CN105879699A - Hyperbranched polysiloxane multilayer compound film and preparation method thereof - Google Patents
Hyperbranched polysiloxane multilayer compound film and preparation method thereof Download PDFInfo
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- CN105879699A CN105879699A CN201410784364.3A CN201410784364A CN105879699A CN 105879699 A CN105879699 A CN 105879699A CN 201410784364 A CN201410784364 A CN 201410784364A CN 105879699 A CN105879699 A CN 105879699A
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Abstract
The invention relates to a hyperbranched polysiloxane multilayer compound film and a preparation method thereof. The preparation method comprises the following steps: 1) causing hyperbranched polysiloxane, solvent, 107 gel and catalyst react for 12h at 60-80 DEG C to form casting film feed liquid, and coating a polyvinylidene fluoride porous base film with the acquired casting film feed liquid, thereby acquiring a hyperbranched polysiloxane film; 2) causing vinyl triethoxy silane, solvent, 107 gel and catalyst react for 6h at 60-80 DEG C to form the casting film feed liquid, and coating the hyperbranched polysiloxane film with the acquired casting film feed liquid, thereby acquiring the hyperbranched polysiloxane multilayer compound film. The hyperbranched polysiloxane multilayer compound film prepared according to the method provided by the invention has a three-layer film structure; a polyvinylidene fluoride ultrafiltration film with non-woven fabric support is arranged as the bottom layer; the hyperbranched polysiloxane film is arranged as the middle layer; the ultra-thin polysiloxane film is arranged as a top separating layer. The porousness of the hyperbranched polysiloxane multilayer compound film prepared according to the method provided by the invention is distributed in a gradient form from top to bottom and the property of separating butanol from water through pervaporation is greatly promoted.
Description
Technical field
The invention belongs to infiltration vaporization separation film preparation field, particularly relate to a kind of novel hyperbranched polyorganosiloxane multilayer complex films
And preparation method thereof.
Background technology
The day by day exhausted and serious pollution of Fossil fuel has expedited the emergence of the research and development of bio-fuel, and wherein biological butanol is considered as
The second filial generation bioenergy that performance is more excellent.But during fermentation method prepares biological butanol, there is the most serious butanol to bacterium
The inhibitory action planted, makes sweat not to be carried out continuously, it is therefore desirable to be separated from fermentation liquid by butanol in time.Infiltration evaporation
Process is considered as the liquid mixture separation process of most promising low energy consumption, high separating efficiency.Some hydrophobic membrane materials
By successively for separating the developmental research of butanol in water.
The fine and close selection that osmosis vaporizing compound membrane is typically one layer thin is placed on one layer of stable support layer of porous mechanical, it is allowed to ooze
Thoroughly under certain pressure reduction, there is high flux and selectivity in vaporescence.In the evolution of high flux membrane, more grind
Study carefully and tend to change membrane structure to form the asymmetric or dense film of composite construction.But, the decline of film thickness is often accompanied
Along with film optionally reduces, this is to create substantial amounts of defect owing to the reduction of film thickness result in film surface, it is impossible to form table
Face zero defect dense film.Therefore, the reason limiting film thickness is many, generally comprises the support aperture of tunic, pore size distribution
And the degree of roughness on surface.
Dissaving polymer is a kind of new polymers with unique topological structure, has that structure height is branched, surface functional group
Density is high, chemical stability good, surface-functionalized simple, be prone to the features such as film forming.The more important thing is, hyperbranched poly
Compound has bigger free volume, and molecular structure is of a relatively loose.Three-dimensional molecular structure special for dissaving polymer is introduced
Inside the stratum disjunctum of polysiloxanes infiltrating and vaporizing membrane, the flux of film is significantly increased, but its separation factor is the highest.
Summary of the invention
It is an object of the invention to provide a kind of hyperbranched polyorganosiloxane multilayer complex films for separating butanol and preparation method thereof,
To overcome the defect of prior art.
