CN107824060A - A kind of polyhedral oligomeric silsesquioxane composite nanometer filter membrane preparation method - Google Patents
A kind of polyhedral oligomeric silsesquioxane composite nanometer filter membrane preparation method Download PDFInfo
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- CN107824060A CN107824060A CN201711006151.8A CN201711006151A CN107824060A CN 107824060 A CN107824060 A CN 107824060A CN 201711006151 A CN201711006151 A CN 201711006151A CN 107824060 A CN107824060 A CN 107824060A
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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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The present invention relates to technology of composite film preparation field, and in particular to a kind of polyhedral oligomeric silsesquioxane composite nanometer filter membrane preparation method, mainly prepares high-molecular porous basement membrane using phase inversion；Alkali process obtains eight amino polyhedral oligomeric silsesquioxane dispersion liquids；Polymerized monomer and ultrafiltration membranes are added in dispersion liquid again polyhedral oligomeric silsesquioxane composite membrane is made by oscillator deposition polymerization.Operating process of the present invention is simple, it is green, organic solvent-free uses, relative to traditional composite nanometer filtering film, polyhedral oligomeric silsesquioxane/poly-dopamine separating layer prepared by this method is very thin, and with abundant mass transfer duct, under ultralow operating pressure (0.1MPa), there is higher water flux and separating property.
Description
Technical field
The present invention relates to technology of composite film preparation field, and in particular to a kind of polyhedral oligomeric silsesquioxane composite nanometer filter
Membrane preparation method.
Background technology
The development of nanofiltration starts from late 1980s, is the one kind of separation accuracy between counter-infiltration and ultrafiltration
Pressure-driven membrane separation technique, it has higher permeation flux, lower operating pressure (0.3- relative to reverse osmosis membrane
1.0MPa), there is good cutoff performance to high price salt ion and small organic molecule, be widely used in bitter desalination,
The fields such as treatment of dyeing wastewater, biochemical preparation and drug purification[1-3]。
At present, NF membrane can be divided into anisotropic membrane and composite membrane by structural shape.Composite membrane is by porous basement membrane and is covered in
Epilamellar fine and close active layer composition, because its excellent performance turns into current main flow membrane structure pattern.Wherein, active layer is used for
Divalent ion or organic molecule are retained, and porous basement membrane provides mechanical support, this composite construction is top active separating layer
Possibility is provided with optimization while bottom support layer[4].Preparing the method for composite nanometer filtering film mainly includes interfacial polymerization, table
Face cladding process, surface grafting polymerization method, LBL self-assembly method and bionical Method for bonding etc..
Wherein bionical Method for bonding is so that its is simple to operate, controllability is strong, advantages of environment protection obtains extensively in technical field of membrane
General concern, and bionical Method for bonding can prepare ultra-thin active layer, cause composite membrane have concurrently under low pressure higher selectivity and
Permeability[5]。
Bionical Method for bonding, which prepares composite membrane, to be inspired by mussel attachment proteins, utilizes catecholamine or Polyphenols polymerized monomer
Michael's addition or schiff base reaction occur in the basic conditions for interior abundant amino and aldehyde radical, so as to be deposited on porous basement membrane
Polymerization forms very thin dense separation layers.Due to polymer layer thickness and deposition polymerization time correlation, when being deposited by Reasonable Regulation And Control
Between, processing of ultra-thin polymeric nitride layer can be made, so that compound permeability of the membrane and selectivity all greatly improve.Conventional polymerized monomer has
Dopamine, tannic acid and levodopa etc., the polymer sheaths such as poly-dopamine, poly- polyphenol or poly- levodopa are formed after polymerization respectively
Layer[6].Wherein it is most common in composite membrane to be prepared by bionical Method for bonding for poly-dopamine, and the most commonly used membrane material of application study
Material.
