CN105327622B - A kind of preparation method of water process flat board hybrid membranes - Google Patents
A kind of preparation method of water process flat board hybrid membranes Download PDFInfo
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- CN105327622B CN105327622B CN201410276344.5A CN201410276344A CN105327622B CN 105327622 B CN105327622 B CN 105327622B CN 201410276344 A CN201410276344 A CN 201410276344A CN 105327622 B CN105327622 B CN 105327622B
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Abstract
The present invention relates to functional material, film preparation and field of environment protection; the preparation method of specifically a kind of water process flat board hybrid membranes; more particularly to a kind of technology of preparing of organic-inorganic flat board hybrid membranes; described flat board hybrid membranes contain the water-soluble oligomerization cyclodextrin of synthesis, and the water-soluble oligomerization cyclodextrin is blended with film polymeric material using blending technology.The preparation method of water process of the present invention flat board hybrid membranes, additive is compounded due to the addition of the organic-inorganic being made up of water-soluble oligomerization cyclodextrin, inorganic nano-particle and the surfactant synthesized, mechanical strength, hydrophily and the Scavenging activity to organic pollutants in water body of obtained flat board hybrid membranes are further enhanced, and equipment needed for the preparation method is common equipment, technique is easy, easily realize industrialization.
Description
Technical field
The present invention relates to functional material, film preparation and field of environment protection, specifically a kind of water process flat board hydridization
The preparation method of milipore filter, espespecially a kind of water-soluble oligomerization cyclodextrin, inorganic nano-particle and surface-active that with the addition of synthesis
The preparation method of the organic and inorganic flat board hybrid membranes of agent.The flat board hybrid membranes can be used for wastewater treatment and reuse.
Background technology
China is one of country of water resource critical shortage, with fast development economic in recent years, large-scale industry
Production also generates a large amount of trade effluents (waste water) while great lot of water resources is consumed, and makes water resource pollution increasingly serious, enters
One step reduces the availability of water resource, therefore difficult to alleviate this in the urgent need to developing suitable sewage recycling technology
Topic.
Membrane separation technique is exactly a kind of effective sewage recycling technology, is 21st century most potential unit
One of operation.Membrane separation technique has many advantages that such as separation process is not undergone phase transition, energy consumption is low, separation is big, can be continuous
Operation, efficiency high, non-secondary pollution, operation temperature is low, device is simple, easy to operate etc..Compared with conventional biologic treating technique,
There is membrane bioreactor in membrane separation technique stable effluent quality, impact resistance to be combined, surplus sludge volume is few, pollutant
The advantages of clearance is high, but membrane pollution problem is frequently present of in the treatment of waste water, making the processing cost of waste water increases, influence film point
From the popularization and application of technology.Therefore how to control fouling membrane, extend the service life of film as in membrane bioreactor research
One focus.
Research finds, the pollutant such as organic matter, inorganic matter, colloidal sol, granular substance and microorganism film surface absorption,
Block the main cause that fenestra is considered as fouling membrane.Material of preparing such as polysulfones compound (such as polysulfones, polyether sulfone) and contain
Fluoropolymer (such as Kynoar) is the material of preparing of high comprehensive performance, but due to these material of preparing in itself dredge
It is aqueous easily to cause macromolecular, colloid, electrolyte and particle etc. in film surface or the deposition of film inside irreversible, thereby result in film dirty
Dye makes membrane flux constantly decline, so that membrane separating process can not be normally carried out.
The hydrophilic modification of hydrophobic film is the effective ways for mitigating fouling membrane, mainly passes through blending and modifying, surface at present
Coat with surface graft modification to improve the hydrophily of film, and then improve the contamination resistance of film.But, surface coating is easily de-
Fall, surface graft modification is difficult to obtain uniform Modified Membrane, and to be then one kind take blending and modifying on the basis of existing membrane material
The long short-cut method for mending short improvement film properties：By the way that hydrophilic component is introduced into casting solution with hydrophilic macromolecule or small molecule blending
In system, so that the performance of film is improved.
In terms of blending and modifying, as theoretical continuous progress is blended in polymer, by two or more polymer or inorganic receive
Rice corpuscles is blended, and preparation polymer organic-inorganic hybrid membrane is had become in theory, membrane material modified, increase membrane material is carried out
Kind, the effective ways for improving film properties, organic blended modifier of the material of preparing such as polysulfones and Kynoar it has been reported that
Tens kinds, and improve film properties using water-soluble oligomerization cyclodextrin, improve the contamination resistance of film and prepare for water process
Hybridized film have not been reported.
The content of the invention
For defect present in prior art, it is an object of the invention to provide a kind of flat board hydridization ultrafiltration of water process
The preparation method of film, milipore filter high mechanical strength that the preparation method is obtained, water flux is big, rejection is moderate, contamination resistance
By force.
To achieve the above objectives, the present invention is adopted the technical scheme that：
A kind of preparation method of water process flat board hybrid membranes, it is characterised in that：
Cyclodextrin is first prepared into water-soluble oligomerization cyclodextrin using crosslinking agent in the basic conditions, blending technology is recycled
By the water-soluble oligomerization cyclodextrin and film polymeric material blending, the filmogen of excellent performance is made；
During inversion of phases, interfacial free energy minimumization can drive the hydrophilic segment of water-soluble oligomerization cyclodextrin in film table
Face forms stable hydrated sheath, the non-specific adsorption of contaminant restraining, and the hydrophobic segment of water-soluble oligomerization cyclodextrin, which passes through, to be dredged
Aqueous interaction is wound with main body material of preparing, stable to be anchored on film surface, it is ensured that film surface anti-pollution performance it is long-term steady
It is qualitative；
Inorganic nano-particle is added in the process for preparation of casting solution, surfactant is added, improves organic phase and nothing
Macromolecule continuous phase and the compatibility of inorganic dispersed phase two-phase interface in the compatibility of machine phase two-phase interface, regulation casting solution, make
Inorganic nano-particle is obtained to be uniformly distributed and be stabilized in casting solution.