A kind of hyperbranched polyorganosiloxane MULTILAYER COMPOSITE membrane preparation method that the present invention proposes, it is characterised in that comprise the steps:
A by hyperbranched polyorganosiloxane 1.5-2 part, solvent 86-89 part, 107 glue 7.5-10 parts, catalyst 0.5-1.0 part at 60～80 DEG C
After lower reaction 12h, form casting film feed liquid, gained casting solution is coated on Kynoar porous counterdie, stand sulfur in air
Change 2h, then proceed to air dry oven and obtain hyperbranched polyorganosiloxane composite membrane in 80 DEG C of dry 12h.
VTES 1.5-2 part, solvent 86-89 part, 107 glue 7.5-10 parts, catalyst 0.5-1.0 part are existed by B
After reacting 6h at 60～80 DEG C, form masking feed liquid, gained coating materials liquid is coated on above-mentioned hyperbranched polyorganosiloxane film, stand
Air vulcanizes 2h, then proceeds to air dry oven in 80 DEG C of dry 12h, obtain hyperbranched polyorganosiloxane multilayer complex films.
Preferably, the degree of branching of described hyperbranched polyorganosiloxane is 0.70,0.75,0.80.
Preferably, described solvent is normal hexane, normal heptane or normal octane.
Preferably, the viscosity of described 107 glue is 1 × 103cs、1×104cs、1×106cs。
Preferably, described catalyst is dibutyl tin dilaurate, Mono-n-butyltin, Dibutyltin oxide.
The present invention also proposes a kind of hyperbranched polyorganosiloxane multilayer complex films, it is characterised in that top layer is silicone layer, formula bag
Include following component: VTES 1.5-2 part, solvent 86-89 part, 107 glue 7.5-10 parts, catalyst 0.5-1.0
Part；Intermediate layer is hyperbranched polyorganosiloxane layer, and formula includes following component: hyperbranched polyorganosiloxane 1.5-2 part, solvent 86-89
Part, 107 glue 7.5-10 parts, catalyst 0.5-1.0 part；Bottom is polyvinylidene fluoride (PVDF) ultrafiltration membrane.
Preferably, the degree of branching of described hyperbranched polyorganosiloxane is 0.70,0.75,0.80.
Preferably, described solvent is normal hexane, normal heptane or normal octane.
Preferably, the viscosity of described 107 glue is 1 × 103cs、1×104cs、1×106cs。
Preferably, described catalyst is dibutyl tin dilaurate, Mono-n-butyltin, Dibutyltin oxide.
The hyperbranched polyorganosiloxane multilayer complex films that the present invention provides, the trilamellar membrane structure existed, bottom is that band non-woven fabrics supports
Polyvinylidene fluoride (PVDF) ultrafiltration membrane, provides higher mechanical strength for hyperbranched polyorganosiloxane multilayer complex films, to meet infiltration evaporation
Required basic demand, intermediate layer hyperbranched polyorganosiloxane film not only has certain separating property, and separates for top layer butanol
Strata siloxane layer provides the supporting surface of surfacing so that top layer polysiloxanes can form the flawless very thin stratum disjunctum in surface.
Top layer stratum disjunctum is polysiloxane film, and very thin stratum disjunctum has higher flux and keeps higher separation factor butanol, its
Body is good with hyperbranched polyorganosiloxane film tackness, it is not easy to fall from hyperbranched polyorganosiloxane pull-up.Hyperbranched polyorganosiloxane multilamellar is multiple
Closing film, from top to bottom, porousness distribution gradient, during infiltration evaporation, organic butanol molecules is easier to pass through, greatly
Improve the performance of butanol in infiltration evaporation separation water.
In sum, the preparation method of the hyperbranched polyorganosiloxane multilayer complex films of the present invention, have the advantage that
1, the present invention uses thermal curing method, and polymerization efficiency is high, and technique is simple, easy to operate, produces reproducible.
2, the present invention uses high-throughout hyperbranched polyorganosiloxane film as intermediate supports material, and itself is with polysiloxanes (PDMS)
Film tackness is good；There is not the situation that polysiloxane film comes off from supporting layer, its final multiple structure composite membrane has good stability,
Physical arrangement is stable.
