CN109012197A - A kind of polyimide composite film and preparation method for infiltration evaporation processing Halite water - Google Patents
A kind of polyimide composite film and preparation method for infiltration evaporation processing Halite water Download PDFInfo
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- CN109012197A CN109012197A CN201810799995.0A CN201810799995A CN109012197A CN 109012197 A CN109012197 A CN 109012197A CN 201810799995 A CN201810799995 A CN 201810799995A CN 109012197 A CN109012197 A CN 109012197A
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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
- B01D71/58—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention belongs to field of seawater desalination, and in particular to MWCNTs-OH is filled to PAN counterdie with vacuum pump, then obtains polyimide composite film using interfacial polymerization techniques by a kind of preparation method of the polyimide composite film for infiltration evaporation processing Halite water.Composite membrane obtained mainly includes three layers, and first layer is the ultra-thin polyimides separating layer with separation function, and the second layer is the MWCNTs sub-layer of vacuum filtration filling, and third layer is the Porous-Organic base membrane layer to play a supportive role.The composite membrane is used for the infiltration evaporation desalination of high concentration salt water, has the desalination preferably to the rejection of salt water and water flux, by infiltration evaporation to high concentration salt water, reduces operating pressure, alleviate damage of the desalination processes to equipment.
Description
Technical field
The invention belongs to field of seawater desalination, and in particular to a kind of infiltration evaporation desalination for high concentration salt water has
The polyimide composite film and preparation method of ultra-thin separating layer.
Background technique
With the fast development of world population and urbanization process, shortage of water resources has become the master that today's society is faced
One of challenge.Desalting technology is one of the effective way solved the problems, such as.Compared with traditional distillation technique, membrane technology Yin Qigao
Efficiency and potential energy conservation and be generally considered the most attractive solution of desalination.Current most mature, cost phase
It is reverse osmosis (RO) to lower sea water desalination membrane technology.In recent years, high total dissolved solidss (TDS) and resistance to certain types are being handled
Pollution aspect, it has been found that the membrane process of this kind of non-depressed power drives of infiltration evaporation (PV) is more attractive.
For PV as a kind of membrane separating method, a possibility that potential desalination, has caused the more and more interest of people.
Although its in sea water desalination using less, PV has proved to be feasible and has the advantages that for some of desalination.
Firstly, PV be to the rejection of salt it is fairly good, especially for monovalent salt, be usually above 99%.Secondly as PV is a kind of
Phase transition process does not need to overcome the osmotic pressure in salt water water supply as RO, therefore PV can handle the salt water of high concentration, same
Under the conditions of small more of required operating pressure ratio RO.And the low-grade heat sources such as solar energy, geothermal energy or industrial waste heat can be with
When being efficiently used for heating raw material to certain temperature, usually within the scope of 40-75 DEG C, PV sea water desalination will be more competitive.
It is high there is presently no preparing MWCNTs/PI composite membrane using interfacial polymerization techniques and being used for infiltration evaporation processing
The relevant report of brackish water.
Summary of the invention
It is multiple that the invention patent provides a kind of ultra-thin polyimide nano material for infiltration evaporation processing Halite water
Film and preparation method thereof is closed, which can realize sea water desalination, effective use water money efficiently to high salt concentration water desalination
Source.
For polyimide composite film of the invention by up of three-layer, first layer is the ultra-thin polyimides with separation function point
Absciss layer, the second layer are multi-walled carbon nanotube (MWCNTs-OH) sub-layer of the hydroxy-functional of vacuum filtration filling, and third layer is
The Porous-Organic base membrane layer to play a supportive role；Wherein, ultra-thin polyimides separating layer is obtained by interfacial polymerization, thickness
Are as follows: 100~250nm, Porous-Organic base membrane layer are hydrophiling polyacrylonitrile (H-PAN) film.It prepares ultra-thin separating layer and incites somebody to action
It is key factor that MWCNTs-OH, which introduces nano-composite material membrane,.
The present invention is reacted on Porous-Organic basement membrane using interfacial polymerization techniques generates polyamic acid and by subsequent Asia
Amination treatment obtains one layer of ultra-thin polyimides separating layer and obtains polyimide composite film.