On the basis of above-mentioned technical proposal, following steps are specifically included：
Step 1: water-soluble oligomerization cyclodextrin CDP preparation：
Sodium hydrate aqueous solution and sodium borohydride are taken, the cyclodextrin that recrystallization is gone after the removal of impurity is added, stirs and be warming up to
40~60 DEG C, crosslinking agent is then added, CDP is obtained；
Step 2: the preparation of casting solution：
Inorganic nano-particle and surfactant are added into a organic solvent and are configured to mixed liquor 1,
Dried polymeric film material is dissolved in another organic solvent and is configured to mixed liquor 2,
Mixed liquor 2 and mixed liquor 1 are mixed, then add CDP prepared by step one thereto, continuing stirring makes it fully molten
Swollen dissolving, stands, filters, casting solution is made in vacuumizing and defoaming；
Or：
In organic solvent, first inorganic nano-particle and surfactant are added, then by dried polymer membrane material
Material addition, finally adds CDP prepared by step one thereto again, and continuing stirring makes it fully be swelled dissolving, stands, filters, takes out
Casting solution is made in vacuum defoamation；
Step 3: being prepared into flat board hybrid membranes with casting solution made from step 2.
On the basis of above-mentioned technical proposal, in step one, the sodium hydroxide that mass percent concentration is 25~45% is taken
The aqueous solution and sodium borohydride, under 80~200rpm rotating speeds, add the cyclodextrin that recrystallization is gone after the removal of impurity, continue permanent at room temperature
Speed stirring 8~12h, be warming up to 40~60 DEG C, then add crosslinking agent react 4~8h after, acid adding regulation mixture pH value to
7, continue to stir 1~4h, stirring obtains CDP after terminating rear rotary evaporation, 70 DEG C of vacuum drying.
On the basis of above-mentioned technical proposal, the addition of each component needs to meet in step one：Every 100~200mL hydrogen-oxygens
Change in sodium water solution, add 50~150ml of crosslinking agent, add 0.1~0.5g of sodium borohydride, 70~120g of addition cyclodextrin.
On the basis of above-mentioned technical proposal, in step 2, inorganic nano-particle and surfactant are added into portion has
Machine solvent, mixed liquor 1 is uniformly configured in 200~400rpm high-speed stirreds,
Dried polymeric film material is dissolved in another organic solvent, heat temperature raising, under the conditions of 50~80 DEG C
It is stirred well to polymeric film material and is completely dissolved and is configured to mixed liquor 2,
Poured into mixed liquor 2 under mixed liquor 1, stirring condition, then add CDP prepared by step one thereto, continue to stir
Mixing makes it fully be swelled dissolving, stands, filters, casting solution is made in vacuumizing and defoaming.
On the basis of above-mentioned technical proposal, the mass percent of each component is respectively in casting solution made from step 2：
Polymeric film material 12~22%, CDP1~10%, inorganic nano-particle 0.1~5%, surfactant 0.05~3%, remaining
For organic solvent.
On the basis of above-mentioned technical proposal, cyclodextrin described in step one is alpha-cyclodextrin, beta-schardinger dextrin, γ-ring paste
The combination of any one or two or more arbitrary proportions in essence.
On the basis of above-mentioned technical proposal, crosslinking agent described in step one is epoxychloropropane, 1,2- ethylene glycol two contracts
Any one in water glycerin ether, toluene di-isocyanate(TDI), 1,2- butanediol diglycidyl ethers.
On the basis of above-mentioned technical proposal, inorganic nano-particle described in step 2 is nano silicon (SiO2)、
Nano titanium oxide (TiO2), nano zirconium dioxide (ZrO2), nano-aluminium oxide (Al2O3) in any one or two kinds
The combination of any of the above ratio.
On the basis of above-mentioned technical proposal, surfactant described in step 2 is dodecyl sodium sulfate, dodecane
Base sodium sulphate, polyoxyethylene sorbitan monolaurate, Tween-80, octyl phenyl polyoxyethylene
Any one in ether, neopelex.
On the basis of above-mentioned technical proposal, organic solvent described in step 2 be DMA (DMAc),
Any one in DMF (DMF), 1-METHYLPYRROLIDONE (NMP) or dimethyl sulfoxide (DMSO).
On the basis of above-mentioned technical proposal, polymeric film material described in step 2 is polysulfones, polyether sulfone, benzodiazine
The combination of any one or two or more arbitrary proportions in polyethersulfone ketone, Kynoar.
On the basis of above-mentioned technical proposal, the preparation process of step 3 flat board hybrid membranes is as follows：
First thickness is installed for 115~125 μm of polyester non-woven fabric basement membrane on knifing machine, then by the casting solution prepared
Pour into knifing machine hopper, adjust the thickness walked between cloth speed and scraper and basement membrane of basement membrane, carry out knifing and obtain nascent multiple
Film is closed, after nascent composite membrane is run in atmosphere, the freezing film into 18 DEG C~30 DEG C of deionized water coagulating bath is submerged initially in, then
After hole processing being protected through washing in 6~12 hours, immersion in 12~24 hours, you can polymer flat plate hybrid membranes are made.
On the basis of above-mentioned technical proposal, the cloth speed of walking of basement membrane is 0.8~1.6m/min, between scraper and basement membrane
Thickness is 100~250 μm.
On the basis of above-mentioned technical proposal, it is that mass percentage concentration is 20~50% that hole processing solution used is protected in immersion
Glycerine water solution.