3, hyperbranched polyorganosiloxane multilayer complex films prepared by the inventive method is used, due to dissaving structure and molecular function group
Impact, good to the permeance property of butanol, thus its separation factor is high.
Detailed description of the invention
The following is the embodiment of hyperbranched polyorganosiloxane multilayer complex films and preparation method thereof, but described embodiment is not constituted this
Bright restriction.
Embodiment one:
1) hyperbranched polyorganosiloxane film is prepared:
It is 1 × 10 by 0.70 degree of branching hyperbranched polyorganosiloxane 1.5 parts, normal hexane 86 parts, viscosity37.5 parts of 107 glue of cs,
After dibutyl tin dilaurate 0.5 part reacts 12h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on poly-
On vinylidene porous counterdie, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched in 80 DEG C of dry 12h
Polysiloxane film.
2) hyperbranched polyorganosiloxane multilayer complex films is prepared:
It is 1 × 10 by VTES 1.5 parts, normal hexane 86 parts, viscosity3107 glue 7.5-parts of cs, dibutyl
0.5 part of tin dilaurate stannum, after 60～80 DEG C of reaction 6h, forms casting film feed liquid, gained casting solution is coated on above-mentioned hyperbranched poly
On silicone film, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched polyorganosiloxane in 80 DEG C of dry 12h
Multilayer complex films.
Above-mentioned hyperbranched polyorganosiloxane multilayer complex films is used for n-butyl alcohol in infiltration evaporation separation water, and its infiltration evaporation result is:
Permeation flux is 199.77g/m2H, its separation factor is 23.6.
Embodiment two:
1) hyperbranched polyorganosiloxane film is prepared:
It is 1 × 10 by 0.70 degree of branching hyperbranched polyorganosiloxane 1.5 parts, normal heptane 89 parts, viscosity310 parts of 107 glue of cs,
After dibutyl tin dilaurate 0.5 part reacts 12h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on poly-
On vinylidene porous counterdie, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched in 80 DEG C of dry 12h
Polysiloxane film.
2) hyperbranched polyorganosiloxane multilayer complex films is prepared:
It is 1 × 10 by VTES 1.5 parts, normal heptane 89 parts, viscosity310 parts of 107 glue of cs, dibutyl two
After tin laurate 0.5 part reacts 6h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on above-mentioned hyperbranched poly
On silicone film, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched polyorganosiloxane in 80 DEG C of dry 12h
Multilayer complex films.
Above-mentioned hyperbranched polyorganosiloxane multilayer complex films is used for n-butyl alcohol in infiltration evaporation separation water, and its infiltration evaporation result is:
Permeation flux is 198.34g/m2H, its separation factor is 24.2.
Embodiment three:
1) hyperbranched polyorganosiloxane film is prepared:
It is 1 × 10 by 0.75 degree of branching hyperbranched polyorganosiloxane 2 parts, normal octane 87 parts, viscosity37.5 parts of 107 glue of cs, two
After 1.0 parts of butyl tin dilaurate stannum reacts 12h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on poly-inclined
On fluorothene porous counterdie, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched poly in 80 DEG C of dry 12h
Silicone film.
2) hyperbranched polyorganosiloxane multilayer complex films is prepared:
It is 1 × 10 by VTES 2 parts, 87 parts of viscosity of normal octane37.5 parts of 107 glue of cs, dibutyl tin
After 1.0 parts of cinnamic acid stannum reacts 6h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on above-mentioned hyperbranched poly silicon
On siloxane film, standing and vulcanize 2h in air, then proceeding to air dry oven, to obtain hyperbranched polyorganosiloxane in 80 DEG C of dry 12h many
Layer composite membrane.
Above-mentioned hyperbranched polyorganosiloxane multilayer complex films is used for n-butyl alcohol in infiltration evaporation separation water, and its infiltration evaporation result is:
Permeation flux is 201.89g/m2H, its separation factor is 24.7.