The MWCNTs-OH sub-layer of filling is filtered by vacuum, provides an efficient path through water, improves water flux；
And by forming one layer of sub-layer being made of carbon nanotube, the chlorine-resistant property and antifouling property of film is effectively enhanced, is reduced
Influence of the solvent to counterdie.Pass through conventional casting solution coating by the polyimides separating layer membrane thickness ratio that interfacial polymerization is formed
Method is thinner, effectively provides rejection and water flux to salt water.
A kind of method that interfacial polymerization prepares polyimides pervaporation membrane, includes the following steps:
Step (1): equal four formyl chloride of benzene (BTAC) is prepared using phosphorus pentachloride method: first adding pyromellitic dianhydride (PMDA)
Enter into flask, excessive phosphorus pentachloride (PCl is then added5), it is heated to reflux 10h, is cooled to room temperature, vacuum distillation, which removes, to be produced
Extra PCl in object5With by-product phosphorus oxychloride (POCl3), methylene chloride is added and dissolves and recrystallizes, obtains pure equal benzene four
Formyl chloride；
Step (2): sodium hydroxide solution is prepared, and impregnates polyacrylonitrile (PAN) film 1h and obtains hydrophiling polyacrylonitrile film
(H-PAN)；
Step (3): the ethanol solution (MWCNTs-OH/ of the multi-walled carbon nanotube (MWCNTs-OH) of hydroxy-functional is prepared
EtOH solution), ultrasonic disperse three times is carried out, every time lasting 15min, and 5min is stood after each dispersion, standing is in order to anti-
Only reunite again after ultrasound between time-out, repeated ultrasonic can reduce or eliminate such phenomenon；
Step (4): the H-PAN counterdie after step (2) are impregnated is placed in sand core funnel, pipettes MWCNTs-OH/EtOH
5~40ml of solution is filtered with the condition of 0.1MPa with vacuum pump, makes its filling to H-PAN counterdie；
Step (5): diamine monomer is dissolved in distilled water, is added acid and is received agent and surfactant, prepares diamines
Aqueous phase solution；
Step (6): equal four formyl chloride of benzene made from step (1) is dissolved in n-hexane, prepares organic phase solution；
Step (7): the H-PAN counterdie that step (4) is handled well is impregnated 5 in the diamines aqueous phase solution made from step (5)
~30min, liquid to the surface for removing excess surface is disposed vertically after taking-up does not have obvious water mark, is put into interface polymerization reaction
In frame；
Step (8): the membrane surface impregnated in organic phase solution made from 5~10ml step (6) to step (7) is pipetted
It is reacted, reacts 0.5~5min, the liquid to its surface volatilizees naturally, with 5ml n-hexane repeated flushing film surface 2~3
It is secondary, the organic phase monomer of excess surface is removed, surface forms polyamic acid (PAA) layer；
Step (9): preparing chemical imines reagent, and by prepared PAA film leaching 4~react for 24 hours, it is multiple to obtain polyimides
Film is closed, taking-up, which is put into distilled water, to be saved.
In the step (1), PCl52:1 need to be greater than with the molar ratio of PMDA, to guarantee phosphorus pentachloride excess, be heated to reflux
Temperature is 160 DEG C, and vacuum distillation temperature is 100~120 DEG C.
In the step (2), the concentration of sodium hydroxide solution prepared is 2mol/L, and soaking temperature is 60 DEG C.
In the step (3), the ethanol solution concentration of the MWCNTs-OH prepared is 0.02g/L.
In the step (5), diamine monomer is m-phenylene diamine (MPD), p-phenylenediamine, ethylenediamine, propane diamine, hexamethylene diamine or tetrem
One or more of five amine of alkene, the diamines aqueous phase solution concentration prepared are 1~5wt%；Acid receive agent be sodium hydroxide,
Potassium hydroxide or sodium carbonate are one such or several, and the concentration in diamines aqueous phase solution is 0.05~0.5wt%；Surface
Activating agent is lauryl sodium sulfate, neopelex, hexadecyltrimethylammonium chloride, sodium alkyl benzene sulfonate or rouge
Fat acid sulfoalkyl ester is one such or several, and the concentration in diamines aqueous phase solution is 0.1~0.5wt%.
In the step (6), the organic phase solution concentration prepared is 0.05~0.5wt%.
In the step (9), chemical imines reagent includes catalyst, dehydrating agent and solvent, wherein catalyst is triethylamine
Or pyridine, dehydrating agent are that acetic anhydride, trifluoro-acetic anhydride or propionic andydride are one such, solvent is benzene or acetone, catalyst, dehydration
Volume ratio between agent, solvent is 1:1~3:10.