At present, to construct efficient mass transfer duct in composite membrane to lift the separating property of ultra-thin active layer, researcher is more
Using inorganic nano material (such as nano silicon, titanium dioxide and stannic oxide/graphene nano piece etc.) is introduced into polymerization process
Method, specific physical structure and chemical property based on nano material improve compound permeability of the membrane, selectivity and antipollution
Characteristic etc..But poly-dopamine composite membrane separating layer prepared by bionical bonding is relatively thin (about 50-100nm), size is less than current
Common nano material, it will be made to protrude film surface above-mentioned nano material introducing separating layer, destroy ultra-thin active layer structure,
Shape film forming defect, reduce separating property.
Polyhedral oligomeric silsesquioxane has less cage type cavity as a kind of emerging molecular scale nano material
Structure (0.32-0.54nm), it is polyamide-based multiple preparing because of its compatibility good with macromolecule and excellent dimensional characteristic
Have been obtained for applying in terms of closing film[7,8].Such as polyhedral oligomeric silsesquioxane reinforcing is added in interfacial polymerization aqueous phase and is gathered
Acid amides nano filter membrane separating property.But so far, the polyhedral oligomeric silsesquioxane of amino functional is introduced bionical viscous
It is legal to be rarely reported with strengthening the research of the ultra-thin nano filter membrane separating property of poly-dopamine.
The content of the invention
A kind of the defects of it is an object of the invention to overcome above-mentioned background technology to exist, there is provided polyhedral oligomeric silsesquioxane
Alkane composite nanometer filter membrane preparation method, by porous basement membrane using functionalization polyhedral oligomeric silsesquioxane as nano-filled
Grain, it is polymerize by being co-deposited with pyrocatechol monomer to obtain.
Technical scheme:A kind of polyhedral oligomeric silsesquioxane composite nanometer filter membrane preparation method, its step is such as
Under：
(1), prepared by high-molecular porous basement membrane：Film-forming high molecular material is dissolved in DMF, is configured to matter
The casting solution that concentration is 15-18% is measured, in 50-70 DEG C of stirring and standing and defoaming, is cooled to after room temperature and casting solution is poured on glass
Knifing on plate, freezing film in water-bath is put into, is soaked after being removed from glass plate with deionized water；
(2), prepared by functionalization polyhedral oligomeric silsesquioxane：Functionalization multiaspect is added into 20ml aqueous buffer solution
Body oligomeric silsesquioxane, its mass fraction are 0.25-0.8%, after ultrasonic disperse processing obtain that polyhedral oligomeric sesquialter can be changed
The scattered cushioning liquid of siloxanes；
(3) it is 0.25-, to prepare high-molecular porous basement membrane to be immersed in step (2) containing mass fraction by above-mentioned steps (1)
In the scattered cushioning liquid of 0.80% functionalization polyhedral oligomeric silsesquioxane；
(4) polymerized monomer that mass fraction is 0.2-0.4%, oscillating deposition polymerization film formation, frequency of oscillation 100-, are added
150r/min, 60-120min；
(5), take out film and 50-70min is heat-treated in 50-80 DEG C.
Film-forming high molecular material is polyacrylonitrile or polyether sulfone in the step (1), and film forming is polyacrylonitrile basement membrane or gathered
Ether sulfone basement membrane.
In the step (2) functionalization polyhedral oligomeric silsesquioxane be eight amino polyhedral oligomeric silsesquioxanes or
Any one in eight ammonium chloride polyhedral oligomeric silsesquioxanes or combination.
Aqueous buffer solution is that trishydroxymethylaminomethane-hydrochloride buffer aqueous solution, phosphoric acid buffer are water-soluble in the step (2)
Any one in liquid or citric acid aqueous buffer solution.
Between 8-9, concentration is controlled in 50mmol for aqueous buffer solution PH controls in the step (2).
Polymerized monomer is any one in dopamine or tannic acid or combination in institute's step (4).
