CN106731886A - A kind of preparation method of composite mesoporous film - Google Patents
A kind of preparation method of composite mesoporous film Download PDFInfo
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- CN106731886A CN106731886A CN201611226194.2A CN201611226194A CN106731886A CN 106731886 A CN106731886 A CN 106731886A CN 201611226194 A CN201611226194 A CN 201611226194A CN 106731886 A CN106731886 A CN 106731886A
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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
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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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- B01J2220/00—Aspects relating to sorbent materials
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- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B01J2220/00—Aspects relating to sorbent materials
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- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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Abstract
The invention provides a kind of preparation method of composite mesoporous film, including：Precursor compound and structure directing agent are carried out into alcoholysis reaction in ethanol, colloidal sol is obtained；Perforated membrane is surface-treated, is soaked in colloidal sol；By the perforated membrane after immersion in being dried under room temperature condition and completing collosol and gel process, then clean, dry, obtain composite mesoporous film.The present invention makes the mesopore size continuously adjustabe of the composite mesoporous film of preparation with PEO PPOX PEO triblock copolymer or cetyl trimethylammonium bromide or lauryl sodium sulfate as structure directing agent.Composite mesoporous film prepared by the present invention has unique meso-hole structure, the composite membrane is because of its organic solvent resistance and special pore structure, or further can modify mesoporous, can be applied to the separating-purifying such as size selectivity ion-transfer and ultrafiltration field in the transfer of selective molecule and the separation, liquid/liquid interface in solution, preparation process is simple, it is environment-friendly.
Description
Technical field
The present invention relates to field of material technology, more particularly to a kind of preparation method of composite mesoporous film.
Background technology
The flexible polymer perforated membrane of various the Nomenclature Composition and Structure of Complexes by many decades development, forming processing technology is suitable
It is ripe.If polypropylene porous film is that there is the polypropylene screen of similar rubber elasticity to be stretched to be made to a certain degree after thermal finalization
, with many applications.Because the film is porous, specific surface area is greatly increased, and it can provide the interior of the effect of reacting to each other
Portion's surface area reaches 20m2/g.Can also according to design object the need for dexterously connect various functions group, original polymer is dredged
It is aqueous to be changed into hydrophily, and match in terms of coordination, compatibility and chelating with filtering medium, assigned in physics and electrochemical conditions change
To absorption and the reversible process of dissociation filtering medium, protein separating purifying can be used for and purified from microculture body and plant
With extraction bacterium and simple substance antibody, the powerful measure as biochemistry and biological medicine technology.In terms of medicine equipment, such as people
Work Rend dialysis instrument, plasmafilter, artificial lung membrane oxygenator and electrocardiograph etc. have its unique effect.In various industrial wastewaters
Treatment, such as water-oil separating, recovery of weak aqua ammonia etc. are also widely used.Therefore, good toughness and be that chemically inert polypropylene is more
Pore membrane, there is very big commercial value.But the disadvantage that above-mentioned similar polymer porous film is present is pore-size distribution wide, intensity
Small, hydrophily is poor, and can not bear larger action of mechanical pressure.
And simple inorganic mesoporous material is because of its single pore-size distribution, specific surface area and porosity high, controllable hole
Size/structure, adjustable skeleton and hole surface chemical property, in catalytic chemistry, bio-molecular separation, water process and sensor etc.
Numerous areas have applications well prospect.But, it is poor pliability using one of problem present in process, and generally mesoporous film
It is supported on solid matrix surface, it is suppressed that duct transports performance.“Self-assembly of a silica–surfactant
Nanocomposite in a porous alumina membrane " are reported to be prepared as template with anodic porous alumina and are situated between
The method of hole composite membrane, document illustrate it is a kind of assembled in multiaperture pellumina one-dimensional mesoporous silica bar prepare it is inorganic multiple
The method for closing mesoporous film.This film shows the channel morphology of uniqueness, has in terms of the separation of molecule to nanoscale and greatly should very much
Use potentiality.However, this composite membrane is also hard and frangible, it is not easy to be processed into appropriate component carry out unit operation.