Compared with prior art, the preparation method of water process of the present invention flat board hybrid membranes, with following
Advantage：
(1) the water-soluble oligomerization cyclodextrin obtained by the present invention is with after the blending of polymer material of preparing, being remarkably improved film
Water flux, the role of network of oligomerization cyclodextrin makes the hydrophily of film improve more lasting, overcomes polymer film
Hydrophily is with the rapid defect of time decay；Meanwhile, after cyclodextrin is aggregated, due to the increase of per unit volume concentration, paste ring
Smart cavity is improved to the inclusion ability of mononuclear aromatics, polycyclic aromatic hydrocarbon, can effectively remove the cyclophane hydrocarbon pollutant of more difficult removing in water removal.
(2) the inorganic nano-particle such as titanium dioxide (TiO that the present invention is added2), zirconium dioxide (ZrO2) etc. have Gao Rong
Point, higher boiling, chemical stability are good, high antibiotic property, high-hydrophilic the features such as, and in alkaline medium and strong electrolytic solution show
Extremely strong stability is shown, therefore addition can improve the mechanical strength and stability of film in casting solution, strengthen the anti-soil of film
Dye ability；In addition, the surfactant that the present invention is added can improve in the agglomeration of inorganic nano-particle, regulation casting solution
Macromolecule continuous phase and the compatibility of inorganic dispersed phase two-phase interface.
(3) preparation of water-soluble oligomerization cyclodextrin and film-forming process technique is simple, reproducible, easy industry in the present invention
Amplification, the organic and inorganic complex additive added in casting solution (the water-soluble oligomerization cyclodextrin of synthesis, inorganic nano-particle and
Surfactant constitutes the organic and inorganic complex additive), collective effect improves the hydrophily of film, further increases
Membrane flux, while making the mechanical strength of film strengthens, antifouling property obtains larger raising, can be widely used for wastewater treatment and reuse
Water treatment system.
Embodiment
The preparation method of water process of the present invention flat board hybrid membranes, first uses cyclodextrin in the basic conditions
Crosslinking agent prepares water-soluble oligomerization cyclodextrin, improves the hydrophilicity of cyclodextrin, recycles blending technology will be water-soluble few
Cyclodextrin polymer and film polymeric material blending, are made the filmogen of excellent performance, during inversion of phases, interfacial free energy
Minimumization can drive the hydrophilic segment of water-soluble oligomerization cyclodextrin to form stable hydrated sheath on film surface, contaminant restraining it is non-
Specific adsorption, the hydrophobic segment of water-soluble oligomerization cyclodextrin is wound by hydrophobic interaction and main body material of preparing, surely
Surely it is anchored on film surface, it is ensured that the long-time stability of film surface anti-pollution performance；Then added in the process for preparation of casting solution
Inorganic nano-particle adds surfactant to improve mechanical strength, resistance to compression and the stability of film, permeated using it,
Emulsification, improves in the compatibility of organic phase and inorganic phase two-phase interface, regulation casting solution macromolecule continuous phase and inorganic point
The compatibility of dephasing two-phase interface so that inorganic nano-particle is uniformly distributed and is stabilized in casting solution, while surface is lived
Property agent can also adjust casting solution and the boundary material exchange velocity of coagulating bath, make the fenestra of prepared film uniform.
The filming technology of the present invention is easy to large-scale production and application, and prepared film without water-soluble oligomerization ring with pasting
The film of the blend components such as essence is compared, and contact angle reduces, water flux and mechanical strength raising, antipollution and fungus resistance can strengthen, can
It is widely used in wastewater treatment and the water treatment system of reuse.
The water process of the present invention preparation method of flat board hybrid membranes, specifically includes following steps：
Step 1: the preparation of water-soluble oligomerization cyclodextrin (CDP)：
Sodium hydrate aqueous solution and sodium borohydride that mass percent concentration is 25~45% are taken, in 80~200rpm rotating speeds
Under, the cyclodextrin that recrystallization is gone after the removal of impurity is added, continues constant speed at room temperature and stirs 8~12h, be warming up to 40~60 DEG C, then
(rapidly joining) crosslinking agent is added to react after 4~8h, the pH value of acid adding (such as hydrochloric acid) regulation mixture to 7, continue to stir 1~
4h, stirring obtains CDP after terminating rear rotary evaporation, 70 DEG C of vacuum drying；
Wherein：The addition of each component needs to meet in step one：In every 100~200mL sodium hydrate aqueous solutions, addition is handed over
Join 50~150ml of agent, add 0.1~0.5g of sodium borohydride, 70~120g of addition cyclodextrin.
Step 2: the preparation of casting solution：
Take organic solvent and be divided into two parts,
Inorganic nano-particle and surfactant are added into a organic solvent, it is uniform in 200~400rpm high-speed stirreds
Mixed liquor 1 is configured to,
Dried polymeric film material is dissolved in another organic solvent, heat temperature raising, under the conditions of 50~80 DEG C
It is stirred well to polymeric film material and is completely dissolved and is configured to mixed liquor 2,
Poured into mixed liquor 2 under mixed liquor 1, stirring condition, then add CDP prepared by step one thereto, continue to stir
Mixing makes it fully be swelled dissolving, stands, filters, casting solution is made in vacuumizing and defoaming；
Or：
Under stirring condition, in organic solvent, first inorganic nano-particle and surfactant are added, then will be dried
Polymeric film material is added, and finally adds CDP prepared by step one thereto again, and continuing stirring makes it fully be swelled dissolving, quiet
Put, filter, casting solution is made in vacuumizing and defoaming；
Wherein：The mass percent of each component is respectively in casting solution made from step 2：Polymeric film material 12~
22%th, CDP1~10%, inorganic nano-particle 0.1~5%, surfactant 0.05~3%, remaining is organic solvent；
Step 3: being prepared into flat board hybrid membranes with casting solution made from step 2.
On the basis of above-mentioned technical proposal, cyclodextrin described in step one is alpha-cyclodextrin, beta-schardinger dextrin, γ-ring paste
The combination of any one or two or more arbitrary proportions in essence, preferably beta-schardinger dextrin.