The preparation method of a kind of polyhedral oligomeric silsesquioxane composite membrane provided by the invention, mainly using inversion of phases
Method prepares polyacrylonitrile ultrafiltration membranes or polyether sulfone ultrafiltration membranes；Alkali process obtains eight amino polyhedral oligomeric silsesquioxanes point
Dispersion liquid；Polymerized monomer and ultrafiltration membranes are added in dispersion liquid again polyhedral oligomeric sesquialter is made by oscillator deposition polymerization
Siloxanes composite membrane.
Compared with prior art, the present invention has the advantage that：The present invention is using polyhedral oligomeric silsesquioxane as nanometer
Filler particles are co-deposited with pyrocatechol polymerized monomer, and process is simple to operation, green, and organic solvent-free uses, relatively
In traditional composite nanometer filtering film, polyhedral oligomeric silsesquioxane/poly-dopamine separating layer prepared by this method is very thin, and has
There is abundant mass transfer duct, under ultralow operating pressure (0.1MPa), there is higher water flux and separating property.
Brief description of the drawings
Fig. 1 is the pure water flux for the polyhedral oligomeric silsesquioxane composite nanometer filtering film that the embodiment of the present invention 2 is prepared
And to orange sodium, methyl blue, Congo red and alcian blue (mass fraction is 0.01%) aqueous solution rejection figure.
Fig. 2 is the sem image on polyacrylonitrile basement membrane surface prepared by embodiment 1.
Fig. 3 is polyhedral oligomeric silsesquioxane composite nanometer filtering film surface sem image prepared by embodiment 1.
Fig. 4 is the sem image of polyether sulfone membrane surface prepared by embodiment 11.
Fig. 5 is polyhedral oligomeric silsesquioxane composite nanometer filtering film surface sem image prepared by embodiment 11.
Embodiment
Below by specific embodiments and the drawings, the present invention is further illustrated.Embodiments of the invention are in order to more
Those skilled in the art is more fully understood the present invention well, any limitation is not made to the present invention.
Embodiment 1, polyhedral oligomeric silsesquioxane composite nanometer filtering film is prepared, step is as follows：
Step 1: the preparation of polyacrylonitrile basement membrane：
Polyacrylonitrile is dissolved in DMF, is configured to the casting film that mass concentration containing polyacrylonitrile is 15%
Liquid, 12h, and the standing and defoaming 12h at 50 DEG C are stirred at 50 DEG C, be cooled to after room temperature and scrape casting solution on a glass
Film, freezing film in 25 DEG C of water-baths is put into, soaks 24h with deionized water after being removed from glass plate, obtain polyacrylonitrile-radical
Film, as shown in Fig. 2；
Step 2: prepared by eight amino polyhedral oligomeric silsesquioxane dispersion liquids：
Eight ammonium chlorides are added into 20ml trishydroxymethylaminomethane-hydrochloride buffer aqueous solution (pH=8.5,50mmol)
Polyhedral oligomeric silsesquioxane, its mass fraction be 0.25%, 40kHz ultrasonic disperses handle 15min after in the basic conditions
It is set to be converted into eight amino polyhedral oligomeric silsesquioxanes, product is that eight amino polyhedral oligomeric silsesquioxanes disperse
Liquid；
Step 3: the preparation of polyhedral oligomeric silsesquioxane composite membrane：
By the polyacrylonitrile basement membrane that step 1 obtains be immersed in 20ml mass fractions for 0.25% the step of two prepare eight
In amino polyhedral oligomeric silsesquioxane dispersion liquid, the dopamine polymerized monomer that mass fraction is 0.2% is added, is being vibrated
Deposition polymerization in device, frequency of oscillation 150r/min, taking-up film is heat-treated 60min in 60 DEG C after polymerizeing 90min, obtains polyhedron
Oligomeric silsesquioxane composite nanometer filtering film 1, the surface electron microscope of the composite nanometer filtering film 1 are as shown in Figure 3.