Polyimide composite film produced by the present invention handles Halite water for infiltration evaporation.
The utility model has the advantages that
The present invention effectively reduces separating layer thickness by interfacial polymerization techniques, improves the infiltration of water to a certain extent
Saturating flux, and polyimides is a kind of organic high molecular polymer with imide ring, has good thermal stability, chemistry
Stability and good chlorine-resistant property.It introduces after MWCNTs-OH, in the case where rejection is held essentially constant, water flux
It has been further upgraded, can achieve 2~3 times of original flux, the chlorine resistance of film when introducing MECNTs-OH appropriate
It can be optimized with contamination resistance.
The prepared polyimides composite nano materials film for infiltration evaporation desalination, the desalination for high concentration salt water
When, the permeation flux of composite membrane is 15~17kg/m2H reaches 99.9% to the rejection of NaCl, can be efficiently to highly concentrated
It spends salt water and carries out desalination, reduce separating step, save equipment and operating cost.Although being added during the preparation process a small amount of
MWCNTs-OH can make hydrophily slightly be declined, but with the increase that MWCNTs-OH volume is added, hydrophily is gradually
Enhancing, improves the water flux in infiltration evaporation desalination processes.
Detailed description of the invention
Fig. 1 is the hydrophily test result of the PI TFC film after the MWCNTs-OH for filtering different volumes, is followed successively by implementation
The water contact angle of PI film in example 5, embodiment 1, embodiment 3, embodiment 4 and embodiment 2.
Fig. 2 is the section SEM of PI film prepared by embodiment 2.
Fig. 3 is the composite membrane of embodiment 1 at 30 DEG C, to 35000ppm NaCl (2000ppm under conditions of pH=7
NaClO the chlorine resistance experimental results of 48h).
Specific embodiment
Embodiment 1
10.4g pyromellitic dianhydride and 21.3g phosphorus pentachloride are weighed in flask, under the conditions of 160 DEG C, heating stirring is returned
Flow 10h.It is evaporated under reduced pressure under the conditions of 120 DEG C, removes extra phosphorus pentachloride and phosphorus oxychloride, methylene chloride dissolving-recrystallization,
Obtain pure four formyl chloride of equal benzene.
Compound concentration is the sodium hydroxide solution of 2mol/L, and temperature impregnates PAN film 1h under the conditions of being 60 DEG C.
H-PAN counterdie after immersion is placed in sand core funnel, 5ml is pipetted and prepares and the 0.02g/L through ultrasonic disperse
MWCNTs-OH/EtOH solution is placed in sand core funnel, is filtered with vacuum pump with the condition of 0.1MPa, is filled MWCNTs-OH
To H-PAN counterdie.
Prepare 1wt% m-phenylene diamine (MPD) aqueous phase solution, wherein be added 0.4g lauryl sodium sulfate, 0.1g sodium hydroxide and
0.3g sodium carbonate；Prepare the equal four formyl chloride n-hexane organic phase solution of benzene of 0.05wt%.MWCNTs-OH pretreatment will be filled through
Basement membrane be immersed in water phase after 5min, remove the aqueous phase monomers of excess surface, pipette 5ml organic phase solution, react 0.5min,
N-hexane repeated flushing.It is put into the triethylamine of pre-prepared volume ratio 1:1:10: acetic anhydride: the chemical imines reagent of acetone
Middle 4h reaction.After reaction, it is put into distilled water and saves backup.
Obtained polyimide composite film is measured to the desalting performance of high concentration salt water, test result is shown in Table 1.
To the infiltration evaporation desalting performance result of 35000ppmNaCl under 1 different temperatures of table
Fig. 1 is the hydrophily test result of the PI TFC film after the MWCNTs-OH for filtering different volumes, is followed successively by implementation
The water contact angle of PI film in example 5, embodiment 1, embodiment 3, embodiment 4 and embodiment 2.Fig. 1 show when introduce MWCNTs-OH it
Afterwards, water contact angle rises, and hydrophily is declined, mainly since the introducing of MWCNTs-OH results in the enhancing of thicknesses of layers,
Carbon increases in film layer, but continually introducing with MWCNTs-OH, the hydrophily of PI film are continuously increased, water contact angle drop
It is low.
Fig. 3 is successfully authenticated the chlorine-resistant for introducing the PI film of MWCNTs-OH by chlorine resistance experiment under certain condition
It is functional, it can be applied to field of seawater desalination.
