CN103599708A - Composite membrane and preparation method thereof - Google Patents
Composite membrane and preparation method thereof Download PDFInfo
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- CN103599708A CN103599708A CN201310639578.7A CN201310639578A CN103599708A CN 103599708 A CN103599708 A CN 103599708A CN 201310639578 A CN201310639578 A CN 201310639578A CN 103599708 A CN103599708 A CN 103599708A
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Abstract
The invention discloses a composite membrane and a preparation method thereof. The composite membrane comprises a porous support membrane, a middle layer coated on the porous support membrane, and a separation layer coated on the middle layer and having a selective separation performance. The composite membrane is characterized in that the material of the middle layer comprises hydroxyl silicone oil and a silicon-containing high polymer, and the pore diameter of the porous support membrane is 10-2000 nm. The composite membrane adopts the hydroxyl silicone oil and silicone-containing high polymer co-mixed material as the middle layer. The addition of the hydrophilic hydroxyl silicone oil allows the skin layer of the middle layer to form uniform hydrophilic dots, so that the affinity with the hydrophilic separation layer is increased, and the composite membrane not only has higher permeability and selective separation performance, but also has high strength and is not easy to strip. The preparation method of the composite membrane is simple and easy to control, is applicable to preparation of gas separation, reversed penetration and nanofiltration composite membranes, and has wide application prospects.
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, compare with traditional isolation technics, have that energy consumption is low, equipment is simple, can normal-temperature operation, the advantage such as strong adaptability, reliability height, be widely used in food, medicine, biology, environmental protection, chemical industry, metallurgy, the energy, oil, water treatment, electronics, the field such as bionical.Membrane material is the basis of a successful film separation process, its permeance property and select separating property directly restricting whole film separation process, so high performance membrane material and advanced masking technique have become the emphasis of various countries' membrane science research.
Composite membrane preparation is on porous support membrane, to form the ultra-thin dense layer surface with centrifugation, and method comprises dip coating, interfacial polymerization, plasma polymerization etc.Dip coating method (dip-coating) is that porous counterdie is immersed and had in the polymer separation materials solution of high selectivity, makes parting material be coated in the method on counterdie, can be used for the preparation of gas separation, counter-infiltration, Nano filtering composite membrane.The casting solution that composite membrane counterdie is normally formed by organic solvent solution and the additive of membrane material is prepared from through inversion of phases, but the porous film surface roughness being prepared from practical operation is higher, is difficult to obtain uniform and smooth cortex.On counterdie, directly apply in this case separating layer material, if coating solution concentration is lower, hole easily occurs and ooze, coating solution directly infiltrates hole, and separating layer surface can form defect, reduces the selection separating property of composite membrane; If coating solution concentration is higher, separating layer is thicker, 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 differential permeability can be excellent, if dimethyl silicone polymer (PDMS) is as intermediate layer, then applies separating layer material thereon and prepares sandwich diaphragm." plug-hole " effect is played in silicon-containing polymer intermediate layer, and coating solution just can form on its surface densification as thin as a wafer and separating layer uniformly, thereby obtains permeability and select all good composite membranes of separation property.But because separating layer material shows as hydrophily as polyethers copolyamide (PEBA), and intermediate layer PDMS etc. are perfect hydrophobic materials, therefore exist intermediate layer to be combined the phenomenon that poor effect easily peels off with separating layer.
Summary of the invention
The object of the invention is to overcome the deficiency of existing composite membrane technology of preparing, a kind of novel sandwich diaphragm and preparation method thereof is provided.Technological core of the present invention is that interlayer surfaces forms uniform hydrophilic points using hydrophilic hydroxy silicon oil and silicon-containing polymer blend as intermediate layer, increases the affinity of itself and hydrophily separating layer.Composite membrane of the present invention has higher selection permeability, and separating layer is difficult for peeling off.
In order to realize object of the present invention, adopt following technical scheme:
A kind of composite membrane, comprise porous support membrane, be coated in the intermediate layer on porous support membrane and be coated in the separating layer of selecting separating property that has on intermediate layer, it is characterized in that, the material in described intermediate layer comprises hydroxy silicon oil and silicon-containing polymer, and the aperture of described porous support membrane is 10-2000nm.