And the high cost of raw material multiaperture pellumina that this inorganic compound mesoporous film is used, easily divide under acid or alkaline environment
, after the inorganic compound mesoporous film of preparation is by roasting removing surfactant, easily there is the contraction of mesoporous material in film in solution
The problem for causing meso-hole structure to cave in fragmentation, therefore have significant limitation in actual applications.So, synthesis is easy to actual
The flexible compound mesoporous film of operation has great significance.Solution to this problem is exactly to select a kind of toughness porous film,
Inorganic mesoporous material is formed in fenestra, flexible meso-hole structure composite film material is prepared.
The B of patent CN 102395420 disclose a kind of porous compound film for liquid filter member, including overlie
Polymeric nanofiber layer on micro- porous membrane, micro- porous membrane has the size grades less than 0.1 micron.It is multiple with this
The pressure drop for closing membrane filtration component is substantially the same or smaller with the pressure drop of micro- porous membrane, and exists in surfactant
Under, the particle of the filter element remains larger than the particle reservation of only described micro- porous membrane under the conditions of same test.The party
Composite membrane prepared by method is straight polymer system, could not still solve the problems, such as that heat-resisting and mechanical strength is relatively low.
The B of patent CN 102228808 disclose a kind of polyethylene terephthalate compound mesoporous film and its preparation side
Method and apply.Assembly mesoporous materials silicon dioxide in polyethylene terephthalate film, forms compound mesoporous film.It is prepared
Method is that inorganic mesoporous material is assembled in the hole in polyethylene terephthalate film using the method for suction filtration mainly
Compound mesoporous film is obtained, the surfactant for recycling the mode of extraction wash-out to remove in the composite membrane intermediary Porous materials, so that
Obtain polyethylene terephthalate compound mesoporous film.The method there are certain requirements to the selection tool of matrix membrane material, such as right
The polymer porous film poor with water logging lubricant nature carries out compound tense, and mesoporous silicon oxide cannot form the boundary of stabilization with polymer
Face acts on, and there is clear gap between silica and polymer, and under external force, silica easily comes off, and institute is in this way
It is not applied for the preparation of universal polymer porous film group compound film.
The content of the invention
Present invention solves the technical problem that be that a kind of preparation method of composite mesoporous film is provided, process is simple, preparation
The mesopore size continuously adjustabe of composite mesoporous film.
In view of this, the invention provides a kind of preparation method of composite mesoporous film, comprise the following steps：Make in catalyst
Under, precursor compound and structure directing agent are carried out into alcoholysis reaction in ethanol, obtain colloidal sol, the precursor compound
Selected from one or more in silicon source compound, titanium source compound, zinc source compound, tin source compound and niobium source compound, institute
State structure directing agent and be selected from PEO-PPOX-PEO triblock copolymer, cetyl trimethyl bromine
Change one or more in ammonium and lauryl sodium sulfate；Perforated membrane is surface-treated, then 2 is soaked in the colloidal sol
~24 hours；By the perforated membrane after immersion in being dried under room temperature condition and completing sol gel process, then clean, dry,
Obtain composite mesoporous film.
Preferably, the precursor compound be selected from tetraethyl orthosilicate, titanium tetrachloride, tetrabutyl titanate, isopropyl titanate,
One or more in dibutyl phthalate, stannic acid ester and niobates.
Preferably, the catalyst is HCl, HNO3、H2SO4Or ammoniacal liquor.
Preferably, the ratio of the precursor compound, structure directing agent, ethanol and catalyst is (1~10) mL：(0.3
~2.0) g：(10~30) mL：(0.5~3.0) g.
Preferably, the temperature of alcoholysis reaction is 20~80 DEG C, and the time is 2~12 hours.
Preferably, the perforated membrane is polypropylene porous film, polyethylene porous membrane, polyimide porous membrane or makrolon
Perforated membrane.
Preferably, the mode of the surface treatment is that oxygen plasma is processed or surface chemical modification treatment.
Preferably, the perforated membrane after immersion is 12~48 hours in the time dried under room temperature condition.
Preferably, the cleaning uses the mixing cleaning solution of second alcohol and water, and scavenging period is 0.5~2 hour, and mixing is clear
The temperature of dilution is 40~50 DEG C.
Preferably, dry temperature is 30~40 DEG C, and the dry time is 0.5~2 hour.
