CN109621754A - A kind of dimethyl silicone polymer composite membrane and preparation method thereof application - Google Patents
A kind of dimethyl silicone polymer composite membrane and preparation method thereof application Download PDFInfo
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- CN109621754A CN109621754A CN201811550641.9A CN201811550641A CN109621754A CN 109621754 A CN109621754 A CN 109621754A CN 201811550641 A CN201811550641 A CN 201811550641A CN 109621754 A CN109621754 A CN 109621754A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/122—Separate manufacturing of ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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Abstract
The invention discloses dimethyl silicone polymer composite membrane and preparation method thereof applications, belong to UF membrane field.The dimethyl silicone polymer composite membrane contains mixed-matrix layer, the mixed-matrix layer is the film formed after the dimethyl silicone polymer of doping porous hybrid material solidifies, the porous hybrid material is the hybrid material of metal-organic framework material with the carbon material for being modified with carboxyl, and the metal-organic framework material is connect with the carbon material for being modified with carboxyl by hydrogen bond.The dimethyl silicone polymer composite membrane also contains supporting layer, any surface of the mixed-matrix layer blade coating in the supporting layer；The supporting layer is that perhaps the supporting layer is non-woven fabrics to polymer film or the supporting layer is the non-woven fabrics for having scratched polymer film.Composite membrane in the present invention is prepared by solution blended process, greatly simplifies filming technology, and inorganic particulate will not be caused to reunite, and obtained composite membrane organic solvent separation factor is high.
Description
Technical field
The invention belongs to UF membrane fields, more particularly, to a kind of dimethyl silicone polymer composite membrane and its preparation side
Method application.
Background technique
Dimethyl silicone polymer composite membrane is common a kind of polymer film in membrane separating process.Due to polydimethylsiloxanes
Alkane has stronger hydrophobicity, and dimethyl silicone polymer composite membrane has widely been studied for ethanol/water separation.Pure poly- two
The separation factor about 5-8 of methylsiloxane film ethanol/water separation, is not able to satisfy industrial application completely.Traditional poly dimethyl
The preparation of silicone film is to prepare symmetrical PDMS membrane, selects layer thicker, influences the flux of ethyl alcohol.Another party
Face directly carries out being modified PDMS membrane into dimethyl silicone polymer matrix by inorganic particle filled, often
The agglomeration that inorganic particulate occurs, can reduce the separation of ethanol performance of dimethyl silicone polymer instead.In addition, poly dimethyl silicon
Oxygen alkane film forming needs suitable catalyst and crosslinking agent.Therefore, how to be prepared it is a kind of it is ultra-thin, film forming is good, ethyl alcohol
The polydimethylsiloxanefilm film composite membrane that flux is high, ethanol/water separation factor is high is to suffer from a problem that at present.
Summary of the invention
It is poor that the present invention solves in PDMS membrane in the prior art separating property caused by inorganic particulate is reunited,
And the technical problem that organic solvent separation factor is low.In order to solve the above-mentioned technical problem, of the invention, pass through solution blending process
The porous hybrid material of metal-organic framework material and the carbon material for having modified carboxyl is filled into PDMS matrix
In, the ultra-thin selection layer of modified dimethyl silicone polymer is obtained, to solve polydimethylsiloxanes traditional at present
Main problem present in alkane film.
It is according to the invention in a first aspect, providing a kind of dimethyl silicone polymer composite membrane, the polydimethylsiloxanes
Alkane composite membrane contains mixed-matrix layer, and the mixed-matrix layer is after the dimethyl silicone polymer of doping porous hybrid material solidifies
The film of formation, the porous hybrid material are the hybrid material of metal-organic framework material with the carbon material for being modified with carboxyl, institute
It states metal-organic framework material and is connect with the carbon material for being modified with carboxyl by hydrogen bond.
The dimethyl silicone polymer composite membrane also contains supporting layer, and the mixed-matrix layer blade coating is in the supporting layer
Any surface；The supporting layer is that perhaps the supporting layer is non-woven fabrics to polymer film or the supporting layer is to have scratched to gather
The non-woven fabrics of compound film；The mixed-matrix layer with a thickness of 8 μm -12 μm.