Water flux of the polyhedral oligomeric silsesquioxane composite membrane 1 under 0.1MPa operating pressures obtained by embodiment 1
For 71.2 L/ (m2H), it is 90.2% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 2, polyhedral oligomeric silsesquioxane composite membrane is prepared, its preparation process is substantially the same manner as Example 1, no
It is same to be only that：In step 3, eight amino polyhedral oligomerics prepared by the step of obtained polyacrylonitrile basement membrane is immersed in 20ml two
In silsesquioxane dispersion liquid, the mass fraction of its eight amino polyhedral oligomeric silsesquioxane aqueous dispersion is 0.60%,
Polymerization time is 75min, finally obtained polyhedral oligomeric silsesquioxane composite membrane 2.
Water flux of the polyhedral oligomeric silsesquioxane composite membrane 2 under 0.1MPa operating pressures obtained by embodiment 2
For 109.9L/ (m2H), it is 90.5% to orange sodium (mass fraction 0.01%) aqueous solution rejection.Fig. 1 is polyhedral oligomeric
Silsesquioxane composite membrane 2 is cut to orange sodium, methyl blue, Congo red, alcian blue (mass fraction is 0.01%) aqueous solution
Stay rate figure.
Embodiment 3, polyhedral oligomeric silsesquioxane composite membrane is prepared, its preparation process is substantially the same manner as Example 1, no
It is same to be only that：In step 3, eight amino polyhedral oligomerics prepared by the step of obtained polyacrylonitrile basement membrane is immersed in 20ml two
In silsesquioxane dispersion liquid, the mass fraction of its eight amino polyhedral oligomeric silsesquioxane aqueous dispersion is 0.80%,
Finally obtained polyhedral oligomeric silsesquioxane composite membrane 3.
Water flux of the polyhedral oligomeric silsesquioxane composite membrane 3 under 0.1MPa operating pressures obtained by embodiment 3
For 86.3L/ (m2H), it is 77.3% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 4, polyhedral oligomeric silsesquioxane composite membrane is prepared, its preparation process is substantially the same manner as Example 2, no
It is same to be only that：In step 3, deposition polymerization, its deposition polymerization time are 60min in an oscillator.
Water flux of the polyhedral oligomeric silsesquioxane composite membrane 4 under 0.1MPa operating pressures obtained by embodiment 4
For 151.7L/ (m2H), it is 80.2% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 5, polyhedral oligomeric silsesquioxane composite membrane is prepared, its preparation process is substantially the same manner as Example 2, no
It is same to be only that：In step 3, deposition polymerization, its deposition polymerization time are 90min in an oscillator.
Water flux of the polyhedral oligomeric silsesquioxane composite membrane 5 under 0.1MPa operating pressures obtained by embodiment 5
For 76.6L/ (m2H), it is 88.2% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 6, polyhedral oligomeric silsesquioxane composite membrane is prepared, its preparation process is substantially the same manner as Example 1, no
It is same to be only that：In step 3, eight amino polyhedral oligomerics prepared by the step of obtained polyacrylonitrile basement membrane is immersed in 20ml two
In silsesquioxane dispersion liquid, the mass fraction of its eight amino polyhedral oligomeric silsesquioxane aqueous dispersion is 0.40%,
Finally obtained polyhedral oligomeric silsesquioxane composite membrane 6.
Water flux of the polyhedral oligomeric silsesquioxane composite membrane 6 under 0.1MPa operating pressures obtained by embodiment 6
For 73.0L/ (m2H), it is 88.5% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 7, polyhedral oligomeric silsesquioxane composite membrane is prepared, its step is as follows：
Step 1: the preparation of polyacrylonitrile basement membrane：
Polyacrylonitrile is dissolved in DMF, is configured to the casting film that mass concentration containing polyacrylonitrile is 16%
Liquid, 12h, and the standing and defoaming 12h at 60 DEG C are stirred at 60 DEG C, be cooled to after room temperature and scrape casting solution on a glass
Film, freezing film in 25 DEG C of water-baths is put into, soaks 24h with deionized water after being removed from glass plate, obtain polyacrylonitrile-radical
Film；
Step 2: prepared by eight amino polyhedral oligomeric silsesquioxane dispersion liquids：
It is more that eight amino are added into 20ml trishydroxymethylaminomethane-hydrochloride buffer aqueous solution (pH=8.5,50mmol)
Face body oligomeric silsesquioxane, its mass fraction are that product is eight amino after 0.25%, 40kHz ultrasonic disperses handle 15min
Polyhedral oligomeric silsesquioxane dispersion liquid；
Step 3: the preparation of polyhedral oligomeric silsesquioxane composite membrane：
By the polyacrylonitrile basement membrane that step 1 obtains be immersed in 20ml mass fractions for 0.25% the step of two prepare eight
In amino polyhedral oligomeric silsesquioxane dispersion liquid, the dopamine polymerized monomer that mass fraction is 0.2% is added, is being vibrated
Deposition polymerization in device, frequency of oscillation 150r/min, taking-up film is heat-treated 60min in 60 DEG C after polymerizeing 90min, is finally made more
Face body oligomeric silsesquioxane composite membrane 7.