The invention provides a kind of preparation method of composite mesoporous film, comprise the following steps：Under catalyst action, will be preceding
Drive body compound and structure directing agent carries out alcoholysis reaction in ethanol, obtains colloidal sol；Perforated membrane is surface-treated, then
Soaked 2~24 hours in the colloidal sol；By the perforated membrane after immersion in being dried under room temperature condition and complete sol gel mistake
Journey, then cleans, and dries, and obtains composite mesoporous film.Compared with prior art, the present invention with PEO-PPOX-
One or more in PEO triblock copolymer or cetyl trimethylammonium bromide and lauryl sodium sulfate are
Structure directing agent, makes the mesopore size continuously adjustabe of the composite mesoporous film of preparation.Composite mesoporous film prepared by the present invention has only
Special meso-hole structure, the composite membrane is because of its organic solvent resistance and special pore structure, or further can modify mesoporous,
Can be applied to size selectivity ion-transfer and ultrafiltration decile in the transfer of selective molecule and the separation, liquid/liquid interface in solution
From purification field, its preparation process is simple is environment-friendly.
Brief description of the drawings
Fig. 1 is flexible compound mesoporous film surface SEM figures prepared by embodiment 1；
Fig. 2 is the nitrogen absorption under low temperature thermoisopleth of flexible compound mesoporous film prepared by embodiment 1；
Fig. 3 is the pore size distribution curve of flexible compound mesoporous film prepared by embodiment 1；
Fig. 4 is flexible compound mesoporous film surface SEM figures prepared by embodiment 2；
Fig. 5 is flexible compound mesoporous film surface SEM figures prepared by embodiment 3；
Fig. 6 is the pore structure TEM figures of flexible compound mesoporous film inside mesopore silicon oxide prepared by embodiment 3；
Fig. 7 is flexible compound mesoporous film surface SEM figures prepared by embodiment 4；
Fig. 8 is flexible compound mesoporous film surface SEM figures prepared by embodiment 5；
Fig. 9 is flexible compound mesoporous film surface SEM figures prepared by embodiment 6；
Figure 10 is the nitrogen absorption under low temperature thermoisopleth of flexible compound mesoporous film prepared by embodiment 7；
Figure 11 is the pore size distribution curve of flexible compound mesoporous film prepared by embodiment 7.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of preparation method of composite mesoporous film, comprise the following steps：In catalyst action
Under, precursor compound and structure directing agent are carried out into alcoholysis reaction in ethanol, obtain colloidal sol, the precursor compound choosing
One or more from silicon source compound, titanium source compound, zinc source compound, tin source compound and niobium source compound, it is described
Structure directing agent is selected from PEO-PPOX-PEO triblock copolymer, cetyl trimethyl bromination
One or more in ammonium and lauryl sodium sulfate；Perforated membrane is surface-treated, then in the colloidal sol immersion 2~
24 hours；By the perforated membrane after immersion in being dried under room temperature condition and completing sol gel process, then clean, dry, obtain
To composite mesoporous film.
In sol preparation step, the catalyst is preferably acid or alkali, more preferably HCl, HNO3、H2SO4Or ammoniacal liquor.
Wherein, HCl, HNO3、H2SO4Concentration be preferably 0.1~0.3M；The NH of the ammoniacal liquor3Content is preferably 30%.
Preferably, the precursor compound is selected from one or more in the salt of following elements and ester：Si、Ti、
Zn, Sn and Nb；It is furthermore preferred that being selected from tetraethyl orthosilicate, titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, phthalic acid two
One or more in zinc ester, stannic acid ester and niobates.
In the structure directing agent that the present invention is used, the PEO-PPOX-PEO three block is total to
Polymers includes but is not limited to F127 or P123.F127 (EO106PO70EO106) weight average molecular weight is preferably 8000~
15000g/mol, more preferably 11500g/mol；P123 (EO20PO70EO20) weight average molecular weight is preferably 4000~8000g/
Mol, more preferably 5800g/mol.Realize continuous tune in the aperture of mesopore oxide of the present invention by structure directing agent to preparing
Section.
The F127 and P123 are the both sexes triblock polymer that ethyoxyl and propoxyl group are formed, but block composition is not
Together.The molecular formula of P123 is EO20PO70EO20, the molecular formula of F127 is EO106PO70EO106, wherein EO represents ethyoxyl, PO tables
Show propoxyl group.As both sexes triblock polymer, F127 and P123 added in water it is a certain amount of after can form micella.Due to
The hydrophily of EO blocks is better than PO blocks, so forming micella in water with PO as kernel, EO is shell.
