping the moisture on film surface, ready PEBA solution is poured on film surface, rocking glass makes film surface vertically dry in the shade after all touching solution 10min, obtains PAN/PEBA(3wt% in an oven after 70 DEG C of dry 10min desolvations) composite membrane.
Test compound film is to pure CO in aforementioned manners2And N2Permeance property and separating property, result is table 1 such as.
Embodiment 3
Prepare the PEBA solution of 50 DEG C according to the method for embodiment 1, wherein PEBA concentration in the solution is 2wt%.
PAN counterdie is laid on glass plate after deionized water cleans, after wiping the moisture on film surface, ready PEBA solution is poured on film surface, rocking glass makes film surface vertically dry in the shade after all touching solution 10min, obtains PAN/PEBA(2wt% in an oven after 70 DEG C of dry 10min desolvations) composite membrane.
Test compound film is to pure CO in aforementioned manners2And N2Permeance property and separating property, result is table 1 such as.
Table 1.
Embodiment 4
PAN counterdie is sealed through plastic packaging machine and makees film forming bag, dip-coating 5wt%PDMS solution (solvent is isobutyltrimethylmethane .) after 3min is dried in the air in reverse osmosis water cleaning suspension, the 8min that at room temperature dries in the shade is taken out after 10s, 70 DEG C of dry 12min desolvations in an oven, taking-up is cooled to room temperature, obtain PAN/PDMS(5wt%) composite membrane, test its contact angle with contact angle tester, result is table 2 such as.PAN/PDMS(5wt%) (solvent is ethanol/water system to the 2wt%PEBA solution of the further dip-coating of composite membrane 50 DEG C, ethanol: water=7:3), take out suspension after 10s to dry in the shade 10min, PAN/PDMS(5wt% is obtained in an oven after 70 DEG C of dry 10min desolvations)/PEBA composite membrane, test it as stated above to the permeability of gas and selectivity, and composite membrane is carried out stripper-resistance test by artificial (hands tears). Result is in Table 2.
Embodiment 5
PAN counterdie is sealed through plastic packaging machine and makees film forming bag, dip-coating 10wt%PDMS solution (solvent is isobutyltrimethylmethane .) after 3min is dried in the air in reverse osmosis water cleaning suspension, the 8min that at room temperature dries in the shade is taken out after 10s, 70 DEG C of dry 12min desolvations in an oven, taking-up is cooled to room temperature, obtain PAN/PDMS(10wt%) composite membrane, test its contact angle with contact angle tester, result is table 2 such as. (solvent is ethanol/water system to the 2wt%PEBA solution of the further dip-coating of PAN/PDMS composite membrane 50 DEG C, ethanol: water=7:3), take out suspension after 10s to dry in the shade 10min, PAN/PDMS(10wt% is obtained in an oven after 70 DEG C of dry 10min desolvations)/PEBA composite membrane, test it as stated above to the permeability of gas and selectivity, and composite membrane is carried out stripper-resistance test by artificial (hands tears). Result is in Table 2.
Embodiment 6
Preparation 5wt% hydroxy silicon oil (hydroxy radical content 2%, viscosity 10000cs) and 5wt%PDMS mixed solution (solvent is isobutyltrimethylmethane .), stand 24h deaeration. PAN counterdie is sealed through plastic packaging machine and makees film forming bag, dip-coating hydroxy silicon oil-PDMS mixed solution after 3min is dried in the air in reverse osmosis water cleaning suspension, the 8min that at room temperature dries in the shade is taken out after 10s, 70 DEG C of dry 12min desolvations in an oven, taking-up is cooled to room temperature, obtain PAN/ hydroxy silicon oil (5wt%)-PDMS(5wt%) composite membrane, test its contact angle with contact angle tester, result is table 2 such as. Then by PAN/ hydroxy silicon oil (5wt%)-PDMS(5wt%) (solvent is ethanol/water system for the 2wt%PEBA solution of the further dip-coating of composite membrane 50 DEG C, ethanol: water=7:3), take out suspension after 10s to dry in the shade 10min, obtain PAN/ hydroxy silicon oil (5wt%)-PDMS(5wt% after 70 DEG C of dry 10min desolvations in an oven)/PEBA composite membrane. Test its permeability and selectivity, and composite membrane is carried out stripper-resistance test by artificial (hands tears). Test result is in Table 2.