Preferably, the metal-organic framework material is ZIF-8, MOF-5, ZIF-67, MIL-53 or HKUST-1；It is described
The carbon material for being modified with carboxyl is graphene oxide, the carbon nanotube for modifying carboxyl, the carbon nano-fiber for modifying carboxyl or modification
The Nano carbon balls of carboxyl；The dimethyl silicone polymer is hydroxy-end capped dimethyl silicone polymer, amino-terminated poly- diformazan
At least one of radical siloxane and the dimethyl silicone polymer of ethenyl blocking；The equal molecule of the number of the dimethyl silicone polymer
Amount is 20000-500000.
Preferably, the polymer film be polyacrylonitrile film, poly (ether sulfone) film, PS membrane, polyimide film, PA membrane,
Polyetherimde films, polyamidoimide film, cellulose acetate film, three cellulose acetate membrane or polyvinylidene fluoride film.
It is another aspect of this invention to provide that the preparation method of any dimethyl silicone polymer composite membrane is provided,
Porous hybrid material is dispersed in boiling point less than or equal in the organic solvent of toluene, polydimethylsiloxanes are then added
Alkane obtains the mixed solution of porous hybrid material and dimethyl silicone polymer；Again to the porous hybrid material and poly dimethyl silicon
Catalyst and crosslinking agent are added in the mixed solution of oxygen alkane, the dimethyl silicone polymer is made to crosslink reaction；To described mixed
Solution is closed to be transformed into due to the crosslinking of dimethyl silicone polymer after thick gradually solidification to get the polydimethylsiloxanes are arrived
Alkane composite membrane；
The porous hybrid material is the hybrid material of metal-organic framework material with the carbon material for being modified with carboxyl, described
Metal-organic framework material is connect with the carbon material for being modified with carboxyl by hydrogen bond.
Preferably, the mixed solution due to dimethyl silicone polymer crosslinking and be transformed into it is thick after, blade coating to prop up
Layer is supportted, dimethyl silicone polymer composite membrane is obtained after solidification；
The supporting layer is that perhaps the supporting layer is non-woven fabrics to polymer film or the supporting layer is to have scratched to gather
The non-woven fabrics of compound film.
Preferably, the quality of the porous hybrid material is the 0.1%-2% of the quality of the dimethyl silicone polymer；
The quality sum of the porous hybrid material and dimethyl silicone polymer accounts for the 15%-20% of mixed solution quality；It is described organic
Solvent is n-hexane, normal heptane, tetrahydrofuran, hexamethylene or toluene.
Preferably, the mixed solution due to dimethyl silicone polymer crosslinking and be transformed into it is thick after, to thick
Liquid is heated, and solidifies viscous liquid to get the dimethyl silicone polymer composite membrane is arrived；The temperature of the heating is
30 DEG C -80 DEG C, the time of heating is 8h-14h.
It preferably, further include the process of heating after the blade coating to supporting layer；The temperature of the heating is 30 DEG C -80
DEG C, the time of heating is 8h-14h；The non-woven fabrics for having scratched polymer film the preparation method comprises the following steps: the polymerization of film will be formed
Object solution scratches on non-woven fabrics, and the method by mutually converting makes the polymer solution form polymer film, is prepared and scrapes
The non-woven fabrics of polymer film is applied；
Preferably, what the phase was converted converts liquid as deionized water, tannic acid coagulating bath, sodium hydrate aqueous solution, nothing
Water-ethanol or anhydrous methanol.
It is used for it is another aspect of this invention to provide that providing any dimethyl silicone polymer composite membrane from organic molten
The application of in the mixed solvent Separation of Organic after agent is miscible with water；
Preferably, the organic solvent is ethyl alcohol, methanol, isopropanol or butanol；
Preferably, the isolated temperature is 40 DEG C -70 DEG C；
Preferably, the mass concentration of the in the mixed solvent organic solvent is 2.5wt%-10wt%.
In general, the optimization of contemplated above technical scheme and experiment condition through the invention, can obtain down
Column the utility model has the advantages that
(1) present invention has selected hybrid material with synergy as filler material, is prepared for dimethyl silicone polymer
Select layer.By simple solution blended process, in the mixed solvent separation of the dimethyl silicone polymer after miscible with water is improved
The separating property (such as ethyl alcohol) of organic solvent, to greatly simplifie filming technology.