Of the present invention have select the separating layer of separating property to refer to for gas separation, counter-infiltration, nanofiltration separation process, component is had selectively to the 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 mixed with after hydroxy silicon oil-silicon-containing polymer blend solution of 1-15wt% for the preparation of intermediate layer, in blend solution, the mass ratio of hydroxy silicon oil and silicon-containing polymer is 1:1-9:1, preferably 6:4-8:2.In the specific embodiment, the hydroxy silicon oil taking 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 and on described porous support membrane, form the intermediate layer that thickness is 0.5-5 μ m, described organic solvent can adopt n-hexane, isooctane, normal heptane, gasoline, the mixed solvent of one or more in benzinum, but be not limited to this, in realizing the scope of technical solution of the present invention, this area is conventional has 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 μ m, more preferably 0.5-2 μ m.
The present invention is not particularly limited for silicon-containing polymer, and in realizing the scope of technical solution of the present invention, the conventional silicon-containing polymer in this area all can adopt, and the present invention preferably adopts a kind of in dimethyl silicone polymer, poly-trimethyl silicane propine.
In technique scheme, the thickness of described porous support membrane is 50-200 μ m, and the thickness of described separating layer is 0.05-5 μ m, more preferably 0.1-2 μ m.
The present invention is not particularly limited for the kind of porous support membrane, in realizing the scope of technical solution of the present invention, the conventional porous support membrane in this area all can adopt, and the membrane material of the preferred porous support membrane of the present invention is one or more in polysulfones (PS), polyether sulfone (PES), polyacrylonitrile (PAN), PEI (PEI), Kynoar (PVDF).
In technique scheme, described separating layer membrane material is preferably a kind of in polyethers copolyamide (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, being configured to concentration is hydroxy silicon oil-silicon-containing polymer blend solution of 1-15wt%, after standing and defoaming, be coated on porous support membrane, at 60-90 ℃ of dry 5-15min desolvation, obtain the composite membrane in porous counterdie/hydroxy silicon oil-silicon-containing polymer intermediate layer;
(2) separating layer material is dissolved in to the separating layer solution that is mixed with 0.5-10wt% in solvent B, after standing and defoaming at 40-60 ℃ dip-coating on the composite membrane in porous counterdie/hydroxy silicon oil-silicon-containing polymer intermediate layer, at 60-90 ℃ of dry 5-15min desolvation, obtain the sandwich diaphragm of porous counterdie/hydroxy silicon oil-silicon-containing polymer intermediate layer/separating layer;
Wherein: at the solvent orange 2 A described in step (1), be one or more the mixed solvent in n-hexane, isooctane, normal heptane, gasoline, benzinum; At the solvent B described in step (2), be a kind of in ethanol/butanol/water, propyl alcohol/butanols, butanols, ethanol/water; The thickness in described hydroxy silicon oil-silicon-containing polymer intermediate layer is 0.5-5 μ m, and the thickness of described separating layer is 0.05-5 μ m.
Composite membrane of the present invention can be for gas separation, counter-infiltration, nanofiltration process.
Compared with prior art, beneficial effect of the present invention is:
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, separating layer solution can form thinner separating layer in interlayer surfaces uniform spreading, has improved the selection separating property of composite membrane.
2, 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 hydrophily hydroxy silicon oil forms uniform hydrophilic points, has increased the adhesion with hydrophily separating layer, and the peel strength of composite membrane is improved.
3, simple, the preparation that is easy to control, be applicable to gas separation, counter-infiltration, Nano filtering composite membrane of the preparation method of composite membrane of the present invention, is with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the structural representation of composite membrane of the present invention
Fig. 2 is the infiltration of gas recombination film and separating property testing arrangement schematic diagram prepared by embodiment
Drawing reference numeral: 1, porous support membrane, 2, intermediate layer, 3, separating layer, 4, N
2gas cylinder, 5, CO
2gas cylinder, 6, pressure-reducing valve, 7, Pressure gauge, 8, film evaluates pond, 9, stop valve; 10, soap bubble flowmeter.