Embodiment four:
1) hyperbranched polyorganosiloxane film is prepared:
It is 1 × 10 by 0.75 degree of branching hyperbranched polyorganosiloxane 1.7 parts, normal heptane 86 parts, viscosity48 parts of 107 glue of cs, list
After butyl stannum oxide 0.5 part reacts 12h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on polyvinylidene fluoride
On alkene porous counterdie, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched poly silica in 80 DEG C of dry 12h
Alkane film.
2) hyperbranched polyorganosiloxane multilayer complex films and post processing are prepared:
It is 1 × 10 by VTES 1.7 parts, normal heptane 86 parts, viscosity4107 glue 7.5-10 parts of cs, only son
After base stannum oxide 0.5 part reacts 6h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on above-mentioned hyperbranched poly
On silicone film, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched polyorganosiloxane in 80 DEG C of dry 12h
Multilayer complex films.
Above-mentioned hyperbranched polyorganosiloxane multilayer complex films is used for n-butyl alcohol in infiltration evaporation separation water, and its infiltration evaporation result is:
Permeation flux is 195.21g/m2H, its separation factor is 22.1.
Embodiment five:
1) hyperbranched polyorganosiloxane film is prepared:
It is 1 × 10 by 0.80 degree of branching hyperbranched polyorganosiloxane 2 parts, normal heptane 88 parts, viscosity69 parts of 107 glue of cs, list
After butyl stannum oxide 1.0 parts reacts 12h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on polyvinylidene fluoride
On alkene porous counterdie, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched poly silica in 80 DEG C of dry 12h
Alkane film.
2) hyperbranched polyorganosiloxane multilayer complex films is prepared:
It is 1 × 10 by VTES 2 parts, normal heptane 88 parts, viscosity69 parts of 107 glue of cs, monobutyl aoxidize
After 1.0 parts of stannum reacts 6h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on above-mentioned hyperbranched polyorganosiloxane
On film, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched polyorganosiloxane multilamellar again in 80 DEG C of dry 12h
Close film.
Above-mentioned hyperbranched polyorganosiloxane multilayer complex films is used for n-butyl alcohol in infiltration evaporation separation water, and its infiltration evaporation result is:
Permeation flux is 298.34g/m2H, its separation factor is 24.3.
Embodiment six:
1) hyperbranched polyorganosiloxane film is prepared:
It is 1 × 10 by 0.80 degree of branching hyperbranched polyorganosiloxane 2 parts, normal heptane 89 parts, viscosity310 parts of 107 glue of cs, two
After butyl stannum oxide 0.5 part reacts 12h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on polyvinylidene fluoride
On alkene porous counterdie, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched poly silica in 80 DEG C of dry 12h
Alkane film.
2) hyperbranched polyorganosiloxane multilayer complex films is prepared:
It is 1 × 10 by VTES 2 parts, normal heptane 89 parts, viscosity310 parts of 107 glue of cs, dibutyl oxygen
After 0.5 part of stannum of change reacts 6h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on above-mentioned hyperbranched poly silica
On alkane film, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched polyorganosiloxane multilamellar in 80 DEG C of dry 12h
Composite membrane.
Above-mentioned hyperbranched polyorganosiloxane multilayer complex films is used for n-butyl alcohol in infiltration evaporation separation water, and its infiltration evaporation result is:
Permeation flux is 302.67g/m2H, its separation factor is 25.4.
Embodiment seven:
1) hyperbranched polyorganosiloxane film is prepared:
It is 1 × 10 by 0.75 degree of branching hyperbranched polyorganosiloxane 1.5 parts, normal heptane 86 parts, viscosity37.5 parts of 107 glue of cs,
After Dibutyltin oxide 0.5 part reacts 12h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on poly-inclined fluorine
On ethylene porous counterdie, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched poly silicon in 80 DEG C of dry 12h
Siloxane film.