(2) composite membrane that the present invention is prepared by simple solution blending process, by adjusting porous hybrid material
The content of middle carbon material, the content and arrangement of metal-organic framework material in adjustable carbon material sheet surfaces.Pass through optimization
The carbon material content of content and porous hybrid material in dimethyl silicone polymer in porous hybrid material obtained high score from
The dimethyl silicone polymer composite membrane of efficiency.Metal-organic framework material ZIF-8 and graphene oxide (GO) hydridization preferably
Material is selected as filler material, is mainly due to the synergistic effect of ZIF-8@GO hybrid material, and GO can be provided to ZIF-8 in poly- diformazan
Dispersibility in radical siloxane, while ZIF-8 provides hydrophobicity to GO.Compared to pure dimethyl silicone polymer composite membrane, identical
Test condition under, the separation factor of the dimethyl silicone polymer composite membrane ethanol/water containing ZIF-8@GO hybrid material improves
287.7%.
(3) hydrophobic porous inorganic particle is introduced in dimethyl silicone polymer composite membrane can be improved poly dimethyl silicon
The flux of the ethyl alcohol of siloxane film and the separation factor of ethanol/water.On the one hand, hydrophobic porous inorganic particle can to ethyl alcohol and
Water selective penetrates, and can play the role of the separation factor for improving ethanol/water, while hydrophobic porous inorganic particle is more
The flux of ethyl alcohol can be improved in the channel in hole.Therefore there is more excellent separation of ethanol than pure PDMS membrane
Energy.On the other hand, by the mixed solution of ZIF-8@GO and dimethyl silicone polymer blade coating on polymer/non-woven fabrics supporting layer,
Available ultra-thin, fine and close selection layer, it is possible to reduce ethyl alcohol is by time of film, therefore than traditional symmetrical poly- diformazan
Radical siloxane film has higher ethyl alcohol flux.In addition to this, the problem of inorganic particulate is reunited in the polymer produces film properties
Raw very big influence.ZIF-8@GO hybrid material is selected as filler material, and the collaboration for being mainly due to ZIF-8@GO hybrid material is made
With GO can provide the dispersibility in dimethyl silicone polymer to ZIF-8, while ZIF-8 provides hydrophobicity to GO.It therefore can
To solve the agglomeration traits of conventional inorganic particles in the polymer.In short, ZIF-8@GO is introduced into PDMS matrix
In, available ultra-thin, high ethano flux, high ethano/water separation factor dimethyl silicone polymer composite membrane.
Detailed description of the invention
Fig. 1 is comparative example 1, embodiment 5, embodiment 3, embodiment 6 and 7 composite membrane FTIR of embodiment figure.
Fig. 2 (a), Fig. 2 (b), Fig. 2 (c), Fig. 2 (d), Fig. 2 (e), Fig. 2 (f) and Fig. 2 (g) are comparative example 1, comparative example respectively
2, comparative example 3, embodiment 5, embodiment 3, embodiment 6, in embodiment 7 film obtained SEM exterior view；Fig. 2 (h), Fig. 2
(i), Fig. 2 (j), Fig. 2 (k) and Fig. 2 (l) are comparative example 1 respectively, embodiment 5, embodiment 3, embodiment 6, are made in embodiment 7
Film SEM sectional view.
Fig. 3 is comparative example 1, comparative example 2, comparative example 3 and embodiment 1-4 composite membrane infiltration evaporation test result.
Fig. 4 is comparative example 1 and embodiment 5,7 composite membrane infiltration evaporation test result of embodiment 3, embodiment 6 and embodiment.
Fig. 5 is influence of the test temperature to the infiltration evaporation test result of 6 composite membrane of embodiment.
Fig. 6 is influence of the feed concentration to the infiltration evaporation test result of 6 composite membrane of embodiment.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The used solution blended process of the present invention, can by adjusting GO in ZIF-8@GO hybrid material content and ZIF-
Content of the 8@GO hybrid materials in dimethyl silicone polymer, optimizes the microcosmic of the dimethyl silicone polymer composite membrane being prepared
Pattern and hydrophilic and hydrophobic reach the regulation to membrane separating property so that modified caudacoria have higher ethanol/water separate because
Sub and excellent ethyl alcohol flux.The GO of ZIF-8@GO hybrid material is selected from the one or more of 1 μm of -5 μm of lamella size.It is making
When standby ZIF-8@GO hybrid material, it is 20mg-50mg that GO, which adds quality, and ZIF-8 production quantity is 0.28g, has obtained different GO and has contained
The ZIF-8@GO hybrid material of amount.The specific preparation process of ZIF-8@GO hybrid material, it is molten to be added to 2-methylimidazole for GO solution
In liquid, zinc nitrate hexahydrate solution is then added at once, stirs 1h at room temperature, finally centrifugation obtains ZIF-8@GO hybrid material.