Cyclodextrin be a class by a kind of cyclic oligosaccharide of the D- glucopyranoses by α-Isosorbide-5-Nitrae glucosides key joint,
The number of wherein glucose residue is generally 6,7,8, is referred to as alpha-cyclodextrin, beta-schardinger dextrin, gamma-cyclodextrin.Its molecule structure
Type is more special, in hollow round table shape, and cavity inside arranges that to match somebody with somebody glycosyloxy bridge atom, the hydrogen on glucopyranose ring C3, C5 former
Son, in cavity and is covered with glycosyloxy atom, cavity inside is turned into hydrophobicity space；Cyclodextrin molecular cavity edge contains
There is hydroxyl, it is hydrophily to make cavity external presentation.Its polymer-cyclodextrin (Cyclodextrin Polymer) is
Refer to by cyclodextrin molecular be chemically bonded or physics compounding method group enter formed by macromolecular structure contain multiple cyclodextrin lists
The polymeric derivative of member.This polymer had both preferably maintained the inclusion recognition capability of cyclodextrin, have concurrently again polymer compared with
Good mechanical strength, stability and chemical adjustability etc., the comprehensive function of cyclodextrin cavity and polymer network improves material
Performance, also made moderate progress in terms of hydrophily in addition.And oligomerization cyclodextrin is then the water for including 2~7 cyclodextrin units
Soluble cyclodextrin oligomer, the cyclodextrin solubility property by crosslinkings such as epoxychloropropane is greatly improved, and such as works as β-ring
When dextrin is crosslinked with the epoxy-terminated oligomer of some bands, the solubility of obtained beta cyclo dextrin polymer even compares beta-schardinger dextrin
It is big 40 times.
On the basis of above-mentioned technical proposal, crosslinking agent described in step one is epoxychloropropane, 1,2- ethylene glycol two contracts
Any one in water glycerin ether, toluene di-isocyanate(TDI), 1,2- butanediol diglycidyl ethers, preferably epoxychloropropane.
On the basis of above-mentioned technical proposal, inorganic nano-particle described in step 2 is nano silicon (SiO2)、
Nano titanium oxide (TiO2), nano zirconium dioxide (ZrO2), nano-aluminium oxide (Al2O3) in any one or two kinds
The combination of any of the above ratio.
On the basis of above-mentioned technical proposal, surfactant described in step 2 is dodecyl sodium sulfate, dodecane
Base sodium sulphate, polyoxyethylene sorbitan monolaurate, Tween-80, octyl phenyl polyoxyethylene
Any one in ether, neopelex, preferably dodecyl sodium sulfate.
On the basis of above-mentioned technical proposal, organic solvent described in step 2 be DMA (DMAc),
Any one in DMF (DMF), 1-METHYLPYRROLIDONE (NMP) or dimethyl sulfoxide (DMSO), preferably N- methyl
Pyrrolidones (NMP).
On the basis of above-mentioned technical proposal, polymeric film material described in step 2 is polysulfones, polyether sulfone, benzodiazine
The combination of any one or two or more arbitrary proportions in polyethersulfone ketone, Kynoar.
On the basis of such scheme, the preparation process of step 3 flat board hybrid membranes is as follows：First by thickness be 115~
125 μm of polyester non-woven fabric basement membrane (commercially available) is installed on knifing machine, then the casting solution prepared is poured into knifing machine hopper,
The thickness walked between cloth speed and scraper and basement membrane of basement membrane is adjusted, knifing is carried out and obtains nascent composite membrane, nascent composite membrane exists
After being run in air, the freezing film into 18 DEG C~30 DEG C of deionized water coagulating bath is submerged initially in, then washed through 6~12 hours,
Immersion in 12~24 hours is protected after the processing of hole, you can polymer flat plate hybrid membranes are made.
On the basis of above-mentioned technical proposal, the cloth speed of walking of basement membrane is 0.8~1.6m/min, between scraper and basement membrane
Thickness is 100~250 μm.
On the basis of above-mentioned technical proposal, it is that mass percentage concentration is 20~50% that hole processing solution used is protected in immersion
Glycerine water solution.
It is specific embodiment below, described embodiment is not construed as limiting the invention only to explain the present invention,
The person skilled in the art in the field can make some nonessential modifications and adaptations according to the content of the invention described above.
The present invention is tested by strainability the performance of prepared polymer flat plate hybrid membranes, hydrophilicity is surveyed
Try and the removal capacity test of PAH is characterized.
1st, strainability is tested
The strainability of polymer flat plate hybrid membranes is characterized by pure water flux, pure water flux by dead end outside
Press filtering device is measured, and the polymer flat plate hybrid membranes that will be prepared are cut into circular film after drying naturally, are put into
In ultrafiltration cup, the first precompressed 30min under 0.15Mpa, until water flux is basicly stable, then the pure water of measure film leads under 0.1MPa
Amount.
2nd, hydrophilicity is tested
The hydrophilicity of polymer flat plate hybrid membranes is characterized by contact angle, i.e., with three-stage distillation water with drop of lying
Method determines contact angle on DSA100 contact angle instruments (KR ü SS GmbH, Germany).
3rd, the removal capacity of PAH is tested
Polymer flat plate hybrid membranes are entered to the removal capacity of PAH by the clearance to phenol in simulated water sample
Row is determined, that is, prepares 2.0mg/ml phenol solution, by the polymer flat plate hybrid membranes submergence of above-mentioned preparation wherein, vibration
Absorption 24 hours, is determined at through the polymer flat plate hybrid membranes with UV-9100 dual-beams ultra-violet and visible spectrophotometer
The concentration of phenol in simulated water sample before and after reason, so as to calculate the clearance of phenol in simulated water sample.