The amount ratio of the precursor compound, structure directing agent, ethanol and catalyst is preferably (1~10) mL：(0.3
~2.0) g：(10~30) mL：(0.5~3.0) g.The temperature of alcoholysis reaction is preferably 20~80 DEG C, more preferably 60 DEG C；Time
Preferably 2~12 hours.
Preferably, the perforated membrane is polypropylene porous film, polyethylene porous membrane, polyimide porous membrane or poly-
Carbonic ester perforated membrane.The thickness of the perforated membrane is preferably 5 μm~60 μm；The diameter in hole is preferably 10nm~500nm；Porosity
Preferably 20~60%.
The mode of the surface treatment is preferably oxygen plasma treatment or surface chemical modification treatment.The oxygen plasma
In body treatment, power is preferably 10~30W, and the time is preferably 10~120 seconds；It is used to change in the surface chemical modification treatment
Property agent be selected from vinyltrimethoxy silane, methacryloxypropyl trimethoxy silane and VTES
In at least one, modification time is preferably 2~12 hours, and temperature is preferably 40~90 DEG C；Or modifying agent is preferably dopamine,
Modified environment is Tris (Hydroxymethyl) aminomethane buffer solutions, and temperature is preferably room temperature, and the time is preferably 0.5
~2 hours.
Preferably, the perforated membrane after immersion is preferably 12~48 hours in the time dried under room temperature condition.Institute
Mixing cleaning solution of the cleaning using second alcohol and water is stated, the volume content of ethanol is preferably 30%~70%, and scavenging period is preferred
It it is 0.5~2 hour, the temperature for mixing cleaning solution is preferably 40~50 DEG C.The dry temperature is preferably 30~40 DEG C, does
The dry time is preferably 0.5~2 hour.
From above scheme as can be seen that the present invention is with apertured polymeric film as base material, with hydrolyzable compound as presoma,
With block copolymer or surfactant as structure directing agent.Apertured polymeric film hole surface is carried out into surface modified, immersion
In the precursor sol after alcoholysis reaction, then mesoporous oxygen is combined inside polymer porous film through sol gel process
Compound etc., it is flexible compound mesoporous film to obtain mesopore oxide@porous composite polymer electrolyte membranes after structure directing agent is removed.It is made
Standby composite membrane has unique meso-hole structure, and the composite membrane is because of its organic solvent resistance and special pore structure, or can enter one
Step is modified mesoporous, can be applied to the selective molecule transfer in solution and separate, on liquid/liquid interface size selectivity from
The separating-purifying field such as son transfer and ultrafiltration, its preparation process is simple is environment-friendly.Test result indicate that, prepared by the present invention
The thickness of flexible compound mesoporous film is 5 μm to 60 μm, and mesopore size scope is that 2nm to 10nm is adjustable, and porosity is 2~20%.
With polymer porous film be combined inorganic matter by the present invention, prepares flexible mesopore oxide@porous polymers and is combined
Film, compound membrane aperture reaches height nanosizing in the lump, improves polymer film performance, while some new features are obtained, it is such as good
Transparency, wetability and strong permeability, or surface modification can be carried out to mesopore oxide, these are for expanding porous membrane material
Further using for material is significant.
For a further understanding of the present invention, the technical scheme that the present invention is provided is carried out specifically with reference to embodiment
Bright, protection scope of the present invention is not limited by the following examples.
The raw material that the embodiment of the present invention is used is purchased in market.
Embodiment 1
The uniaxial tension type PP perforated membranes (hole size about 40nm × 200nm) that thickness is 25 μm are soaked in a large amount of anhydrous second
It is cleaned by ultrasonic 0.5h in alcohol, and dries, it is dust-proof；To clean and dry porous PP film is placed in and 20s is processed in plasma, so
After be sealed in valve bag.2.0g F127 are dissolved in 6.0g ethanol, the hydrochloric acid solution of 0.2molL~1 is added while stirring
1.5g, adds 6.0g TEOS in mixed liquor, and 2h is stirred at room temperature, obtains the silicon dioxide gel of water white transparency.Will be by place
24h in the PP perforated membranes immersion colloidal sol of reason, until film is permeated completely and becomes transparent.The film that colloidal sol soaked is taken out, in
Further natural air drying 48h in atmosphere under 60~80% relative humidity, makes the sol-gel process of silica fully enter
OK, the silica of the film surface residual that will be completely dried carefully is peeled off, and finally repeatedly washes away table with substantial amounts of water and ethanol
Face activating agent, obtains flexible compound mesoporous film.