Reaction solution is selected from one of secondary water, anhydrous methanol, dehydrated alcohol, tetrahydrofuran or a variety of, and the quality of reaction solution is dense
Degree is 0.01wt%-0.5wt%.The size of GO lamella can divide ZIF-8@GO hybrid material in PDMS matrix
Scattered property can have a certain impact, and GO lamella is excessive, be not easy in PDMS matrix evenly dispersed；GO lamella is too
Small, the ZIF-8 of carrying is very few, is easy to reunite.ZIF-8 content on the surface GO also can be to ZIF-8@GO hybrid material in poly- diformazan
Dispersibility can have a certain impact in radical siloxane matrix, and GO content is very few, compare relative to the ZIF-8 carried on GO lamella
It is more, cause ZIF-8 to reunite on GO lamella；It is more loose to will lead to the ratio that ZIF-8 is arranged in GO for GO too high levels.ZIF-8@GO
Additive amount of the hybrid material in PDMS matrix is 0.1wt%-2wt%.Additive amount is different, not only will affect
Dispersibility of the ZIF-8 GO hybrid material in PDMS matrix, and influence whether that dimethyl silicone polymer is multiple
Film is closed to the separating property of ethyl alcohol.
Polymer/non-woven fabrics supporting layer is microfiltration membranes or ultrafiltration membrane, when preparation, will form the polymer solution blade coating of film
On non-woven fabrics, the method then mutually converted prepares porous supporting layer, and the mass concentration of polymer solution is 10wt%-
20wt%.Conversion liquid when polymer/non-woven fabrics supporting layer is mutually converted is selected to secondary water, tannic acid coagulating bath, hydroxide
One of sodium water solution, dehydrated alcohol and anhydrous methanol are a variety of.
The following are specific embodiments
Comparative example 1
The polymer of the composite membrane of comparative example/non-woven fabrics supporting layer is Kynoar/non-woven fabrics microfiltration membranes.The composite membrane
Preparation process include following step:
(1) the dimethyl silicone polymer tetrahydrofuran solution that mass fraction is 20wt% is prepared, the case where being stirred at room temperature
Under make it completely dissolved, obtain uniform dimethyl silicone polymer solution.
(2) crosslinking agent and catalyst are added to dimethyl silicone polymer solution, dimethyl silicone polymer: crosslinking agent: urged
Agent mass ratio 50:8:1, is stirred at room temperature, is increased to solution viscosity, is scratched Kynoar/non-woven fabrics microfiltration membranes
Upper carry out film-forming.The crosslinking agent is phenyl triethoxysilane, ethyl orthosilicate, methyltriethoxysilane, hydrogeneous
It is one or more in silicone oil or vinyltriethoxysilane.The catalyst be chloroplatinic acid, dibutyl tin dilaurate or 1,
It is one or more in 3- divinyl -1,1,3,3- tetramethyl disiloxane platinum (0).
Comparative example 2
(1) ZIF-8 and dimethyl silicone polymer tetrahydrofuran mixed solution that mass fraction is 20wt% are prepared, first will
The ZIF-8 of 0.005g is added in 4.5ml tetrahydrofuran solution, and ultrasonic agitation 12h makes it be uniformly dispersed, and is then added
0.995g dimethyl silicone polymer continues that 12h is stirred by ultrasonic, so that it is obtained uniform mixed solution, ZIF-8 in the mixed solution
Quality account for dimethyl silicone polymer quality 0.5wt%.
(2) crosslinking agent and catalyst are added to ZIF-8 and dimethyl silicone polymer tetrahydrofuran mixed solution, poly- diformazan
Radical siloxane: crosslinking agent: catalyst quality ratio 50:8:1 is stirred at room temperature, is increased to solution viscosity, is scratched and gather inclined fluorine
Film-forming is carried out in ethylene/non-woven fabrics microfiltration membranes.The crosslinking agent is phenyl triethoxysilane, ethyl orthosilicate, methyl
It is one or more in triethoxysilane, containing hydrogen silicone oil or vinyltriethoxysilane.The catalyst is chloroplatinic acid, February
It is one or more in dilaurylate or 1,3- divinyl -1,1,3,3- tetramethyl disiloxane platinum (0).