Embodiment 7
Preparation 8wt% hydroxy silicon oil (hydroxy radical content 2%, viscosity 10000cs) and 2wt%PDMS mixed solution (solvent is isobutyltrimethylmethane .), stand 24h deaeration. Counterdie seals through plastic packaging machine and makees film forming bag, dip-coating hydroxy silicon oil-PDMS mixed solution after 3min is dried in the air in reverse osmosis water cleaning suspension, the 8min that at room temperature dries in the shade is taken out after 10s, 70 DEG C of dry 12min desolvations in an oven, taking-up is cooled to room temperature, obtain PAN/ hydroxy silicon oil (8wt%)-PDMS(2wt%) composite membrane, test its contact angle with contact angle tester, result is table 2 such as. Then by PAN/ hydroxy silicon oil (8wt%)-PDMS(2wt%) (solvent is ethanol/water system for the 2wt%PEBA solution of the further dip-coating of composite membrane 50 DEG C, ethanol: water=7:3), take out suspension after 10s to dry in the shade 10min, obtain PAN/ hydroxy silicon oil (8wt%)-PDMS(2wt% after 70 DEG C of dry 10min desolvations in an oven)/PEBA composite membrane. Test its permeability and selectivity, and composite membrane is carried out stripper-resistance test by artificial (hands tears).Test result is in Table 2.
Embodiment 8
Preparation 8wt% hydroxy silicon oil (hydroxy radical content 1.5%, viscosity 20000cs) and 2wt%PDMS mixed solution (solvent is isobutyltrimethylmethane .), stand 24h deaeration. Counterdie seals through plastic packaging machine and makees film forming bag, dip-coating hydroxy silicon oil-PDMS mixed solution after 3min is dried in the air in reverse osmosis water cleaning suspension, the 8min that at room temperature dries in the shade is taken out after 10s, 70 DEG C of dry 12min desolvations in an oven, taking-up is cooled to room temperature, obtaining PAN/ hydroxy silicon oil (hydroxy radical content 1.5%)-PDMS composite membrane, test its contact angle with contact angle tester, result is table 2 such as. Then by the 2wt%PEBA solution of the further dip-coating of PAN/ hydroxy silicon oil (hydroxy radical content 1.5%)-PDMS composite membrane 50 DEG C, (solvent is ethanol/water system, ethanol: water=7:3), take out suspension after 10s to dry in the shade 10min, obtain PAN/ hydroxy silicon oil (hydroxy radical content 1.5%)-PDMS/PEBA composite membrane after 70 DEG C of dry 10min desolvations in an oven. Test its permeability and selectivity, and composite membrane is carried out stripper-resistance test by artificial (hands tears). Test result is in Table 2.
Table 2.
Interpretation of result:
The result of table 1 shows:
In embodiment 1, as PEBA concentration relatively low (1wt%), the stratum disjunctum formed in solvent volatilization process, hole counterdie on can not be completely covered owing to hole blends the too low reason of solution concentration, namely flawless stratum disjunctum can not be formed on counterdie, therefore the composite membrane infiltration rate prepared is higher, and selectivity is far below material's eigenvalue [1]. When embodiment 2 increases PEBA concentration (3wt%) further, although comparatively complete stratum disjunctum can be formed after solvent volatilization, show as selectivity ratios and be closer to material's eigenvalue[1], but the stratum disjunctum formed is blocked up, causes composite membrane infiltration rate relatively low. Applicant finds through many experiments, when adopting 2wt%PEBA concentration in embodiment 3, the relatively thin relatively complete stratum disjunctum of ratio can be basically formed after solvent volatilization, infiltration rate and the selectivity ratios of composite membrane are more satisfactory, so adopting 2wt%PEBA solution preparative separation layer in other embodiments of the present invention.
The result of table 2 shows:
Adopting PDMS as intermediate layer in embodiment 4, the hole reduced in PEBA solution coating process is oozed. But owing to PDMS shows as relatively strong-hydrophobicity, between PEBA and PDMS, affinity is poor, and PEBA solution is difficult to sprawl on PDMS cortex, the stratum disjunctum surface therefore formed is defective, shows as selectivity far below material's eigenvalue[1]. Simultaneously because affinity is not good, stratum disjunctum and intermediate layer are very easily peeled off.
Embodiment 5 further increases PDMS solution concentration, but composite membrane performance impact is little, and the data of infiltration and selectivity and embodiment 4 relatively, also very easily peel off by stratum disjunctum and intermediate layer.
Blended in PDMS solution in embodiment 6 have certain hydrophilic hydroxy silicon oil, and intermediate layer hydrophilic improves, and shows as contact angle and significantly reduces. The affinity of intermediate layer and PEBA strengthens, and PEBA solution can launch by uniform spreading on the intermediate layer, along with solvent volatilization and then form the stratum disjunctum almost without defect, the selectivity shown far above embodiment 4, relatively material's eigenvalue[1]. Simultaneously because affinity increases, stratum disjunctum and intermediate layer are not easily stripped, and compound film strength significantly improves.
Embodiment 7 further increases the content of hydroxy silicon oil in intermediate layer solution, intermediate layer hydrophilic improves further, increases further with PEBA affinity so that PEBA solution is easier to sprawl on the intermediate layer, therefore the selectivity of composite membrane slightly improves, closely material's eigenvalue[1], and be not easily stripped.