Sem analysis are carried out to flexible compound mesoporous film manufactured in the present embodiment, as shown in figure 1, for embodiment 1 prepare it is soft
Property compound mesoporous film surface SEM figure.The average pore size of flexible compound mesoporous film manufactured in the present embodiment is about 4.5nm, hole
Slope is about 12%, and ultra-filtration flux is 1.35mL cm-2h-1.Fig. 2 is flexible compound mesoporous film cryogenic nitrogen manufactured in the present embodiment
Adsorption isotherm.Fig. 3 is flexible compound mesoporous film pore size distribution curve manufactured in the present embodiment.
Embodiment 2
The uniaxial tension type PP perforated membranes (hole size about 40nm × 200nm) that thickness is 25 μm are soaked in a large amount of anhydrous second
It is cleaned by ultrasonic 0.5h in alcohol, and dries, it is dust-proof；Tris (Hydroxymethyl) aminomethane for taking 50mL 0.1M is molten
Liquid, adds the HCl of 14.7mL 0.1M, adjusts pH value to 8.5, is diluted to 100mL, obtains the TrisHCl buffer solutions of 0.05M.Again
The TrisHCl buffer solutions for taking 50mL 0.05M are diluted to 250mL, obtain the buffer solution of 0.01M.0.5g Dopamine is molten
In the TrisHCl buffer solutions of 250mL 0.01M, the PP films for then infiltrating ethanol are soaked in mixed solution, ultrasound
Treatment 0.5h, stands 12h, finally takes out PP films a large amount of deionized waters and washes of absolute alcohol and dries；2.0g F127 is molten
In 6.0g ethanol, the hydrochloric acid solution 1.5g of 0.2molL~1 is added while stirring, 6.0g TEOS are added in mixed liquor,
2h is stirred at room temperature, obtains the silicon dioxide gel of water white transparency.Unprocessed and treated PP perforated membranes are immersed molten
24h in glue, until film is permeated completely and becomes transparent.The film that colloidal sol soaked is taken out, under 60~80% relative humidity
Further natural air drying 48h in atmosphere, making the sol-gel process of silica is fully carried out, the film table that will be completely dried
The remaining silica in face is carefully peeled off, and finally repeatedly washes away surfactant with substantial amounts of water and ethanol, obtains flexible multiple
Close mesoporous film.
Sem analysis are carried out to flexible compound mesoporous film manufactured in the present embodiment, as shown in figure 4, for embodiment 2 prepare it is soft
Property compound mesoporous film surface SEM figure.The average pore size of flexible compound mesoporous film manufactured in the present embodiment is about 4.4nm, hole
Slope is about 12%, and ultra-filtration flux is 1.33mL cm-2h-1。
Embodiment 3
The uniaxial tension type PP perforated membranes (hole size about 40nm × 200nm) that thickness is 25 μm are soaked in a large amount of anhydrous second
It is cleaned by ultrasonic 0.5h in alcohol, and dries, it is dust-proof；2mL methyclyloxypropyls trimethoxy silane (MPS) are dissolved in 100mL
In toluene, 0.05g dibenzoyl peroxides (BPO) is added, treat that BPO is completely dissolved, be put into several pieces PP films, in reaction in 80 DEG C
6h, after naturally cool to room temperature, takes out a large amount of toluene of PP films and absolute ethyl alcohol is cleaned by ultrasonic for several times and dries；By 2.0g
F127 is dissolved in 6.0g ethanol, and the hydrochloric acid solution 1.5g of 0.2molL~1 is added while stirring, and 6.0g is added in mixed liquor
TEOS, stirs 2h at room temperature, obtains the silicon dioxide gel of water white transparency.By the leaching of unprocessed and treated PP perforated membranes
Enter 24h in colloidal sol, until film is permeated completely and becomes transparent.The film that colloidal sol soaked is taken out, it is relatively wet in 60~80%
Further natural air drying 48h in atmosphere under degree, making the sol-gel process of silica is fully carried out, by what is be completely dried
The silica of film surface residual is carefully peeled off, and finally repeatedly washes away surfactant with substantial amounts of water and ethanol, obtains soft
Property compound mesoporous film.