Comparative example 3
(1) GO and dimethyl silicone polymer tetrahydrofuran mixed solution that mass fraction is 20wt% are prepared, first will
The GO of 0.005g is added in 4.5ml tetrahydrofuran solution, and ultrasonic agitation 12h makes it be uniformly dispersed, and it is poly- that 0.995g is then added
Dimethyl siloxane continues that 12h is stirred by ultrasonic, so that it is obtained uniform mixed solution, the quality of GO accounts for poly- in the mixed solution
The 0.5wt% of the quality of dimethyl siloxane.
(2) crosslinking agent and catalyst are added to GO and dimethyl silicone polymer tetrahydrofuran mixed solution, poly dimethyl
Siloxanes: crosslinking agent: catalyst quality ratio 50:8:1 is stirred at room temperature, is increased to solution viscosity, is scratched polyvinylidene fluoride
Film-forming is carried out in alkene/non-woven fabrics microfiltration membranes.The crosslinking agent is phenyl triethoxysilane, ethyl orthosilicate, methyl three
It is one or more in Ethoxysilane, containing hydrogen silicone oil or vinyltriethoxysilane.The catalyst is chloroplatinic acid, two laurels
It is one or more in sour dibutyl tin or 1,3- divinyl -1,1,3,3- tetramethyl disiloxane platinum (0).
Embodiment 1
(1) ZIF-8@GO and dimethyl silicone polymer tetrahydrofuran mixed solution, ZIF-8@in the mixed solution are prepared
The mass fraction of GO and dimethyl silicone polymer is 20wt%, first that the ZIF-8@GO of the content of GO containing 20mg of 0.005g is miscellaneous
Change material to be added in 4.5ml tetrahydrofuran solution, ultrasonic agitation 12h makes it be uniformly dispersed, and the poly- diformazan of 0.995g is then added
Radical siloxane continues that 12h is stirred by ultrasonic, so that it is obtained uniform mixed solution, the quality of ZIF-8@GO accounts for polydimethylsiloxanes
The 0.5wt% of the quality of alkane.
(2) crosslinking agent and catalyst are added to ZIF-8@GO and dimethyl silicone polymer tetrahydrofuran mixed solution, gathered
Dimethyl siloxane: crosslinking agent: catalyst quality ratio 50:8:1 is stirred at room temperature, is increased to solution viscosity, is scratched poly-
Film-forming is carried out in vinylidene/non-woven fabrics microfiltration membranes.The crosslinking agent be phenyl triethoxysilane, ethyl orthosilicate,
It is one or more in methyltriethoxysilane, containing hydrogen silicone oil or vinyltriethoxysilane.The catalyst be chloroplatinic acid,
It is one or more in dibutyl tin dilaurate or 1,3- divinyl -1,1,3,3- tetramethyl disiloxane platinum (0).
Embodiment 2
With embodiment 1, difference is experimental implementation, and in step (1), the content of GO is 30mg in ZIF-8@GO.
Embodiment 3
With embodiment 1, difference is experimental implementation, and in step (1), the content of GO is 40mg in ZIF-8@GO.
Embodiment 4
With embodiment 1, difference is experimental implementation, and in step (1), the content of GO is 50mg in ZIF-8@GO.
Embodiment 5
With embodiment 3, difference is experimental implementation, and in step (1), the quality of ZIF-8@GO accounts for dimethyl silicone polymer
Quality 0.25wt%.
Embodiment 6
With embodiment 3, difference is experimental implementation, and in step (1), the quality of ZIF-8@GO accounts for dimethyl silicone polymer
Quality 0.75wt%.
Embodiment 7
With embodiment 3, difference is experimental implementation, and in step (1), the quality of ZIF-8@GO accounts for dimethyl silicone polymer
Quality 1.0wt%.
The following are analysis of experimental results
Table 1 is comparative example 1, comparative example 2, comparative example 3, embodiment 3,7 composite membrane of embodiment 5, embodiment 6 and embodiment
Contact angular data.It is compared to comparative example 1, reduction slightly occurs in the water contact angle value of comparative example 3, due to the surface GO
There are hydrophilic oxygen-containing functional groups.It is compared to comparative example 1, with the increase of ZIF-8@GO loading, embodiment 5, embodiment
3, the water contact angle value of embodiment 6 and embodiment 7 gradually increases, and illustrates hydrophobic enhancing.It is compared to comparative example 1, it is right
Increasing occur in the ethyl alcohol contact angle values of ratio 3, and illustrate the performance enhancement for dredging alcohol.It is compared to comparative example 1, with ZIF-8@
The increase of GO loading, embodiment 5, embodiment 3, the ethyl alcohol contact angle values of embodiment 6 and embodiment 7 are gradually reduced, illustrate
Close alcohol enhancing, is conducive to passing through for ethyl alcohol.