Embodiment 1
The sodium hydrate aqueous solution that 150mL mass percentage concentrations are 35% is measured, is mixed with 0.2g sodium borohydrides,
Under 100rpm rotating speeds, the beta-schardinger dextrin 90g added after recrystallization, constant speed stirring 10h, is rapidly joined after being warming up to 50 DEG C at room temperature
After 70mL epichlorohydrin reactions 6h, acid adding regulation mixture ph continues to stir 2 hours up to 7, and stirring rotates steaming after terminating
Oligomerization cyclodextrin CDP is obtained after hair, 70 DEG C of vacuum drying.
Under 300rpm rotating speed stirring conditions, by 20g inorganic nano-particle additives nano titanium oxide, 5g surfactants
Polyoxyethylene sorbitan monolaurate is dissolved in 500g organic solvent 1-METHYLPYRROLIDONEs, is stirred and is configured to mixing
Liquid, then the 275g 1-METHYLPYRROLIDONE solution of the dried polyether sulfone containing 150g is added into the mixed liquor, it is heated to
70 DEG C, it is stirred well to polymeric film material and is completely dissolved, continue under stirring condition, adds prepared by step one to above-mentioned solution
CDP50g, continuing stirring makes it fully be swelled dissolving, stands, filters, casting solution is made in vacuumizing and defoaming.
Polyester non-woven fabric basement membrane is installed on knifing machine, then the casting solution prepared is poured into knifing machine hopper, is adjusted
The cloth speed of walking of integral basis film is 1.0m/min, and the thickness between scraper and basement membrane is 150 μm, carries out knifing and obtains nascent compound
Film, after nascent composite membrane is run in atmosphere, is immersed in freezing film in 25 DEG C of deionized water coagulating baths, is washed through 12 hours,
Again after hole processing is protected in immersion for 24 hours during concentration is 20% glycerine water solution, polymer flat plate hybrid membranes, warp are made
It is 1219.9L/h.m to determine obtained polymer flat plate hybrid membranes its pure water flux under the conditions of 0.1MPa2, contact angle
For 69.1 °, the clearance to phenol in simulated water sample is 95.6%.
Embodiment 2
The sodium hydrate aqueous solution that 100mL mass percentage concentrations are 45% is measured, is mixed with 0.1g sodium borohydrides,
Under 80rpm rotating speeds, the alpha-cyclodextrin 70g added after recrystallization, constant speed stirring 8h, is rapidly joined after being warming up to 40 DEG C at room temperature
After 50mL1,2- ethylene glycol diglycidylether reaction 8h, acid adding regulation continues to stir 1 hour, stirred until mixture ph to 7
Oligomerization cyclodextrin CDP is obtained after mixing the rotated evaporation of reactant after end, 70 DEG C of vacuum drying.
Under the conditions of 400rpm high-speed stirreds, by 1g inorganic nano-particle additives nano silicon, 0.5g surface-actives
Agent Tween-80 is dissolved in 500g organic solvent DMAs, is stirred and is configured to mix
Liquid is closed, then the 368.5g DMAs of the dried polysulfones containing 120g are added into the mixed liquor, is heated to
50 DEG C, it is stirred well to polymeric film material and is completely dissolved, continue under stirring condition, adds prepared by step one to above-mentioned solution
CDP10g, continuing stirring makes it fully be swelled dissolving, stands, filters, casting solution is made in vacuumizing and defoaming.
Polyester non-woven fabric basement membrane is installed on knifing machine, then the casting solution prepared is poured into knifing machine hopper, is adjusted
The cloth speed of walking of integral basis film is 1.2m/min, and the thickness between scraper and basement membrane is 250 μm, carries out knifing and obtains nascent compound
Film, after nascent composite membrane is run in atmosphere, is immersed in freezing film in 18 DEG C of deionized water coagulating baths, is washed through 10 hours,
Again after hole processing is protected in immersion for 12 hours during concentration is 30% glycerine water solution, polymer flat plate hybrid membranes, warp are made
It is 921.4L/h.m to determine obtained polymer flat plate hybrid membranes its pure water flux under the conditions of 0.1MPa2, contact angle
For 84.6 °, the clearance to phenol in simulated water sample is 75.3%.
Embodiment 3
The sodium hydrate aqueous solution that 200mL mass percentage concentrations are 25% is measured, is mixed with 0.3g sodium borohydrides,
Under 120rpm rotating speeds, the gamma-cyclodextrin 100g added after recrystallization, constant speed stirring 12h, is warming up to after 60 DEG C and quickly adds at room temperature
Enter after 120mL toluene di-isocyanate(TDI)s reaction 4h, acid adding continues to stir 4 hours, after stirring terminates until mixture ph to 7
Oligomerization cyclodextrin CDP is obtained after rotated evaporation, 70 DEG C of vacuum drying.
Under 300rpm rotating speed stirring conditions, by 50g inorganic nano-particle additives nano zirconium dioxide, 30g surface-actives
Agent neopelex is dissolved in 400g organic solvent DMFs, is stirred and is configured to mixed liquor, then
The 200g DMFs of the dried benzodiazine polyethersulfone ketone containing 220g are added into the mixed liquor, heating rises
Temperature is stirred well to polymeric film material and is completely dissolved to 80 DEG C, continues under stirring condition, and adding step one to above-mentioned solution makes
Standby CDP100g, continuing stirring makes it fully be swelled dissolving, stands, filters, casting solution is made in vacuumizing and defoaming.
Polyester non-woven fabric basement membrane is installed on knifing machine, then the casting solution prepared is poured into knifing machine hopper, is adjusted
The cloth speed of walking of integral basis film is 1.6m/min, and the thickness between scraper and basement membrane is 200 μm, carries out knifing and obtains nascent compound
Film, after nascent composite membrane is run in atmosphere, is immersed in freezing film in 30 DEG C of deionized water coagulating baths, is washed through 6 hours, then
After hole processing is protected in immersion for 20 hours during concentration is 50% glycerine water solution, polymer flat plate hybrid membranes are made, through surveying
Fixed obtained polymer flat plate hybrid membranes its pure water flux under the conditions of 0.1MPa is 786.3L/h.m2, contact angle is
89.7 °, the clearance to phenol in simulated water sample is 92.1%.