Flexible compound mesoporous film manufactured in the present embodiment is analyzed, as shown in figure 5, for this flexible compound for preparing is situated between
Pore membrane surface SEM schemes, and Fig. 6 is the pore structure TEM figures of flexible compound mesoporous film inside manufactured in the present embodiment mesopore oxide.This
The average pore size of porous polyethylene membrane prepared by embodiment is about 4.5nm, and hole deviation rate is about 12%, and ultra-filtration flux is
1.34mL cm-2h-1。
Embodiment 4
The biaxial stretch-formed type PE perforated membranes that thickness is 20 μm are soaked in and are cleaned by ultrasonic 0.5h in a large amount of absolute ethyl alcohols, and done
It is dry, it is dust-proof；To clean and dry porous PE films are placed in and 20s is processed in plasma, be then sealed in valve bag；Will
2.0g F127 are dissolved in 6.0g ethanol, and the hydrochloric acid solution 1.5g of 0.2molL~1 is added while stirring, are added in mixed liquor
6.0g TEOS, stir 2h at room temperature, obtain the silicon dioxide gel of water white transparency.Unprocessed and treated PE is more
24h in pore membrane immersion colloidal sol, until film is permeated completely and becomes transparent.The film that colloidal sol soaked is taken out, in 60~80%
Further natural air drying 48h in atmosphere under relative humidity, making the sol-gel process of silica is fully carried out, will be complete
The silica of dry film surface residual is carefully peeled off, and finally repeatedly washes away surfactant with substantial amounts of water and ethanol,
Obtain flexible compound mesoporous film.
Sem analysis are carried out to flexible compound mesoporous film manufactured in the present embodiment, as shown in fig. 7, for embodiment 4 prepare it is soft
Property compound mesoporous film surface SEM figure.The average pore size of flexible compound mesoporous film manufactured in the present embodiment is about 4.5nm, hole
Slope is about 14%, and ultra-filtration flux is 1.35mL cm-2h-1。
Embodiment 5
The biaxial stretch-formed type PE perforated membranes that thickness is 20 μm are soaked in and are cleaned by ultrasonic 0.5h in a large amount of absolute ethyl alcohols, and done
It is dry, it is dust-proof；Tris (Hydroxymethyl) aminomethane solution of 50mL 0.1M is taken, adds 14.7mL 0.1M's
HCl, adjusts pH value to 8.5, is diluted to 100mL, obtains the TrisHCl buffer solutions of 0.05M.The Tris of 50mL 0.05M is taken again
HCl buffer solutions are diluted to 250mL, obtain the buffer solution of 0.01M.0.5g Dopamine are dissolved in the Tris of 250mL 0.01M
In HCl buffer solutions, the PE films for then infiltrating ethanol are soaked in mixed solution, ultrasonically treated 0.5h, stand 12h, finally
Take out PE films a large amount of deionized waters and washes of absolute alcohol and dry；2.0g F127 are dissolved in 6.0g ethanol, while stirring
The hydrochloric acid solution 1.5g of 0.2molL~1 is added, 6.0g TEOS are added in mixed liquor, 2h is stirred at room temperature, obtain colourless
Transparent silicon dioxide gel.Unprocessed and treated PE perforated membranes are immersed into 24h in colloidal sol, until film is oozed completely
Thoroughly and become transparent.The film that soaked of colloidal sol is taken out, in further natural air drying in atmosphere under 60~80% relative humidity
48h, making the sol-gel process of silica is fully carried out, and the silica of the film surface residual that will be completely dried is carefully
Peel off, finally repeatedly wash away surfactant with substantial amounts of water and ethanol, obtain flexible compound mesoporous film.