Table 1
Fig. 1 shows that comparative example 1, embodiment 5, embodiment 3, embodiment 6 and 7 composite membrane FTIR of embodiment figure, right figure are
FTIR partial enlarged view.As can be seen that 1340cm from partial enlarged view-1The characteristic peak at place belongs on ZIF-8@GO phenyl ring
C-H stretching vibration peak.It is compared to comparative example 1, with the increase of ZIF-8@GO loading, 1340cm-1Peak intensity gradually increase
By force, illustrate that ZIF-8@GO is successfully filled into PDMS matrix, to be successfully prepared poly dimethyl
Siloxanes composite membrane.
Fig. 2 (a), Fig. 2 (b), Fig. 2 (c), Fig. 2 (d), Fig. 2 (e), Fig. 2 (f) and Fig. 2 (g) are comparative example 1, comparative example respectively
2, comparative example 3, embodiment 5, embodiment 3, embodiment 6, in embodiment 7 film obtained SEM exterior view；Fig. 2 (h), Fig. 2
(i), Fig. 2 (j), Fig. 2 (k) and Fig. 2 (l) are comparative example 1 respectively, embodiment 5, embodiment 3, embodiment 6, are made in embodiment 7
Film SEM sectional view.As Fig. 2 (a) and Fig. 2 (c) it is found that the surface of film made from comparative example 1 and comparative example 3 is almost without change
Change, illustrates that the introducing of GO has not been changed surface topography, there is good compatibility.By Fig. 2 (a) and Fig. 2 (b) it is found that being compared to
Film obtained in comparative example 1, there is the particle of some reunions in the surface of film obtained in comparative example 2, illustrates ZIF-8
There is agglomeration in the introducing of son.Fig. 2 (a) and Fig. 2 (e) are it is found that in contrast to comparative example 1, composite membrane obtained in embodiment 3
Surface particle disperses more evenly, to illustrate to make ZIF-8 have preferably dispersibility and compatibility using GO as carrier.In contrast to right
Ratio, with the increase of ZIF-8@GO loading, by Fig. 2 (d), Fig. 2 (e), Fig. 2 (f) and Fig. 2 (g) it is found that embodiment 5, implementation
The surface particle of composite membrane obtained gradually increases in example 3, embodiment 6 and embodiment 7, and is uniformly dispersed, until loading
Reach 1wt% and agglomeration just occur, illustrates the dispersibility for improving ZIF-8 using GO as carrier.By Fig. 2 (h), Fig. 2 (i),
Fig. 2 (j), Fig. 2 (k) and Fig. 2 (l) are it is found that be filled with the dimethyl silicone polymer selection layer surface table of ZIF-8@GO hybrid material
Reveal smoother, illustrates to have between ZIF-8@GO hybrid material and dimethyl silicone polymer good dispersed and compatible
Property.Furthermore it is also possible to learn, comparative example 1, embodiment 5, embodiment 3, embodiment 6, in embodiment 7 film obtained thickness point
Wei not be 11.6 μm, 10.75 μm, 9.7 μm, 10.2 μm and 8.5 μm, about 8 μm -12 μm of thickness of layer are selected, illustrate selection layer
Thinner thickness.
Fig. 3 shows comparative example 1, comparative example 2, comparative example 3 and embodiment 1-4 composite membrane infiltration evaporation test result.From
As can be seen that being compared to comparative example 1 in figure, all there is downward trend, this phenomenon in the flux and separation factor of comparative example 3
It is mainly due to the introducing of GO, GO lamellar structure hinders passing through for feed liquid, to reduce flux；The surface GO is contained greatly simultaneously
The oxygen-containing function functional group of amount, increases hydrophily, therefore reduce separation factor.It is compared to comparative example 1, embodiment 1-4
Flux there is increased trend after first reducing, reduction trend is attributed to the introducing of GO lamella, hinders passing through for feed liquid.With
From embodiment 1 to embodiment 4, GO content is gradually increased, therefore has gone out first the reduced trend of flux.Increase trend may attribution
In the thinner thickness of the film of embodiment 4.It is compared to comparative example 1, first increasing occurs in the separation factor of embodiment 1-4 to be reduced afterwards
Trend, increased trend be attributed to using GO as carrier make ZIF-8 dispersibility improve, to improve the separation of ethanol/water
The factor；It is less that reduced trend is attributed to the ZIF-8 amount on the surface GO, is not enough to improve the hydrophobicity of GO, so as to cause second
Alcohol/water separation factor downward trend.As seen from Figure 3, the ethanol/water separation factor of embodiment 3 is maximum, reaches
13.7。
Fig. 4 is comparative example 1 and embodiment 5,7 composite membrane infiltration evaporation test result of embodiment 3, embodiment 6 and embodiment.