Water flux of the polyhedral oligomeric silsesquioxane composite membrane 7 under 0.1MPa operating pressures obtained by embodiment 7
For 73.3L/ (m2H), it is 90.2% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 8, polyhedral oligomeric silsesquioxane composite membrane is prepared, its preparation process is substantially the same manner as Example 1, no
It is same to be only that：In step 3, the tannic acid polymerized monomer that mass fraction is 0.4% is added, finally obtained polyhedral oligomeric times
Half siloxanes composite membrane 8.
Water flux of the polyhedral oligomeric silsesquioxane composite membrane 8 under 0.1MPa operating pressures obtained by embodiment 8
For 51.2L/ (m2H), it is 95.2% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 9, polyhedral oligomeric silsesquioxane composite membrane is prepared, its preparation process is substantially the same manner as Example 1, no
It is same to be only that：In step 2, eight ammonium chloride polyhedrons are added into 20ml aqueous phosphate buffer (pH=8.5,50mmol)
Oligomeric silsesquioxane, polyhedral oligomeric silsesquioxane composite membrane 9 is finally made.
Water flux of the polyhedral oligomeric silsesquioxane composite membrane 9 under 0.1MPa operating pressures obtained by embodiment 9
For 61.1L/ (m2H), it is 80.1% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 10, polyhedral oligomeric silsesquioxane composite membrane being prepared, its preparation process is substantially the same manner as Example 1,
It is different only in that：In step 2, it is more that eight ammonium chlorides are added into 20ml citric acid aqueous buffer solution (pH=8.5,50mmol)
Face body oligomeric silsesquioxane, polyhedral oligomeric silsesquioxane composite membrane 10 is finally made.
Water of the polyhedral oligomeric silsesquioxane composite membrane 10 under 0.1MPa operating pressures obtained by embodiment 10 leads to
Measure as 80.1L/ (m2H), it is 70.7% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 11, polyhedral oligomeric silsesquioxane composite nanometer filtering film is prepared, step is as follows：
Step 1: the preparation of polyether sulfone basement membrane：
Polyether sulfone is dissolved in DMF, is configured to the casting solution that mass concentration containing polyether sulfone is 18%,
12h, and the standing and defoaming 12h at 70 DEG C are stirred at 70 DEG C, is cooled to casting solution knifing on a glass after room temperature, is put into
Freezing film in 25 DEG C of water-baths, 24h is soaked with deionized water after being removed from glass plate, obtains polyether sulfone basement membrane, electron microscope is such as
Shown in Fig. 4；
Step 2: prepared by eight amino polyhedral oligomeric silsesquioxane dispersion liquids：
Eight ammonium chlorides are added into 20ml trishydroxymethylaminomethane-hydrochloride buffer aqueous solution (pH=8.5,50mmol)
Polyhedral oligomeric silsesquioxane, in alkalescence condition after making its mass fraction be 0.25%, 40kHz ultrasonic disperses processing 15min
Under it is converted into eight amino polyhedral oligomeric silsesquioxanes, product is that eight amino polyhedral oligomeric silsesquioxanes disperse
Liquid；
Step 3: the preparation of polyhedral oligomeric silsesquioxane composite membrane：
The polyether sulfone basement membrane that step 1 obtains is immersed in two eight ammonia prepared of the step of 20ml mass fractions are 0.25%
In polyhedral oligomeric silsesquioxane dispersion liquid, the dopamine polymerized monomer that mass fraction is 0.2% is added, in oscillator
Middle deposition polymerization, frequency of oscillation 150r/min, taking-up film is heat-treated 60min in 60 DEG C after polymerizeing 90min, and it is low to obtain polyhedron
Polysilsesquioxane composite nanometer filtering film 11, electron microscope is as shown in Figure 5.