Sem analysis are carried out to flexible compound mesoporous film manufactured in the present embodiment, as shown in figure 8, for embodiment 5 prepare it is soft
Property compound mesoporous film surface SEM figure.The average pore size of flexible compound mesoporous film manufactured in the present embodiment is about 4.5nm, hole
Slope is about 14%, and ultra-filtration flux is 1.36mL cm-2h-1。
Embodiment 6
The biaxial stretch-formed type PE perforated membranes that thickness is 20 μm are soaked in and are cleaned by ultrasonic 0.5h in a large amount of absolute ethyl alcohols, and done
It is dry, it is dust-proof；2mL methyclyloxypropyls trimethoxy silane (MPS) are dissolved in 100mL toluene, 0.05g peroxidating is added
Dibenzoyl (BPO), treats that BPO is completely dissolved, and is put into PE films, in 6h is reacted in 80 DEG C, after naturally cool to room temperature, takes out PP films
It is cleaned by ultrasonic for several times and is dried with a large amount of toluene and absolute ethyl alcohol；2.0g F127 are dissolved in 6.0g ethanol, are added while stirring
The hydrochloric acid solution 1.5g of 0.2mo lL~1, adds 6.0g TEOS in mixed liquor, and 2h is stirred at room temperature, obtains water white transparency
Silicon dioxide gel.Unprocessed and treated PE perforated membranes are immersed into 24h in colloidal sol, until film is permeated simultaneously completely
Become transparent.The film that soaked of colloidal sol is taken out, in further natural air drying 48h in atmosphere under 60~80% relative humidity,
Making the sol-gel process of silica is fully carried out, and the silica of the film surface residual that will be completely dried carefully is peeled off,
Surfactant repeatedly finally is washed away with substantial amounts of water and ethanol, flexible compound mesoporous film is obtained.
Sem analysis are carried out to flexible compound mesoporous film manufactured in the present embodiment, as shown in figure 9, for embodiment 6 prepare it is soft
Property compound mesoporous film surface SEM figure.The average pore size of flexible compound mesoporous film manufactured in the present embodiment is about 4.5nm, hole
Slope is about 14%, and ultra-filtration flux is 1.35mL cm-2h-1。
Embodiment 7
The biaxial stretch-formed type PE perforated membranes that thickness is 20 μm are soaked in and are cleaned by ultrasonic 0.5h in a large amount of absolute ethyl alcohols, and done
It is dry, it is dust-proof；To clean and dry porous PE films are placed in and 20s is processed in plasma, be then sealed in valve bag；Will
2.0g P123 are dissolved in 6.0g ethanol, and the hydrochloric acid solution 1.5g of 0.2molL~1 is added while stirring, are added in mixed liquor
6.0g TEOS, stir 2h at room temperature, obtain the silicon dioxide gel of water white transparency.Unprocessed and treated PE is more
24h in pore membrane immersion colloidal sol, until film is permeated completely and becomes transparent.The film that colloidal sol soaked is taken out, in 60~80%
Further natural air drying 48h in atmosphere under relative humidity, making the sol-gel process of silica is fully carried out, will be complete
The silica of dry film surface residual is carefully peeled off, and finally repeatedly washes away surfactant with substantial amounts of water and ethanol,
Obtain flexible compound mesoporous film.
The average pore size of flexible compound mesoporous film manufactured in the present embodiment is about 4.0nm, and hole deviation rate is about 13%, surpasses
Filtration flux is 1.32mL cm-2h-1.Figure 10 is flexible compound mesoporous film nitrogen absorption under low temperature thermoisopleth manufactured in the present embodiment.Figure 11
It is flexible compound mesoporous film pore size distribution curve manufactured in the present embodiment.
Embodiment 8
The uniaxial tension type PP perforated membranes (hole size about 40nm × 200nm) that thickness is 25 μm are soaked in a large amount of anhydrous second
It is cleaned by ultrasonic 0.5h in alcohol, and dries, it is dust-proof；Tris (Hydroxymethyl) aminomethane for taking 50mL 0.1M is molten
Liquid, adds the HCl of 14.7mL 0.1M, adjusts pH value to 8.5, is diluted to 100mL, obtains the TrisHCl buffer solutions of 0.05M.Again
The TrisHCl buffer solutions for taking 50mL 0.05M are diluted to 250mL, obtain the buffer solution of 0.01M.0.5g Dopamine is molten
In the TrisHCl buffer solutions of 250mL 0.01M, the PE films for then infiltrating ethanol are soaked in mixed solution, ultrasound
Treatment 0.5h, stands 12h, finally takes out PE films a large amount of deionized waters and washes of absolute alcohol and dries；2.0g P123 is molten
In 6.0g ethanol, the hydrochloric acid solution 1.5g of 0.2molL~1 is added while stirring, 6.0g TEOS are added in mixed liquor,
2h is stirred at room temperature, obtains the silicon dioxide gel of water white transparency.Unprocessed and treated PE perforated membranes are immersed molten
24h in glue, until film is permeated completely and becomes transparent.The film that colloidal sol soaked is taken out, under 60~80% relative humidity
Further natural air drying 48h in atmosphere, making the sol-gel process of silica is fully carried out, the film table that will be completely dried
The remaining silica in face is carefully peeled off, and finally repeatedly washes away surfactant with substantial amounts of water and ethanol, obtains flexible multiple
Close mesoporous film.