The specific embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.In following embodiment, if no special instructions, the experimental technique using is conventional method, and agents useful for same Deng Junkecong chemical reagents corporation buys.It is pure that chemical reagent used is analysis.
The infiltration of composite membrane prepared by the embodiment of the present invention and separating property adopt pure CO
2and N
2infiltration rate J and CO
2/ N
2gas selectivity α
cO2/N2characterize.Testing arrangement as shown in Figure 2.
The circular film cutting is put into film and evaluate pond 8, fit sealing.Open N
2gas cylinder 4 passes into N
2, open 9 pairs of film feed sides of stop valve simultaneously and carry out N
2purge.After 2min, close stop valve 9, regulate pressure-reducing valve 6, make the registration of Pressure gauge 7 be shown as 6atm.The soap bubble of the soap bubble flowmeter 10 being connected with film per-meate side with stopwatch test after system stability 1h pass by 5ml time used record.Open CO
2gas cylinder 5, carries out composite membrane to CO
2infiltration and separating property test, the same N of method of testing
2.
CO
2and N
2infiltration rate J by following formula, calculate and obtain:
In formula:
Under V-test condition, permeate the flux of gas, cm
3
T-testing time, s
A-effective film area, cm
2
Δ p-permeable membrane pressure reduction, cmHg
T
0, p
0temperature and pressure under-test condition, K, cmHg
CO
2with N
2gas selectivity α
cO2/N2be the infiltration rate J of two kinds of gases
cO2and J
n2ratio:
The raw material information relating in following embodiment:
PAN counterdie: counterdie thickness is 150 μ m, and average pore size is 30nm.
Polyethers copolyamide (PEBA): Arkema company, product type is
Embodiment 1
(1) polyethers copolyamide (PEBA) is dissolved in to ethanol/water (ethanol: water=7:3) be configured to the PEBA solution of 1wt% in mixed solvent, place 24h deaeration;
(2) PAN counterdie is laid on glass plate after washed with de-ionized water, after wiping the moisture on film surface, 50 ℃ of PEBA solution of step (1) are poured on film surface, rock glass and film surface all can be touched vertically dry in the shade after solution 10min, in baking oven, after 70 ℃ of dry 10min desolvations, obtain PAN/PEBA(1wt%) composite membrane.
With said method test compound film to pure CO
2and N
2permeance property and separating property, result is as table 1.
Embodiment 2
According to the method for embodiment 1, prepare the PEBA solution of 50 ℃, wherein the concentration of PEBA in solution is 3wt%.
PAN counterdie is laid on glass plate after washed with de-ionized water, after wiping the moisture on film surface, ready PEBA solution is poured on film surface, rock glass and film surface all can be touched vertically dry in the shade after solution 10min, in baking oven, after 70 ℃ of dry 10min desolvations, obtain PAN/PEBA(3wt%) composite membrane.
With said method test compound film to pure CO
2and N
2permeance property and separating property, result is as table 1.
Embodiment 3
According to the method for embodiment 1, prepare the PEBA solution of 50 ℃, wherein the concentration of PEBA in solution is 2wt%.
PAN counterdie is laid on glass plate after washed with de-ionized water, after wiping the moisture on film surface, ready PEBA solution is poured on film surface, rock glass and film surface all can be touched vertically dry in the shade after solution 10min, in baking oven, after 70 ℃ of dry 10min desolvations, obtain PAN/PEBA(2wt%) composite membrane.
With said method test compound film to pure CO
2and N
2permeance property and separating property, result is as table 1.
Table 1.