Be compared to comparative example 1, embodiment with ZIF-8@GO content increase, it can be seen that flux increased trend after first reducing,
It is mainly due to the increase of ZIF-8@GO content, increases along with GO content, to hinder passing through for feed liquid, results in flux
Reduction；But increasing occurs again in the flux of embodiment 7, the reason is that the thinner thickness of the composite membrane of embodiment 7.It simultaneously can also be with
As can be seen from Figure 4, it is compared to comparative example 1, with the increase of ZIF-8@GO content, ethanol/water separation factor embodiment occurs
Downward trend after first increasing, is mainly due to the increase of ZIF-8@GO content, along with the increase of ZIF-8 content, to increase
Add hydrophobic nanochannel, improves the separation factor of ethanol/water；But the separation factor of the ethanol/water of embodiment 7 occurs
Due to ZIF-8@GO content is too high there is the phenomenon that reunion in PDMS matrix in downward trend.By
Fig. 4 can be seen that the separation factor highest of the ethanol/water of embodiment 6, reach 22.1, compared with comparative example 1, improve
287.7%.
Fig. 5 is influence of the test temperature to the infiltration evaporation test result of 6 composite membrane of embodiment.By Fig. 5 it is found that with
The increase of test temperature, flux gradually increase, and are mainly due to both sides reason: (1) with the increase of test temperature, gathering
The movement of dimethyl siloxane segment is more flexible, is conducive to passing through for feed liquid.(2) with the increase of test temperature, feed liquid point
The movement of son is accelerated, and is conducive to feed liquid molecule and passes through dimethyl silicone polymer composite membrane.With the increase of test temperature, ethyl alcohol/
The separation factor of water gradually decreases, due to ethyl alcohol is higher than activation energy of the water by composite membrane by the activation energy of composite membrane.Through
Optimization of the test temperature to embodiment 6 is crossed, 40 DEG C of discovery is optimal test temperature.
Fig. 6 is influence of the feed concentration to the infiltration evaporation test result of 6 composite membrane of embodiment.It can be seen from Fig. 6
With the increase of concentration of alcohol in feed liquid, total flux shows the trend gradually increased, is mainly due to the introducing of ZIF-8@GO,
Improve the flux of ethyl alcohol；With the increase of concentration of alcohol in feed liquid, ethanol/water separation factor shows becoming of being gradually reduced
Gesture, is mainly due to that concentration of alcohol is lower, when separation respond it is faster, therefore in feed liquid concentration of alcohol it is lower show separation because
Son is higher.From Fig. 6 it can also be seen that when concentration of alcohol is 2.5wt%, the separation factor highest of ethanol/water is 23.1.
Above-mentioned test is carried out to remaining embodiment, also can get similar result.
By the above test result it is found that the present invention is not necessarily to other modified methods, directly pass through simple solution blended process, system
It is standby to have obtained a kind of high performance composite membrane, greatly simplifie filming technology.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of dimethyl silicone polymer composite membrane, which is characterized in that the dimethyl silicone polymer composite membrane contains mixed base
Matter layer, the mixed-matrix layer is the film formed after the dimethyl silicone polymer of doping porous hybrid material solidifies, described porous
Hybrid material is the hybrid material of metal-organic framework material with the carbon material for being modified with carboxyl, the metal-organic framework material
It is connect with the carbon material for being modified with carboxyl by hydrogen bond.
2. dimethyl silicone polymer composite membrane as described in claim 1, which is characterized in that the dimethyl silicone polymer is compound
Film also contains supporting layer, any surface of the mixed-matrix layer blade coating in the supporting layer；The supporting layer is polymer film,
Perhaps the supporting layer is non-woven fabrics or the supporting layer is the non-woven fabrics for having scratched polymer film；The mixed-matrix layer
With a thickness of 8 μm -12 μm.