The average pore size of flexible compound mesoporous film manufactured in the present embodiment is about 3.9nm, and hole deviation rate is about 12%, surpasses
Filtration flux is 1.32mL cm-2h-1。
Embodiment 9
The uniaxial tension type PP perforated membranes (hole size about 40nm × 200nm) that thickness is 25 μm are soaked in a large amount of anhydrous second
It is cleaned by ultrasonic 0.5h in alcohol, and dries, it is dust-proof；2mL methyclyloxypropyls trimethoxy silane (MPS) are dissolved in 100mL
In toluene, 0.05g dibenzoyl peroxides (BPO) is added, treat that BPO is completely dissolved, be put into PE films, in 6h is reacted in 80 DEG C, treated
Room temperature is naturally cooled to, a large amount of toluene of PP films is taken out and absolute ethyl alcohol is cleaned by ultrasonic for several times and dries；2.0g P123 are dissolved in
In 6.0g ethanol, the hydrochloric acid solution 1.5g of 0.2molL~1 is added while stirring, 6.0g TEOS, room are added in mixed liquor
The lower stirring 2h of temperature, obtains the silicon dioxide gel of water white transparency.Unprocessed and treated PE perforated membranes are immersed into colloidal sol
Middle 24h, until film is permeated completely and becomes transparent.Take out the film that soaked of colloidal sol, under 60~80% relative humidity
Further natural air drying 48h in air, making the sol-gel process of silica is fully carried out, the film surface that will be completely dried
Remaining silica is carefully peeled off, and finally repeatedly washes away surfactant with substantial amounts of water and ethanol, obtains flexible compound
Mesoporous film.
The average pore size of flexible compound mesoporous film manufactured in the present embodiment is about 3.9nm, and hole deviation rate is about 13%, surpasses
Filtration flux is 1.33mL cm-2h-1。
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or uses the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The scope most wide for causing.
Claims (10)
1. a kind of preparation method of composite mesoporous film, it is characterised in that comprise the following steps：
Under catalyst action, precursor compound and structure directing agent are carried out into alcoholysis reaction in ethanol, obtain colloidal sol, institute
Precursor compound is stated to be selected from silicon source compound, titanium source compound, zinc source compound, tin source compound and niobium source compound
One or more, the structure directing agent is selected from PEO-PPOX-PEO triblock copolymer, ten
One or more in six alkyl trimethyl ammonium bromides and lauryl sodium sulfate；
Perforated membrane is surface-treated, is then soaked 2~24 hours in the colloidal sol；
By the perforated membrane after immersion in being dried under room temperature condition and completing sol gel process, then clean, dry, obtain
Composite mesoporous film.
2. preparation method according to claim 1, it is characterised in that the precursor compound be selected from tetraethyl orthosilicate,
One or more in titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, dibutyl phthalate, stannic acid ester and niobates.
3. preparation method according to claim 1, it is characterised in that the catalyst is HCl, HNO3、H2SO4Or ammoniacal liquor.
4. preparation method according to claim 1, it is characterised in that the precursor compound, structure directing agent, ethanol
It is (1~10) mL with the ratio of catalyst：(0.3~2.0) g：(10~30) mL：(0.5~3.0) g.
5. preparation method according to claim 1, it is characterised in that the temperature of alcoholysis reaction is 20~80 DEG C, and the time is 2
~12 hours.
6. preparation method according to claim 1, it is characterised in that the perforated membrane is polypropylene porous film, polyethylene
Perforated membrane, polyimide porous membrane or makrolon perforated membrane.
7. preparation method according to claim 1, it is characterised in that the mode of the surface treatment is at oxygen plasma
Reason or surface chemical modification treatment.
8. preparation method according to claim 1, it is characterised in that perforated membrane after immersion under room temperature condition in drying
Time is 12~48 hours.
9. preparation method according to claim 1, it is characterised in that the cleaning is molten using the mixing cleaning of second alcohol and water
Liquid, scavenging period is 0.5~2 hour, and the temperature for mixing cleaning solution is 40~50 DEG C.
10. preparation method according to claim 1, it is characterised in that dry temperature is 30~40 DEG C, dry time
It is 0.5~2 hour.
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