Water of the polyhedral oligomeric silsesquioxane composite membrane 11 under 0.1MPa operating pressures obtained by embodiment 11 leads to
Measure as 36.9L/ (m2H), it is 87.1% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 12, polyhedral oligomeric silsesquioxane composite membrane being prepared, its preparation process is substantially the same manner as Example 1,
It is different only in that：In step 3, the polymerized monomer of addition combines (both bodies for the tannic acid and dopamine of mass fraction 0.4%
Product ratio 1: 1), taking-up film is heat-treated 60min in 60 DEG C after polymerizeing 120min, and finally obtained polyhedral oligomeric silsesquioxane is answered
Close film 12.
Water of the polyhedral oligomeric silsesquioxane composite membrane 12 under 0.1MPa operating pressures obtained by embodiment 12 leads to
Measure as 23.6L/ (m2H), it is 93.1% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 13, polyhedral oligomeric silsesquioxane composite membrane being prepared, its preparation process is substantially the same manner as Example 11,
It is different only in that：In step 2, into 20ml trishydroxymethylaminomethane-hydrochloride buffer aqueous solution (pH=9.0,50mmol)
Eight ammonium chloride polyhedral oligomeric silsesquioxanes are added, finally obtained polyhedral oligomeric silsesquioxane composite membrane 13.
Water of the polyhedral oligomeric silsesquioxane composite membrane 13 under 0.1MPa operating pressures obtained by embodiment 13 leads to
Measure as 33.1L/ (m2H), it is 89.1% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 14, polyhedral oligomeric silsesquioxane composite membrane being prepared, its preparation process is substantially the same manner as Example 11,
It is different only in that：In step 2, into 20ml trishydroxymethylaminomethane-hydrochloride buffer aqueous solution (pH=8.0,50mmol)
Eight ammonium chloride polyhedral oligomeric silsesquioxanes are added, finally obtained polyhedral oligomeric silsesquioxane composite membrane 14.
Water of the polyhedral oligomeric silsesquioxane composite membrane 14 under 0.1MPa operating pressures obtained by embodiment 14 leads to
Measure as 41.8L/ (m2H), it is 76.6% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 15, polyhedral oligomeric silsesquioxane composite membrane being prepared, its preparation process is substantially the same manner as Example 11,
It is different only in that：In step 3, deposition polymerization, frequency of oscillation 100r/min, is finally made polyhedral oligomeric times in an oscillator
Half siloxanes composite membrane 15.
Water of the polyhedral oligomeric silsesquioxane composite membrane 15 under 0.1MPa operating pressures obtained by embodiment 15 leads to
Measure as 30.1L/ (m2H), it is 90.1% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 16, polyhedral oligomeric silsesquioxane composite membrane being prepared, its preparation process is substantially the same manner as Example 11,
It is different only in that：In step 3, deposition polymerization, frequency of oscillation 120r/min, is finally made polyhedral oligomeric in an oscillator
Silsesquioxane composite membrane 16.
Water of the polyhedral oligomeric silsesquioxane composite membrane 16 under 0.1MPa operating pressures obtained by embodiment 16 leads to
Measure as 34.1L/ (m2H), it is 88.2% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 17, polyhedral oligomeric silsesquioxane composite membrane being prepared, its preparation process is substantially the same manner as Example 11,
It is different only in that：In step 3, taking-up film is heat-treated 50min in 60 DEG C after polymerizeing 90min, finally obtained polyhedral oligomeric times
Half siloxanes composite membrane 17.