Embodiment 4
PAN counterdie is made to film forming bag through plastic packaging machine sealing, dip-coating 5wt%PDMS solution (solvent is isooctane) after the 3min that dries in the air is hung in reverse osmosis water cleaning, after 10s, take out the 8min that at room temperature dries in the shade, 70 ℃ of dry 12min desolvations in baking oven, taking-up is cooled to room temperature, obtain PAN/PDMS(5wt%) composite membrane, with contact angle tester, test its contact angle, result is as table 2.PAN/PDMS(5wt%) (solvent is ethanol/water system to the 2wt%PEBA solution of 50 ℃ of further dip-coatings of composite membrane, ethanol: water=7:3), after 10s, take out and hang the 10min that dries in the shade, in baking oven, after 70 ℃ of dry 10min desolvations, obtain PAN/PDMS(5wt%)/PEBA composite membrane, test as stated above it to the permeability of gas and selective, and artificial (hand tears) carries out stripper-resistance test to composite membrane.The results are shown in Table 2.
Embodiment 5
PAN counterdie is made to film forming bag through plastic packaging machine sealing, dip-coating 10wt%PDMS solution (solvent is isooctane) after the 3min that dries in the air is hung in reverse osmosis water cleaning, after 10s, take out the 8min that at room temperature dries in the shade, 70 ℃ of dry 12min desolvations in baking oven, taking-up is cooled to room temperature, obtain PAN/PDMS(10wt%) composite membrane, with contact angle tester, test its contact angle, result is as table 2.(solvent is ethanol/water system to the 2wt%PEBA solution that the further dip-coating of PAN/PDMS composite membrane is 50 ℃, ethanol: water=7:3), after 10s, take out and hang the 10min that dries in the shade, in baking oven, after 70 ℃ of dry 10min desolvations, obtain PAN/PDMS(10wt%)/PEBA composite membrane, test as stated above it to the permeability of gas and selective, and artificial (hand tears) carries out stripper-resistance test to composite membrane.The results are shown in Table 2.
Embodiment 6
Preparation 5wt% hydroxy silicon oil (hydroxy radical content 2%, viscosity 10000cs) and 5wt%PDMS mixed solution (solvent is isooctane), standing 24h deaeration.PAN counterdie is made to film forming bag through plastic packaging machine sealing, dip-coating hydroxy silicon oil-PDMS mixed solution after the 3min that dries in the air is hung in reverse osmosis water cleaning, after 10s, take out the 8min that at room temperature dries in the shade, 70 ℃ of dry 12min desolvations in baking oven, taking-up is cooled to room temperature, obtain PAN/ hydroxy silicon oil (5wt%)-PDMS(5wt%) composite membrane, with contact angle tester, test its contact angle, result is as table 2.Then by PAN/ hydroxy silicon oil (5wt%)-PDMS(5wt%) (solvent is ethanol/water system for the 2wt%PEBA solution of 50 ℃ of further dip-coatings of composite membrane, ethanol: water=7:3), after 10s, take out and hang the 10min that dries in the shade, in baking oven, after 70 ℃ of dry 10min desolvations, obtain PAN/ hydroxy silicon oil (5wt%)-PDMS(5wt%)/PEBA composite membrane.Test its permeability and selective, and artificial (hand tears) carries out stripper-resistance test to composite membrane.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 isooctane), standing 24h deaeration.Counterdie is made film forming bag through plastic packaging machine sealing, dip-coating hydroxy silicon oil-PDMS mixed solution after the 3min that dries in the air is hung in reverse osmosis water cleaning, after 10s, take out the 8min that at room temperature dries in the shade, 70 ℃ of dry 12min desolvations in baking oven, taking-up is cooled to room temperature, obtain PAN/ hydroxy silicon oil (8wt%)-PDMS(2wt%) composite membrane, with contact angle tester, test its contact angle, result is as table 2.Then by PAN/ hydroxy silicon oil (8wt%)-PDMS(2wt%) (solvent is ethanol/water system for the 2wt%PEBA solution of 50 ℃ of further dip-coatings of composite membrane, ethanol: water=7:3), after 10s, take out and hang the 10min that dries in the shade, in baking oven, after 70 ℃ of dry 10min desolvations, obtain PAN/ hydroxy silicon oil (8wt%)-PDMS(2wt%)/PEBA composite membrane.Test its permeability and selective, and artificial (hand tears) carries out stripper-resistance test to composite membrane.