Embodiment 4
The sodium hydrate aqueous solution that 180mL mass percentage concentrations are 40% is measured, is mixed with 0.5g sodium borohydrides,
Under 100rpm rotating speeds, alpha-cyclodextrin 60g, the gamma-cyclodextrin 60g added after recrystallization, constant speed stirring 9h, is warming up to 50 at room temperature
Rapidly joined after DEG C after 150mL1,2- butanediol diglycidyl ethers reaction 5h, acid adding is adjusted until mixture ph to 7, after
Continuous stirring 3 hours, stirring obtains oligomerization cyclodextrin CDP after terminating after rotary evaporation, 70 DEG C of vacuum drying.
Under 250rpm rotating speed stirring conditions, 10g nano titanium oxides and 10g nano silicon inorganic nano-particles are added
Plus agent, 10g surfactant sodium dodecyl base sodium sulfonates are dissolved in 500g organic solvent 1-METHYLPYRROLIDONEs, stir preparation
Into mixed liquor, then add into the mixed liquor 250g 1-METHYLPYRROLIDONEs of the dried Kynoar containing 140g, heating
80 DEG C are warming up to, polymeric film material is stirred well to and is completely dissolved, is continued under stirring condition, step one is added to above-mentioned solution
The CDP80g of preparation, continuing stirring makes it fully be swelled dissolving, stands, filters, casting solution is made in vacuumizing and defoaming.
Polyester non-woven fabric basement membrane is installed on knifing machine, then the casting solution prepared is poured into knifing machine hopper, is adjusted
The cloth speed of walking of integral basis film is 0.8m/min, and the thickness between scraper and basement membrane is 100 μm, carries out knifing and obtains nascent compound
Film, after nascent composite membrane is run in atmosphere, is immersed in freezing film in 20 DEG C of deionized water coagulating baths, is washed through 8 hours, then
After hole processing is protected in immersion for 18 hours during concentration is 50% glycerine water solution, polymer flat plate hybrid membranes are made, through surveying
Fixed obtained polymer flat plate hybrid membranes its pure water flux under the conditions of 0.1MPa is 1078.5L/h.m2, contact angle is
78.3 °, the clearance to phenol in simulated water sample is 90.6%.
Embodiment 5
The sodium hydrate aqueous solution that 120mL mass percentage concentrations are 30% is measured, is mixed with 0.4g sodium borohydrides,
Under 90rpm rotating speeds, alpha-cyclodextrin 30g, beta-schardinger dextrin 50g, the gamma-cyclodextrin cyclodextrin 30g added after recrystallization is permanent at room temperature
Speed stirring 10h, is warming up to after 60 DEG C and rapidly joins after 100mL epichlorohydrin reactions 4h, acid adding until mixture ph is to 7,
Continue to stir 2 hours, stirring obtains oligomerization cyclodextrin CDP after terminating after rotary evaporation, 70 DEG C of vacuum drying.
Under 220rpm rotating speed stirring conditions, by 10g nano zirconium dioxides and 10g nano silicons and 10g nano-silicas
Change Ti-inorganic nano particle additive, 20g Surfactant SDSs and be dissolved in 500g organic solvent N- methylpyrroles
In alkanone, stir and be configured to mixed liquor, then add into the mixed liquor containing the dried polyether sulfones of 100g and 60g polysulfones
230g 1-METHYLPYRROLIDONEs, are heated to 70 DEG C, are stirred well to polymeric film material and are completely dissolved, and continue stirring bar
Under part, CDP60g prepared by step one is added to above-mentioned solution, continuing stirring makes it fully be swelled dissolving, stands, filters, and takes out true
Casting solution is made in empty deaeration.
Polyester non-woven fabric basement membrane is installed on knifing machine, then the casting solution prepared is poured into knifing machine hopper, is adjusted
The cloth speed of walking of integral basis film is 1.1m/min, and the thickness between scraper and basement membrane is 120 μm, carries out knifing and obtains nascent compound
Film, after nascent composite membrane is run in atmosphere, is immersed in freezing film in 25 DEG C of deionized water coagulating baths, is washed through 12 hours,
Again after hole processing is protected in immersion for 18 hours during concentration is 40% glycerine water solution, polymer flat plate hybrid membranes, warp are made
It is 621.4L/h.m to determine obtained polymer flat plate hybrid membranes its pure water flux under the conditions of 0.1MPa2, contact angle
For 91.2 °, the clearance to phenol in simulated water sample is 85.3%.
Embodiment 6
The sodium hydrate aqueous solution that 160mL mass percentage concentrations are 30% is measured, is mixed with 0.3g sodium borohydrides,
Under 110rpm rotating speeds, add recrystallization after alpha-cyclodextrin 20g, beta-schardinger dextrin 40g, gamma-cyclodextrin 20g, at room temperature constant speed stir
11h is mixed, is warming up to after 50 DEG C and rapidly joins 100mL1, after 2- ethylene glycol diglycidylethers reaction 6h, acid adding is until mixture
PH value continues to stir 2 hours to 7, and stirring obtains oligomerization cyclodextrin CDP after terminating after rotary evaporation, 70 DEG C of vacuum drying.
Under the conditions of 350rpm high-speed stirreds, 30g inorganic nano-particle additives nano-aluminium oxide, 25g surfaces are lived
Property agent octyl phenyl polyoxyethylene ether be dissolved in 400g organic solvent DMAs, stir be configured to mixing
Liquid, then add into the mixed liquor 275g N, N- bis- containing the dried Kynoar of 80g, 80g polysulfones and 40g polyether sulfones
Methylacetamide, is heated to 80 DEG C, is stirred well to polymeric film material and is completely dissolved, and continues under stirring condition, upwards
State solution and add CDP70g prepared by step one, continuing stirring makes it fully be swelled dissolving, stands, filters, vacuumizing and defoaming system
Obtain casting solution.