Embodiment 2
9.2g pyromellitic dianhydride and 19.8g phosphorus pentachloride are weighed in flask, under the conditions of 160 DEG C, heating stirring is returned
Flow 10h.It is evaporated under reduced pressure under the conditions of 120 DEG C, removes extra phosphorus pentachloride and phosphorus oxychloride, methylene chloride dissolving-recrystallization,
Obtain pure four formyl chloride of equal benzene.
Compound concentration is the sodium hydroxide solution of 2mol/L, and temperature impregnates PAN film 1h under the conditions of being 60 DEG C.
H-PAN counterdie after immersion is placed in sand core funnel, 40ml is pipetted and prepares and the 0.02g/L through ultrasonic disperse
MWCNTs-OH/EtOH solution is placed in sand core funnel, is filtered with vacuum pump with the condition of 0.1MPa, is filled MWCNTs-OH
To H-PAN counterdie.
The hexamethylene diamine aqueous phase solution of 2wt% is prepared, wherein 0.25g neopelex is added, 0.3g potassium carbonate is matched
The equal four formyl chloride n-hexane organic phase solution of benzene of 0.1wt% processed.The basement membrane pre-processed is immersed in 10min in hexamethylene diamine water phase
Afterwards, the aqueous phase monomers for removing excess surface pipette 5ml organic phase solution, react 1min, n-hexane repeated flushing.It is put into advance
The triethylamine of prepared volume ratio 1:2:10: propionic andydride: 12h reacts in the chemical imines reagent of benzene.After reaction, it is put into
It is saved backup in distilled water.
Obtained polyimide composite film is measured to the desalting performance of high concentration salt water, test result is shown in Table 2.
To the infiltration evaporation desalting performance result of 35000ppmNaCl under 2 different temperatures of table
Fig. 2 is the section SEM of PI film prepared by embodiment 2, there is the presence of MWCNTs-OH as we can clearly see from the figure,
Confirm the validity of method.
Embodiment 3
14.2g pyromellitic dianhydride and 33.6g phosphorus pentachloride are weighed in flask, under the conditions of 160 DEG C, heating stirring is returned
Flow 10h.It is evaporated under reduced pressure under the conditions of 110 DEG C, removes extra phosphorus pentachloride and phosphorus oxychloride, methylene chloride dissolving-recrystallization,
Obtain pure four formyl chloride of equal benzene.
Compound concentration is the sodium hydroxide solution of 2mol/L, and temperature impregnates PAN film 1h under the conditions of being 60 DEG C.
H-PAN counterdie after immersion is placed in sand core funnel, 10ml is pipetted and prepares and the 0.02g/L through ultrasonic disperse
MWCNTs-OH/EtOH solution is placed in sand core funnel, is filtered with vacuum pump with the condition of 0.1MPa, is filled MWCNTs-OH
To H-PAN counterdie.
The propane diamine aqueous phase solution of 3wt% is prepared, wherein 0.1g sodium alkyl benzene sulfonate, 0.1g potassium carbonate and 0.15g is added
Sodium carbonate prepares the equal four formyl chloride n-hexane organic phase solution of benzene of 0.2wt%.The basement membrane pre-processed is immersed in water phase
After 30min, the aqueous phase monomers of excess surface are removed, pipette 10ml organic phase solution, react 5min, n-hexane repeated flushing.It puts
Enter the pyridine of pre-prepared volume ratio 1:3:10: trifluoro-acetic anhydride: being reacted for 24 hours in the chemical imines reagent of benzene.Reaction knot
Shu Hou is put into distilled water and saves backup.
Obtained polyimide composite film is measured to the desalting performance of high concentration salt water, test result is shown in Table 3.
To the infiltration evaporation desalting performance result of 35000ppm NaCl under 3 different temperatures of table
Embodiment 4
12.6g pyromellitic dianhydride and 31.2g phosphorus pentachloride are weighed in flask, under the conditions of 160 DEG C, heating stirring is returned
Flow 10h.It is evaporated under reduced pressure under the conditions of 120 DEG C, removes extra phosphorus pentachloride and phosphorus oxychloride, methylene chloride dissolving-recrystallization,
Obtain pure four formyl chloride of equal benzene.
Compound concentration is the sodium hydroxide solution of 2mol/L, and temperature impregnates PAN film 1h under the conditions of being 60 DEG C.