Water of the polyhedral oligomeric silsesquioxane composite membrane 17 under 0.1MPa operating pressures obtained by embodiment 17 leads to
Measure as 34.1L/ (m2H), it is 88.2% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 18, polyhedral oligomeric silsesquioxane composite membrane being prepared, its preparation process is substantially the same manner as Example 11,
It is different only in that：In step 3, taking-up film is heat-treated 70min in 60 DEG C after polymerizeing 90min, finally obtained polyhedral oligomeric times
Half siloxanes composite membrane 18.
Water of the polyhedral oligomeric silsesquioxane composite membrane 18 under 0.1MPa operating pressures obtained by embodiment 18 leads to
Measure as 30.1L/ (m2H), it is 90.2% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 19, polyhedral oligomeric silsesquioxane composite membrane being prepared, its preparation process is substantially the same manner as Example 11,
It is different only in that：In step 3, taking-up film is heat-treated 60min in 50 DEG C after polymerizeing 90min, finally obtained polyhedral oligomeric times
Half siloxanes composite membrane 19.
Water of the polyhedral oligomeric silsesquioxane composite membrane 19 under 0.1MPa operating pressures obtained by embodiment 19 leads to
Measure as 41.1L/ (m2H), it is 85.2% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Embodiment 20, polyhedral oligomeric silsesquioxane composite membrane being prepared, its preparation process is substantially the same manner as Example 11,
It is different only in that：Aqueous buffer solution is trishydroxymethylaminomethane-hydrochloric acid, phosphoric acid or citric acid aqueous buffer solution group in step 2
Close (three's volume ratio is 1: 2: 1), in step 3, taking-up film is heat-treated 60min in 80 DEG C after polymerizeing 90min, final to be made
Polyhedral oligomeric silsesquioxane composite membrane 20.
Water of the polyhedral oligomeric silsesquioxane composite membrane 20 under 0.1MPa operating pressures obtained by embodiment 20 leads to
Measure as 29.1L/ (m2H), it is 94.2% to orange sodium (mass fraction 0.01%) aqueous solution rejection.
Comparative example, prepare polyacrylonitrile basement membrane, as comparative film in the way of the step 1 of embodiment 1.
The water flux of comparative film prepared by comparative example under 0.1MPa operating pressures is 261.7L/ (m2H), to orange sodium
(mass fraction 0.01%) aqueous solution rejection is 39.2%.
Composite membrane made from various embodiments of the present invention and the flux of comparative film made from comparative example compared with separating property as
Shown in table 1：
Table 1
It should be appreciated that embodiment and example discussed herein simply to illustrate that, to those skilled in the art
For, it can be improved or be converted, and all these modifications and variations should all belong to the protection of appended claims of the present invention
Scope.
Pertinent literature：
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Claims (6)
1. a kind of polyhedral oligomeric silsesquioxane composite nanometer filter membrane preparation method, it is characterised in that step is as follows：
(1), prepared by high-molecular porous basement membrane：Film-forming high molecular material is dissolved in DMF, it is dense to be configured to quality
The casting solution for 15-18% is spent, in 50-70 DEG C of stirring and standing and defoaming, is cooled to casting solution after room temperature on a glass
Knifing, freezing film in water-bath is put into, is soaked after being removed from glass plate with deionized water；
(2), prepared by functionalization polyhedral oligomeric silsesquioxane：It is low that functionalization polyhedron is added into 20ml aqueous buffer solution
Polysilsesquioxane, its mass fraction are 0.25-0.8%, after ultrasonic disperse processing obtain that polyhedral oligomeric silsesquioxane can be changed
The scattered cushioning liquid of alkane；
(3) it is 0.25-0.80%, to prepare high-molecular porous basement membrane to be immersed in step (2) containing mass fraction by above-mentioned steps (1)
Functionalization polyhedral oligomeric silsesquioxane scattered cushioning liquid in；
(4) polymerized monomer that mass fraction is 0.2-0.4%, oscillating deposition polymerization film formation, frequency of oscillation 100-150r/, are added
Min, 60-120min；
(5), take out film and 50-70min is heat-treated in 50-80 DEG C.