Polyester non-woven fabric basement membrane is installed on knifing machine, then the casting solution prepared is poured into knifing machine hopper, is adjusted
The cloth speed of walking of integral basis film is 1.3m/min, and the thickness between scraper and basement membrane is 180 μm, carries out knifing and obtains nascent compound
Film, after nascent composite membrane is run in atmosphere, is immersed in freezing film in 22 DEG C of deionized water coagulating baths, is washed through 12 hours,
Again after hole processing is protected in immersion for 24 hours during concentration is 20% glycerine water solution, polymer flat plate hybrid membranes, warp are made
It is 981.9L/h.m to determine obtained polymer flat plate hybrid membranes its pure water flux under the conditions of 0.1MPa2, contact angle
For 79.1 °, the clearance to phenol in simulated water sample is 87.6%.
Comparative example 1
Under 300rpm rotating speed stirring conditions, by 20g inorganic nano-particle additives nano titanium oxide, 5g surface-actives
Agent polyoxyethylene sorbitan monolaurate is dissolved in 500g organic solvent 1-METHYLPYRROLIDONEs, is stirred and is configured to mix
Liquid is closed, then the 325g 1-METHYLPYRROLIDONEs of the dried polyether sulfone containing 150g are added into the mixed liquor, 70 are heated to
DEG C, it is stirred well to polymeric film material and is completely dissolved, continuing stirring makes it fully be swelled dissolving, stands, filters, vacuumize de-
It is brewed to obtain casting solution.
Polyester non-woven fabric basement membrane is installed on knifing machine, then the casting solution prepared is poured into knifing machine hopper, is adjusted
The cloth speed of walking of integral basis film is 1.0m/min, and the thickness between scraper and basement membrane is 150 μm, carries out knifing and obtains nascent compound
Film, after nascent composite membrane is run in atmosphere, is immersed in freezing film in 25 DEG C of deionized water coagulating baths, is washed through 12 hours,
Again after hole processing is protected in immersion for 24 hours during concentration is 20% glycerine water solution, polymer flat plate hybrid membranes, warp are made
It is 421.9L/h.m to determine obtained polymer flat plate hybrid membranes its pure water flux under the conditions of 0.1MPa2, contact angle
For 99.1 °, the clearance to phenol in simulated water sample is 13.9%.
Comparative example 2
The sodium hydrate aqueous solution that 100mL mass percentage concentrations are 45% is measured, is mixed with 0.1g sodium borohydrides,
Under 100rpm rotating speeds, the alpha-cyclodextrin 70g added after recrystallization, constant speed stirring 8h, is rapidly joined after being warming up to 40 DEG C at room temperature
After 50mL1,2- ethylene glycol diglycidylether reaction 8h, acid adding continues to stir 1 hour until mixture ph to 7, stirring knot
Oligomerization cyclodextrin CDP is obtained after Shu Houjing rotary evaporations, 70 DEG C of vacuum drying.
Under stirring condition, the dried polysulfones of 120g is dissolved in 870g organic solvent DMAs, heated
50 DEG C are warming up to, polymeric film material is stirred well to and is completely dissolved, is continued under stirring condition, adds what is prepared to above-mentioned solution
CDP10g, continuing stirring makes it fully be swelled dissolving, stands, filters, casting solution is made in vacuumizing and defoaming.
Polyester non-woven fabric basement membrane is installed on knifing machine, then the casting solution prepared is poured into knifing machine hopper, is adjusted
The cloth speed of walking of integral basis film is 1.2m/min, and the thickness between scraper and basement membrane is 100 μm, carries out knifing and obtains nascent compound
Film, after nascent composite membrane is run in atmosphere, is immersed in freezing film in 18 DEG C of deionized water coagulating baths, is washed through 10 hours,
Again after hole processing is protected in immersion for 12 hours during concentration is 30% glycerine water solution, polymer flat plate hybrid membranes, warp are made
It is 611.4L/h.m to determine obtained polymer flat plate hybrid membranes its pure water flux under the conditions of 0.1MPa2, contact angle
For 86.6 °, the clearance to phenol in simulated water sample is 65.3%.
The content not being described in detail in this specification belongs to prior art known to professional and technical personnel in the field.
Claims (14)
1. a kind of water process preparation method of flat board hybrid membranes, it is characterised in that：
Cyclodextrin is first prepared into water-soluble oligomerization cyclodextrin using crosslinking agent in the basic conditions, recycles blending technology should
Water-soluble oligomerization cyclodextrin and film polymeric material blending, are made the filmogen of excellent performance；
During inversion of phases, interfacial free energy minimumization can drive the hydrophilic segment of water-soluble oligomerization cyclodextrin in film surface shape
Into stable hydrated sheath, the non-specific adsorption of contaminant restraining, the hydrophobic segment of water-soluble oligomerization cyclodextrin passes through hydrophobicity
Interaction is wound with main body material of preparing, stable to be anchored on film surface, it is ensured that the long-time stability of film surface anti-pollution performance；
Inorganic nano-particle is added in the process for preparation of casting solution, surfactant is added, improves organic phase and inorganic phase
Macromolecule continuous phase and the compatibility of inorganic dispersed phase two-phase interface in the compatibility of two-phase interface, regulation casting solution so that nothing
Machine nano-particle is uniformly distributed and is stabilized in casting solution；
Specifically include following steps：
Step 1: water-soluble oligomerization cyclodextrin CDP preparation：
Take sodium hydrate aqueous solution and sodium borohydride, add the cyclodextrin that recrystallization is gone after the removal of impurity, stir and it is warming up to 40~
60 DEG C, crosslinking agent is then added, CDP is obtained；
Step 2: the preparation of casting solution：
Inorganic nano-particle and surfactant are added into a organic solvent and are configured to mixed liquor 1,
Dried polymeric film material is dissolved in another organic solvent and is configured to mixed liquor 2,
Mixed liquor 2 and mixed liquor 1 are mixed, then add CDP prepared by step one thereto, it is molten that continuation stirring makes it fully be swelled
Solution, stands, filters, casting solution is made in vacuumizing and defoaming；
Or：
In organic solvent, first inorganic nano-particle and surfactant are added, then dried polymeric film material is added
Enter, finally add CDP prepared by step one thereto again, continuing stirring makes it fully be swelled dissolving, stands, filters, vacuumizes
Casting solution is made in deaeration；
Step 3: being prepared into flat board hybrid membranes with casting solution made from step 2.