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 isooctane), standing 24h deaeration.Counterdie is made film forming bag through plastic packaging machine sealing, dip-coating hydroxy silicon oil-PDMS mixed solution after the 3min that dries in the air is hung in reverse osmosis water cleaning, after 10s, take out the 8min that at room temperature dries in the shade, 70 ℃ of dry 12min desolvations in baking oven, taking-up is cooled to room temperature, obtain PAN/ hydroxy silicon oil (hydroxy radical content 1.5%)-PDMS composite membrane, with contact angle tester, test its contact angle, result is as table 2.Then by the 2wt%PEBA solution of 50 ℃ of the further dip-coatings of PAN/ hydroxy silicon oil (hydroxy radical content 1.5%)-PDMS composite membrane, (solvent is ethanol/water system, ethanol: water=7:3), after 10s, take out and hang the 10min that dries in the shade, in baking oven, after 70 ℃ of dry 10min desolvations, obtain PAN/ hydroxy silicon oil (hydroxy radical content 1.5%)-PDMS/PEBA composite membrane.Test its permeability and selective, and artificial (hand tears) carries out stripper-resistance test to composite membrane.Test result is in Table 2.
Table 2.
Interpretation of result:
The result of table 1 shows:
In embodiment 1, when PEBA concentration lower (1wt%), formed separating layer in solvent evaporates process, because blending the reason that solution concentration is too low, hole can not cover the hole on counterdie completely, can not on counterdie, form flawless separating layer, therefore the composite membrane infiltration rate of preparation is higher, and selectively far below material's eigenvalue [1].While further increasing PEBA concentration (3wt%) in embodiment 2, although can form comparatively complete separating layer after solvent evaporates, show as selectivity ratios and approach material's eigenvalue
[1], but the separating layer forming is blocked up, causes composite membrane infiltration rate lower.Applicant finds through many experiments, in adopting embodiment 3 during 2wt%PEBA concentration, after solvent evaporates, can basically form thinner relatively complete separating layer, infiltration rate and the selectivity ratios of composite membrane are more satisfactory, so adopt 2wt%PEBA solution to prepare separating layer in other embodiments of the present invention.
The result of table 2 shows:
In embodiment 4, adopt PDMS as intermediate layer, ooze in the hole having reduced in PEBA solution coating procedure.But because PDMS shows as compared with strong-hydrophobicity, between PEBA and PDMS, affinity is poor, and PEBA solution is difficult to sprawl on PDMS cortex, therefore formed separating layer surface defectiveness, shows as selectively far below material's eigenvalue
[1].Because compatibility is not good, very easily peel off in separating layer and intermediate layer simultaneously.
In embodiment 5, further increased PDMS solution concentration, but little to composite membrane performance impact, the data of infiltration and selective and embodiment 4 are more approaching, and also very easily peel off in separating layer and intermediate layer.
In embodiment 6 in PDMS solution blend there is certain hydrophilic hydroxy silicon oil, intermediate layer hydrophily 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 intermediate layer, along with solvent evaporates and then form and almost do not have defective separating layer, show selectively far above embodiment 4, relatively approach material's eigenvalue
[1].Because compatibility increases, separating layer and intermediate layer are difficult for peeling off simultaneously, and compound film strength obviously improves.
In embodiment 7, further improved the content of hydroxy silicon oil in the solution of intermediate layer, intermediate layer hydrophily further improves, and further increases with PEBA compatibility, and PEBA solution is more easily sprawled on intermediate layer, therefore being selectively slightly improved of composite membrane approaches material's eigenvalue very much
[1], and be difficult for peeling off.
In embodiment 8, adopted the slightly low and higher hydroxy silicon oil of viscosity of hydroxy radical content, intermediate layer hydrophily declines to some extent, decreases with PEBA compatibility, compare with embodiment 6, and selectively slightly the declining of composite membrane, intensity is still higher, is difficult for peeling off.