H-PAN counterdie after immersion is placed in sand core funnel, 20ml is pipetted and prepares and the 0.02g/L through ultrasonic disperse
MWCNTs-OH/EtOH solution is placed in sand core funnel, is filtered with vacuum pump with the condition of 0.1MPa, is filled MWCNTs-OH
To H-PAN counterdie.
The tetraethylenepentamine aqueous phase solution of 5wt% is prepared, wherein 0.1g lauryl sodium sulfate and 0.2g fatty acid is added
Sulfoalkyl ester, 0.1g sodium hydroxide and 0.2g sodium carbonate prepare the equal four formyl chloride n-hexane organic phase solution of benzene of 0.5wt%.It will
The basement membrane pre-processed is immersed in water phase after 30min, removes the aqueous phase monomers of excess surface, pipettes 10ml organic phase solution,
React 5min, n-hexane repeated flushing.Be put into the pyridine of pre-prepared volume ratio 1:3:10: acetic anhydride: the chemistry of benzene is sub-
It is reacted for 24 hours in amine reagent.After reaction, it is put into distilled water and saves backup.
Obtained polyimide composite film is measured to the desalting performance of high concentration salt water, test result is shown in Table 4.
To the infiltration evaporation desalting performance result of 35000ppm NaCl under 4 different temperatures of table
Embodiment 5
9.2g pyromellitic dianhydride and 19.8g phosphorus pentachloride are weighed in flask, under the conditions of 160 DEG C, heating stirring is returned
Flow 10h.It is evaporated under reduced pressure under the conditions of 120 DEG C, removes extra phosphorus pentachloride and phosphorus oxychloride, methylene chloride dissolving-recrystallization,
Obtain pure four formyl chloride of equal benzene.
Compound concentration is the sodium hydroxide solution of 2mol/L, and temperature impregnates PAN film 1h under the conditions of being 60 DEG C.
The hexamethylene diamine aqueous phase solution of 2wt% is prepared, wherein 0.25g neopelex is added, 0.3g potassium carbonate is matched
The equal four formyl chloride n-hexane organic phase solution of benzene of 0.1wt% processed.The basement membrane pre-processed is immersed in water phase after 10min, is removed
The aqueous phase monomers for removing excess surface pipette 5ml organic phase solution, react 1min, n-hexane repeated flushing.It is put into and prepares in advance
Volume ratio 1:2:10 triethylamine: propionic andydride: in the chemical imines reagent of benzene 12h react.After reaction, it is put into distilled water
In save backup.
Obtained polyimide composite film is measured to the desalting performance of high concentration salt water, test result is shown in Table 5
To the infiltration evaporation desalting performance result of 35000ppm NaCl under 5 different temperatures of table
Embodiment 6
Compound concentration is the sodium hydroxide solution of 2mol/L, and temperature impregnates PAN film 1h under the conditions of being 60 DEG C.
By 50 mMs of tetraethylenepentamine, after 50 mMs of pyromellitic acid anhydrides and 25 milliliters of NMP mixing, in room temperature machine
Tool stirs 20min, and 3h is stirred to react under ice bath, nitrogen atmosphere, and reaction terminates to obtain PAA solution after deaeration.Using dipping
Czochralski method prepares composite membrane, and PAA casting solution is uniformly coated to hydrophiling modified polyacrylonitrile (H-PAN) film surface, keeps PAA molten
Composite membrane, at composite membrane, is then put into three second of pre-prepared volume ratio 1:2:10 in its surface spreading open form by liquid
Amine: propionic andydride: 12h reacts in the chemical imines reagent of benzene.The composite membrane that polyimides separating layer is 30 μm.
Obtained polyimide composite film is measured to the desalting performance of high concentration salt water, test result is shown in Table 6.
To the infiltration evaporation desalting performance result of 35000ppm NaCl under 6 different temperatures of table
Claims (9)
1. a kind of polyimide composite film, which is characterized in that for the composite membrane by up of three-layer, first layer is with separation function
Polyimides separating layer, the second layer is that the multi-walled carbon nanotube (MWCNTs-OH) of the hydroxy-functional of vacuum filtration filling is sub-
Layer, third layer is the Porous-Organic base membrane layer to play a supportive role, wherein polyimides separating layer is obtained by interfacial polymerization
, thickness are as follows: 100~250nm, Porous-Organic base membrane layer are polyacrylonitrile (H-PAN) film of hydrophilic modification.