2. the water process as claimed in claim 1 preparation method of flat board hybrid membranes, it is characterised in that：In step one,
Sodium hydrate aqueous solution and sodium borohydride that mass percent concentration is 25~45% are taken, under 80~200rpm rotating speeds, is added
The cyclodextrin gone after the removal of impurity is recrystallized, continues constant speed at room temperature and stirs 8~12h, be warming up to 40~60 DEG C, then add crosslinking
Agent is reacted after 4~8h, and the pH value of acid adding regulation mixture continues to stir 1~4h to 7, stirring terminate rear rotary evaporation, 70 DEG C it is true
Sky obtains CDP after drying.
3. the water process as claimed in claim 1 preparation method of flat board hybrid membranes, it is characterised in that：It is each in step one
The addition of component needs to meet：In every 100~200mL sodium hydrate aqueous solutions, 50~150ml of crosslinking agent is added, boron hydrogen is added
Change 0.1~0.5g of sodium, 70~120g of addition cyclodextrin.
4. the water process as claimed in claim 1 preparation method of flat board hybrid membranes, it is characterised in that：In step 2,
Inorganic nano-particle and surfactant are added into a organic solvent, are uniformly configured to mix in 200~400rpm high-speed stirreds
Liquid 1 is closed,
Dried polymeric film material is dissolved in another organic solvent, heat temperature raising, under the conditions of 50~80 DEG C fully
Stirring is completely dissolved to polymeric film material is configured to mixed liquor 2,
Poured into mixed liquor 2 under mixed liquor 1, stirring condition, then add CDP prepared by step one thereto, continuing stirring makes
It is fully swelled dissolving, stands, filters, casting solution is made in vacuumizing and defoaming.
5. the water process as claimed in claim 1 preparation method of flat board hybrid membranes, it is characterised in that：Step 2 is made
Casting solution in the mass percent of each component be respectively：Polymeric film material 12~22%, CDP 1~10%, inorganic nano
Particle 0.1~5%, surfactant 0.05~3%, remaining is organic solvent.
6. the water process as claimed in claim 1 preparation method of flat board hybrid membranes, it is characterised in that：Institute in step one
State combination of the cyclodextrin for any one in alpha-cyclodextrin, beta-schardinger dextrin, gamma-cyclodextrin or two or more arbitrary proportions.
7. the water process as claimed in claim 1 preparation method of flat board hybrid membranes, it is characterised in that：Institute in step one
State crosslinking agent and shrink sweet for epoxychloropropane, 1,2- ethylene glycol diglycidylethers, toluene di-isocyanate(TDI), 1,2- butanediols two
Any one in oily ether.
8. the water process as claimed in claim 1 preparation method of flat board hybrid membranes, it is characterised in that：Institute in step 2
Inorganic nano-particle is stated for nano silicon (SiO2), nano titanium oxide (TiO2), nano zirconium dioxide (ZrO2), nanometer
The combination of any one or two or more arbitrary proportions in alundum (Al2O3) (Al2O3).
9. the water process as claimed in claim 1 preparation method of flat board hybrid membranes, it is characterised in that：Institute in step 2
Surfactant is stated for dodecyl sodium sulfate, lauryl sodium sulfate, polyoxyethylene sorbitan monolaurate, polyoxy second
Any one in alkene sorbitan mono-oleic acid ester, octyl phenyl polyoxyethylene ether, neopelex.
10. the water process as claimed in claim 1 preparation method of flat board hybrid membranes, it is characterised in that：In step 2
The organic solvent is DMA (DMAc), DMF (DMF), 1-METHYLPYRROLIDONE
(NMP) any one or in dimethyl sulfoxide (DMSO).
11. the water process as claimed in claim 1 preparation method of flat board hybrid membranes, it is characterised in that：In step 2
The polymeric film material be any one or two kinds in polysulfones, polyether sulfone, benzodiazine polyethersulfone ketone, Kynoar with
The combination of upper arbitrary proportion.
12. the water process as claimed in claim 1 preparation method of flat board hybrid membranes, it is characterised in that：Step 3 is put down
The preparation process of plate hybrid membranes is as follows：
First thickness is installed for 115~125 μm of polyester non-woven fabric basement membrane on knifing machine, then the casting solution prepared is poured into
In knifing machine hopper, the thickness walked between cloth speed and scraper and basement membrane of basement membrane is adjusted, knifing is carried out and obtains nascent composite membrane,
After nascent composite membrane is run in atmosphere, the freezing film into 18 DEG C~30 DEG C of deionized water coagulating bath is submerged initially in, then through 6~
Washing in 12 hours, immersion in 12~24 hours are protected after the processing of hole, you can polymer flat plate hybrid membranes are made.
13. the water process as claimed in claim 12 preparation method of flat board hybrid membranes, it is characterised in that：Basement membrane is walked
Cloth speed is 0.8~1.6m/min, and the thickness between scraper and basement membrane is 100~250 μm.
14. the water process as claimed in claim 12 preparation method of flat board hybrid membranes, it is characterised in that：Hole is protected in immersion
Processing solution used is the glycerine water solution that mass percentage concentration is 20~50%.
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