2) hyperbranched polyorganosiloxane multilayer complex films is prepared:
It is 1 × 10 by VTES 1.5 parts, normal heptane 86 parts, viscosity37.5 parts of 107 glue of cs, dibutyl
After stannum oxide 0.5 part reacts 6h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on above-mentioned hyperbranched poly silicon
On siloxane film, standing and vulcanize 2h in air, then proceeding to air dry oven, to obtain hyperbranched polyorganosiloxane in 80 DEG C of dry 12h many
Layer composite membrane.
Above-mentioned hyperbranched polyorganosiloxane multilayer complex films is used for n-butyl alcohol in infiltration evaporation separation water, and its infiltration evaporation result is:
Permeation flux is 326.54g/m2H, its separation factor is 16.2.
Embodiment eight:
1) hyperbranched polyorganosiloxane film is prepared:
It is 1 × 10 by 0.80 degree of branching hyperbranched polyorganosiloxane 2 parts, normal hexane 89 parts, viscosity610 parts of 107 glue of cs, two
After 1.0 parts of butyl tin dilaurate stannum reacts 12h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on poly-inclined
On fluorothene porous counterdie, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched poly in 80 DEG C of dry 12h
Silicone film.
2) hyperbranched polyorganosiloxane multilayer complex films is prepared:
It is 1 × 10 by VTES 2 parts, normal hexane 89 parts, viscosity610 parts of 107 glue of cs, dibutyl two
After tin laurate 1.0 parts reacts 6h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on above-mentioned hyperbranched poly
On silicone film, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched polyorganosiloxane in 80 DEG C of dry 12h
Multilayer complex films.
Above-mentioned hyperbranched polyorganosiloxane multilayer complex films is used for n-butyl alcohol in infiltration evaporation separation water, and its infiltration evaporation result is:
Permeation flux is 298.34g/m2H, its separation factor is 24.3.
Embodiment nine:
1) hyperbranched polyorganosiloxane film is prepared:
It is 1 × 10 by 0.70 degree of branching hyperbranched polyorganosiloxane 1.7 parts, normal hexane 88 parts, viscosity48.5 parts of 107 glue of cs,
After Mono-n-butyltin 0.8 part reacts 12h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on poly-inclined fluorine
On ethylene porous counterdie, stand and air vulcanizes 2h, then proceed to air dry oven and obtain hyperbranched poly silicon in 80 DEG C of dry 12h
Siloxane film.
2) hyperbranched polyorganosiloxane multilayer complex films is prepared:
It is 1 × 10 by VTES 1.7 parts, normal hexane 88 parts, viscosity48.5 parts of 107 glue of cs, monobutyl
After stannum oxide 0.8 part reacts 6h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on above-mentioned hyperbranched poly silicon
On siloxane film, standing and vulcanize 2h in air, then proceeding to air dry oven, to obtain hyperbranched polyorganosiloxane in 80 DEG C of dry 12h many
Layer composite membrane.
Above-mentioned hyperbranched polyorganosiloxane multilayer complex films is used for n-butyl alcohol in infiltration evaporation separation water, and its infiltration evaporation result is:
Permeation flux is 178.44g/m2H, its separation factor is 29.5.
The description of above-described embodiment should be considered explanation, it is easy to is understood by, can be without departing from illustrating the most in detail in the claims
The present invention in the case of use many changes and the combination of feature described above, this kind of change has been not to be regarded as a departure from this
Bright spirit and scope, and all such change be included in the range of claims below.
Claims (10)
1. the preparation method of a hyperbranched polyorganosiloxane multilayer complex films, it is characterised in that comprise the steps, formula forms by weight
Number meter:
A by hyperbranched polyorganosiloxane 1.5-2 part, solvent 86-89 part, 107 glue 7.5-10 parts, catalyst 0.5-1.0 part at 60～80 DEG C
After lower reaction 12h, form casting film feed liquid, gained casting solution is coated on Kynoar porous counterdie, stand sulfur in air
Change 2h, then proceed to air dry oven and obtain hyperbranched polyorganosiloxane composite membrane in 80 DEG C of dry 12h；
VTES 1.5-2 part, solvent 86-89 part, 107 glue 7.5-10 parts, catalyst 0.5-1.0 part are existed by B
After reacting 6h at 60～80 DEG C, form casting film feed liquid, gained casting solution is coated on above-mentioned hyperbranched polyorganosiloxane film, stand
Air vulcanizes 2h, then proceeds to air dry oven in 80 DEG C of dry 12h, obtain hyperbranched polyorganosiloxane multilayer complex films.