Have employed the hydroxy silicon oil that hydroxy radical content is slightly lower and viscosity is higher in embodiment 8, intermediate layer hydrophilic declines to some extent, decreases with PEBA affinity, and compared with embodiment 6, the selectivity of composite membrane slightly declines, and intensity is still higher, is not easily stripped.
Result above and analyze known, the composite membrane of the present invention, intermediate layer adopts the intermingling material of hydroxy silicon oil and PDMS, its adhesion with hydrophilic stratum disjunctum is more than the PDMS composite membrane (embodiment 4-5) separately as intermediate layer, intermediate layer and stratum disjunctum are not easily stripped, and composite membrane significantly improves for infiltration and the selectivity of gas. It addition, increase concentration and the hydroxy radical content of hydroxy silicon oil, infiltration and the selectivity of the intermediate layer of composite membrane of the present invention and the bond strength of stratum disjunctum and composite membrane are consequently increased.
Document [1]: " Gaspermeationofpoly (amide-6-b-ethyleneoxide) copolymer ", JournalofMembraneScience, 190 (2001): 179-193.
Claims (9)
1. a composite membrane, including porous support membrane, the intermediate layer being coated on porous support membrane and coating on the intermediate layer have select separating property stratum disjunctum, it is characterized in that, the material in described intermediate layer includes hydroxy silicon oil and silicon-containing polymer, and the aperture of described porous support membrane is 10-2000nm.
2. composite membrane according to claim 1, it is characterized in that, described hydroxy silicon oil and silicon-containing polymer are configured to after the hydroxy silicon oil-silicon-containing polymer blend solution of 1-15wt% for preparing intermediate layer, and in blend solution, hydroxy silicon oil is 1:1-9:1 with the mass ratio of silicon-containing polymer.
3. composite membrane according to claim 1, it is characterised in that described Hydroxyl Content in Hydroxysilicone fluid is 0.5-3%, hydroxy silicon oil viscosity is 25-100000cs.
4. composite membrane according to claim 1, it is characterised in that the thickness in described intermediate layer is 0.5-5 ��m.
5. the composite membrane according to any one of claim 1-4, it is characterised in that described silicon-containing polymer is the one in polydimethylsiloxane, poly-trimethyl silicane propine.
6. composite membrane according to claim 1, it is characterised in that the thickness of described porous support membrane is 50-200 ��m, the thickness of described stratum disjunctum is 0.05-5 ��m.
7. composite membrane according to claim 1, it is characterised in that the membrane material of described porous support membrane is one or more in polysulfones, polyacrylonitrile, Polyetherimide, Kynoar.
8. composite membrane according to claim 1, it is characterised in that the membrane material of described stratum disjunctum is the one in polyether co-polyamide, polyvinyl alcohol, polyamide.
9. the preparation method of the composite membrane described in claim 1, comprises the steps:
(1) 1:1-9:1 in mass ratio, hydroxy silicon oil and silicon-containing polymer are dissolved in solvent orange 2 A, it is configured to hydroxy silicon oil-silicon-containing polymer blend solution that concentration is 1-15wt%, it is coated in after standing and defoaming on porous support membrane, at 60-90 DEG C of dry 5-15min desolvation, obtain the composite membrane in porous counterdie/hydroxy silicon oil-silicon-containing polymer intermediate layer;
(2) separation layer materials is dissolved in the stratum disjunctum solution being configured to 0.5-10wt% in solvent B, after standing and defoaming at 40-60 DEG C dip-coating on the composite membrane in porous counterdie/hydroxy silicon oil-silicon-containing polymer intermediate layer, at 60-90 DEG C of dry 5-15min desolvation, obtain the sandwich diaphragm of porous counterdie/hydroxy silicon oil-silicon-containing polymer intermediate layer/stratum disjunctum;
Wherein: the solvent orange 2 A described in step (1) is one or more the mixed solvent in normal hexane, isobutyltrimethylmethane., normal heptane, gasoline, petroleum ether; Solvent B described in step (2) is the one in ethanol/butanol/water, propanol/butanol, butanol, ethanol/water; The thickness in described hydroxy silicon oil-silicon-containing polymer intermediate layer is 0.5-5 ��m, and the thickness of described stratum disjunctum is 0.05-5 ��m.
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| CN111744375B (en) * | 2020-07-21 | 2021-08-06 | 天津工业大学 | Mixed matrix membrane with high-selectivity gas channel and preparation method thereof |
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| CN1451465A (en) * | 2002-04-12 | 2003-10-29 | 四川大学 | Method for making composite membrane for separation of polymer fluid |
| CN101185854A (en) * | 2007-08-29 | 2008-05-28 | 江南大学 | Silicon rubber oxygen-enriched film doped silicon dioxide and preparation method thereof |
| CN101455947A (en) * | 2008-12-09 | 2009-06-17 | 浙江大学 | Hydrophobic modified PDMS membrane and preparation method thereof |
| CN102068914A (en) * | 2010-12-13 | 2011-05-25 | 大连欧科膜技术工程有限公司 | Preparation method of gas separation composite film |
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