3. dimethyl silicone polymer composite membrane as described in claim 1, which is characterized in that the metal-organic framework material is
ZIF-8, MOF-5, ZIF-67, MIL-53 or HKUST-1；The carbon material for being modified with carboxyl is graphene oxide, modification carboxylic
The carbon nanotube of base, the carbon nano-fiber for modifying carboxyl or the Nano carbon balls for modifying carboxyl；The dimethyl silicone polymer is hydroxyl
In the dimethyl silicone polymer of dimethyl silicone polymer, amino-terminated dimethyl silicone polymer and ethenyl blocking that base blocks
At least one；The number-average molecular weight of the dimethyl silicone polymer is 20000-500000.
4. dimethyl silicone polymer composite membrane as claimed in claim 2, which is characterized in that the polymer film is polyacrylonitrile
Film, poly (ether sulfone) film, PS membrane, polyimide film, PA membrane, polyetherimde films, polyamidoimide film, cellulose acetate
Film, three cellulose acetate membrane or polyvinylidene fluoride film.
5. the preparation method of dimethyl silicone polymer composite membrane described in claim 1 or 3, which is characterized in that by porous hybrid
Material is dispersed in boiling point less than or equal in the organic solvent of toluene, and dimethyl silicone polymer is then added, obtains porous
The mixed solution of hybrid material and dimethyl silicone polymer；It is molten to the mixing of the porous hybrid material and dimethyl silicone polymer again
Catalyst and crosslinking agent are added in liquid, the dimethyl silicone polymer is made to crosslink reaction；To the mixed solution due to poly-
The crosslinking of dimethyl siloxane and be transformed into it is thick after gradually solidify to get to the dimethyl silicone polymer composite membrane；
The porous hybrid material is the hybrid material of metal-organic framework material with the carbon material for being modified with carboxyl, the metal
Organic framework materials are connect with the carbon material for being modified with carboxyl by hydrogen bond.
6. the preparation method of dimethyl silicone polymer composite membrane as claimed in claim 5, which is characterized in that the mixed solution
Due to dimethyl silicone polymer crosslinking and be transformed into it is thick after, blade coating obtains poly dimethyl silicon to supporting layer after solidification
Oxygen alkane composite membrane；
The supporting layer is that perhaps the supporting layer is non-woven fabrics to polymer film or the supporting layer is to have scratched polymer
The non-woven fabrics of film.
7. the preparation method of dimethyl silicone polymer composite membrane as claimed in claim 5, which is characterized in that the porous hybrid
The quality of material is the 0.1%-2% of the quality of the dimethyl silicone polymer；The porous hybrid material and poly dimethyl silicon
The quality sum of oxygen alkane accounts for the 15%-20% of mixed solution quality；The organic solvent be n-hexane, normal heptane, tetrahydrofuran,
Hexamethylene or toluene.
8. the preparation method of dimethyl silicone polymer composite membrane as claimed in claim 5, which is characterized in that the mixed solution
Due to dimethyl silicone polymer crosslinking and be transformed into it is thick after, viscous liquid is heated, viscous liquid is consolidated
Change to get the dimethyl silicone polymer composite membrane is arrived；The temperature of the heating is 30 DEG C -80 DEG C, and the time of heating is 8h-
14h。
9. the preparation method of dimethyl silicone polymer composite membrane as claimed in claim 6, which is characterized in that the blade coating to branch
It further include the process of heating after supportting layer；The temperature of the heating is 30 DEG C -80 DEG C, and the time of heating is 8h-14h；It is described to scrape
Applied the non-woven fabrics of polymer film the preparation method comprises the following steps: the polymer solution that will form film scratches on non-woven fabrics, passes through phase
The method of conversion makes the polymer solution form polymer film, the non-woven fabrics for having scratched polymer film is prepared；
Preferably, what the phase was converted converts liquid as deionized water, tannic acid coagulating bath, sodium hydrate aqueous solution, anhydrous second
Alcohol or anhydrous methanol.
10. any dimethyl silicone polymer composite membrane of claim 1-4 is used for mixed after miscible with water from organic solvent
The application of Separation of Organic in bonding solvent；
Preferably, the organic solvent is ethyl alcohol, methanol, isopropanol or butanol；Preferably, the isolated temperature be 40 DEG C-
70℃；
Preferably, the mass concentration of the in the mixed solvent organic solvent is 2.5wt%-10wt%.
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