Hyperbranched polyorganosiloxane MULTILAYER COMPOSITE membrane preparation method the most according to claim 1, it is characterised in that described hyperbranched poly silica
The degree of branching of alkane is 0.70,0.75,0.80.
3. according to hyperbranched polyorganosiloxane MULTILAYER COMPOSITE membrane preparation method described in claim 1-2, it is characterised in that described solvent is just own
Alkane, normal heptane, normal octane.
4. according to hyperbranched polyorganosiloxane MULTILAYER COMPOSITE membrane preparation method described in claim 1-3, it is characterised in that gluing of described 107 glue
Degree is 1 × 103cs、1×104cs、1×106cs。
5. according to hyperbranched polyorganosiloxane MULTILAYER COMPOSITE membrane preparation method described in claim 1-4, it is characterised in that described catalyst is two
Butyl tin dilaurate stannum, Mono-n-butyltin, Dibutyltin oxide.
6. a hyperbranched polyorganosiloxane multilayer complex films, it is characterised in that top layer is silicone layer, formula includes following component: second
Thiazolinyl triethoxysilane 1.5-2 part, solvent 86-89 part, 107 glue 7.5-10 parts, catalyst 0.5-1.0 part；Intermediate layer is
Hyperbranched polyorganosiloxane layer, formula includes following component: hyperbranched polyorganosiloxane 1.5-2 part, solvent 86-89 part, 107 glue 7.5-10
Part, catalyst 0.5-1.0 part；Bottom is polyvinylidene fluoride (PVDF) ultrafiltration membrane.
Hyperbranched polyorganosiloxane multilayer complex films the most according to claim 6, it is characterised in that propping up of described hyperbranched polyorganosiloxane
Change degree is 0.70,0.75,0.80.
8. according to hyperbranched polyorganosiloxane multilayer complex films described in claim 6-7, it is characterised in that described solvent is normal hexane, just
Heptane, normal octane.
9. according to hyperbranched polyorganosiloxane multilayer complex films described in claim 6-8, it is characterised in that the viscosity of described 107 glue is
1×103cs、1×104cs、1×106cs。
10. according to hyperbranched polyorganosiloxane multilayer complex films described in claim 6-9, it is characterised in that described catalyst is dibutyl
Tin dilaurate stannum, Mono-n-butyltin, Dibutyltin oxide.
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| CN101279212A (en) * | 2008-04-15 | 2008-10-08 | 中国石油化工股份有限公司 | Preparation of intercrossed network water dealcoholizing pervaporation membrane |
| CN102698621A (en) * | 2012-06-11 | 2012-10-03 | 江南大学 | High-flux hyperbranched polysiloxane pervaporation membrane and preparation method thereof |
| US20120270976A1 (en) * | 2011-04-21 | 2012-10-25 | Hiroyoshi Kawakami | Room temperature curable organopolysiloxane composition and gas separation membrane |
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2014
- 2014-12-16 CN CN201410784364.3A patent/CN105879699A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279212A (en) * | 2008-04-15 | 2008-10-08 | 中国石油化工股份有限公司 | Preparation of intercrossed network water dealcoholizing pervaporation membrane |
| US20120270976A1 (en) * | 2011-04-21 | 2012-10-25 | Hiroyoshi Kawakami | Room temperature curable organopolysiloxane composition and gas separation membrane |
| CN102698621A (en) * | 2012-06-11 | 2012-10-03 | 江南大学 | High-flux hyperbranched polysiloxane pervaporation membrane and preparation method thereof |
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