Above result and analyze known, composite membrane of the present invention, intermediate layer adopts the intermingling material of hydroxy silicon oil and PDMS, the adhesion of itself and hydrophily separating layer is greater than PDMS separately as the composite membrane (embodiment 4-5) in intermediate layer, intermediate layer and separating layer are difficult for peeling off, and composite membrane is for infiltration and the selective obviously raising of gas.In addition, increase concentration and the hydroxy radical content of hydroxy silicon oil, the infiltration of the intermediate layer of composite membrane of the present invention and the bond strength of separating layer and composite membrane and selectively also increase thereupon.
Document [1]: < < Gas permeation of poly (amide-6-b-ethylene oxide) copolymer > >, Journal of Membrane Science, 190 (2001): 179-193.
Claims (9)
1. a composite membrane, comprise porous support membrane, be coated in the intermediate layer on porous support membrane and be coated in the separating layer of selecting separating property that has on intermediate layer, it is characterized in that, the material in described intermediate layer comprises 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 mixed with after hydroxy silicon oil-silicon-containing polymer blend solution of 1-15wt% for the preparation of intermediate layer, and in blend solution, the mass ratio of hydroxy silicon oil and silicon-containing polymer is 1:1-9:1.
3. composite membrane according to claim 1, is characterized in that, described Hydroxyl Content in Hydroxysilicone fluid is 0.5-3%, and hydroxy silicon oil viscosity is 25-100000cs.
4. composite membrane according to claim 1, is characterized in that, the thickness in described intermediate layer is 0.5-5 μ m.
5. according to the composite membrane described in any one of claim 1-4, it is characterized in that, described silicon-containing polymer is a kind of in dimethyl silicone polymer, poly-trimethyl silicane propine.
6. composite membrane according to claim 1, is characterized in that, the thickness of described porous support membrane is 50-200 μ m, and the thickness of described separating layer is 0.05-5 μ m.
7. composite membrane according to claim 1, is characterized in that, the membrane material of described porous support membrane is one or more in polysulfones, polyether sulfone, polyacrylonitrile, PEI, Kynoar.
8. composite membrane according to claim 1, is characterized in that, the membrane material of described separating layer is a kind of in polyethers copolyamide, polyvinyl alcohol, polyamide.
9. the preparation method of composite membrane claimed 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, being configured to concentration is hydroxy silicon oil-silicon-containing polymer blend solution of 1-15wt%, after standing and defoaming, be coated on porous support membrane, at 60-90 ℃ of dry 5-15min desolvation, obtain the composite membrane in porous counterdie/hydroxy silicon oil-silicon-containing polymer intermediate layer;
(2) separating layer material is dissolved in to the separating layer solution that is mixed with 0.5-10wt% in solvent B, after standing and defoaming at 40-60 ℃ dip-coating on the composite membrane in porous counterdie/hydroxy silicon oil-silicon-containing polymer intermediate layer, at 60-90 ℃ of dry 5-15min desolvation, obtain the sandwich diaphragm of porous counterdie/hydroxy silicon oil-silicon-containing polymer intermediate layer/separating layer;
Wherein: at the solvent orange 2 A described in step (1), be one or more the mixed solvent in n-hexane, isooctane, normal heptane, gasoline, benzinum; At the solvent B described in step (2), be a kind of in ethanol/butanol/water, propyl alcohol/butanols, butanols, ethanol/water; The thickness in described hydroxy silicon oil-silicon-containing polymer intermediate layer is 0.5-5 μ m, and the thickness of described separating layer is 0.05-5 μ m.
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| CN103657458A (en) * | 2013-12-25 | 2014-03-26 | 大连欧科膜技术工程有限公司 | PEBA (Polyether block amide) composite film as well as preparation method and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20110042315A1 (en) * | 2009-08-19 | 2011-02-24 | University Of Connecticut | Pervaporation composite membrane for aqueous solution separation and methods for using the same |
| 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 |
-
2013
- 2013-11-30 CN CN201310639578.7A patent/CN103599708B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451465A (en) * | 2002-04-12 | 2003-10-29 | 四川大学 | Method for making composite membrane for separation of polymer fluid |
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