2. a kind of preparation method of polyimide composite film as described in claim 1, which is characterized in that the preparation method packet
Include following steps:
(1), pyromellitic dianhydride (PMDA) is added in flask, excessive phosphorus pentachloride (PCl is then added5), it is heated to reflux
10h, is cooled to room temperature, and vacuum distillation removes PCl extra in product5With by-product phosphorus oxychloride (POCl3), dichloro is added
Methane is dissolved and is recrystallized, and obtains pure four formyl chloride of equal benzene (BTAC)；
(2), sodium hydroxide solution is prepared, and impregnates PAN film 1h, obtains hydrophiling polyacrylonitrile (H-PAN) counterdie；
(3), the ethanol solution of MWCNTs-OH is prepared, ultrasonic disperse three times is carried out, every time lasting 15min, and after each dispersion
5min is stood, MWCNTs-OH/EtOH solution is obtained；
(4), by step (2) impregnate after H-PAN counterdie be placed in sand core funnel, pipette MWCNTs-OH/EtOH solution 5~
40ml is filtered with the condition of 0.1MPa with vacuum pump, makes its filling to H-PAN counterdie；
(5), diamine monomer is dissolved in distilled water, adds acid and receive agent and surfactant, prepares diamines aqueous phase solution；
(6), equal four formyl chloride of benzene made from step (1) is dissolved in n-hexane, prepares organic phase solution；
(7), 5~30min is impregnated in the H-PAN counterdie for handling step (4) well diamines aqueous phase solution made from step (5),
It is disposed vertically after taking-up, liquid to the surface for removing excess surface does not have obvious water mark, is put into the frame of interface polymerization reaction；
(8), the membrane surface impregnated in organic phase solution made from 5~10ml step (6) to step (7), reaction 0.5 are pipetted
~5min, the liquid to its surface volatilize naturally, with 5ml n-hexane repeated flushing film surface 2~3 times, remove excess surface
Organic phase monomer, surface form polyamic acid (PAA) layer；
(9), it prepares chemical imines reagent, and by prepared PAA film leaching 4~react for 24 hours, obtains polyimide composite film, take
It is put into distilled water and saves out.
3. the preparation method of polyimide composite film as claimed in claim 2, which is characterized in that in the step (1), PCl5
It is greater than 2:1 with the molar ratio of PMDA, being heated to reflux temperature is 160 DEG C, and vacuum distillation temperature is 100~120 DEG C.
4. the preparation method of polyimide composite film as claimed in claim 2, which is characterized in that in the step (2), prepare
Obtained concentration of sodium hydroxide solution is 2mol/L, and soaking temperature is 60 DEG C.
5. the preparation method of polyimide composite film as claimed in claim 2, which is characterized in that in the step (3), prepare
The ethanol solution concentration of obtained MWCNTs-OH is 0.02g/L.
6. the preparation method of polyimide composite film as claimed in claim 2, which is characterized in that in the step (5), diamines
Monomer is one or more of m-phenylene diamine (MPD), p-phenylenediamine, ethylenediamine, propane diamine, hexamethylene diamine or tetraethylenepentamine, with obtained
The diamines aqueous phase solution concentration arrived is 1~5wt%；Acid receive agent be one of sodium hydroxide, potassium hydroxide or sodium carbonate or
Several, concentration is 0.05~0.5wt%；Surfactant is lauryl sodium sulfate, neopelex, hexadecane
One or more of base trimethyl ammonium chloride, sodium alkyl benzene sulfonate or fatty acid sulfoalkyl ester, concentration be 0.1~
0.5wt%.
7. the preparation method of polyimide composite film as claimed in claim 2, which is characterized in that in the step (6), prepare
Obtained organic phase solution concentration is 0.05~0.5wt%.
8. the preparation method of polyimide composite film as claimed in claim 2, which is characterized in that in the step (9), chemistry
Imines reagent includes catalyst, dehydrating agent and solvent, wherein catalyst is triethylamine or pyridine, and dehydrating agent is acetic anhydride, trifluoro
One of acetic anhydride or propionic andydride, solvent are benzene or acetone, and the volume ratio of catalyst, dehydrating agent and solvent is 1:1~3:10.
9. a kind of application of polyimide composite film as described in claim 1, which is characterized in that the polyimide composite film
Infiltration evaporation desalination for high concentration salt water.
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