2. preparation method according to claim 1, it is characterised in that film-forming high molecular material is poly- in the step (1)
Acrylonitrile or polyether sulfone, film forming are polyacrylonitrile basement membrane or polyether sulfone basement membrane.
3. preparation method according to claim 1, it is characterised in that functionalization polyhedral oligomeric times in the step (2)
Half siloxanes is any one in eight amino polyhedral oligomeric silsesquioxanes or eight ammonium chloride polyhedral oligomeric silsesquioxanes
Kind or combination.
4. preparation method according to claim 1, it is characterised in that aqueous buffer solution is three hydroxyl first in the step (2)
Any one in the base aminomethane-hydrochloride buffer aqueous solution, aqueous phosphate buffer or citric acid aqueous buffer solution.
5. preparation method according to claim 1, it is characterised in that aqueous buffer solution PH controls exist in the step (2)
Between 8-9, concentration is controlled in 50mmol.
6. preparation method according to claim 1, it is characterised in that polymerized monomer is dopamine or list in institute's step (4)
Any one in peaceful acid or combination.
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| CN108912366A (en) * | 2018-06-06 | 2018-11-30 | 计冲 | A kind of three-dimensional structure and deformation order are adjustable from moulding material and preparation method thereof |
| CN109012183A (en) * | 2018-07-09 | 2018-12-18 | 天津大学 | A kind of preparation method of the ultra-thin antipollution composite nanometer filtering film of phytic acid assembling |
| CN112221362A (en) * | 2020-10-21 | 2021-01-15 | 天津大学 | Quaternized polysulfone homogeneous membrane with ion cluster structure, and preparation and application thereof |
| CN113509845A (en) * | 2021-04-27 | 2021-10-19 | 北京工业大学 | Preparation method of graphene oxide-cage type oligomeric silsesquioxane hybrid membrane for preferential alcohol permeation |
| CN115093703A (en) * | 2022-06-02 | 2022-09-23 | 湖南美柏生物医药有限公司 | Polymer carrier with nano-pore structure for cell culture and preparation method and application thereof |
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| CN108912366A (en) * | 2018-06-06 | 2018-11-30 | 计冲 | A kind of three-dimensional structure and deformation order are adjustable from moulding material and preparation method thereof |
| CN108912366B (en) * | 2018-06-06 | 2021-08-06 | 计冲 | Self-shaping material with adjustable three-dimensional structure and deformation sequence and preparation method thereof |
| CN109012183A (en) * | 2018-07-09 | 2018-12-18 | 天津大学 | A kind of preparation method of the ultra-thin antipollution composite nanometer filtering film of phytic acid assembling |
| CN109012183B (en) * | 2018-07-09 | 2021-02-09 | 天津大学 | Preparation method of ultra-thin anti-pollution composite nanofiltration membrane assembled by phytic acid |
| CN112221362A (en) * | 2020-10-21 | 2021-01-15 | 天津大学 | Quaternized polysulfone homogeneous membrane with ion cluster structure, and preparation and application thereof |
| CN113509845A (en) * | 2021-04-27 | 2021-10-19 | 北京工业大学 | Preparation method of graphene oxide-cage type oligomeric silsesquioxane hybrid membrane for preferential alcohol permeation |
| CN115093703A (en) * | 2022-06-02 | 2022-09-23 | 湖南美柏生物医药有限公司 | Polymer carrier with nano-pore structure for cell culture and preparation method and application thereof |
| CN115093703B (en) * | 2022-06-02 | 2024-02-02 | 湖南美柏生物医药有限公司 | Polymer carrier with nano-pore structure for cell culture and preparation method and application thereof |
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