CN103933881B - A kind of method using interfacial polymerization to prepare composite nanometer filtering film - Google Patents
A kind of method using interfacial polymerization to prepare composite nanometer filtering film Download PDFInfo
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Abstract
The invention provides a kind of method using interfacial polymerization to prepare composite nanometer filtering film.The method is with ultrafilter membrane as porous support layer, select Cyanuric Chloride and/or hexachlorocyclotriph,sphazene as oil phase solute, with aqueous solutes in two-phase interface generation polyreaction, by controlling each group in reaction temperature activating reaction monomer, substep introduces different active nucleophilic agent and connects specific group, thus the film having synthesized short texture on porous support layer surface selects layer.It is experimentally confirmed that the composite hyperfiltration membrane utilizing the method for the present invention to prepare can be used in low-molecular-weight organic matter, inorganic salt, the separation of Yi Jiyi, divalent ion etc., and there is low operation pressure, effectively save energy consumption, therefore had a good application prospect.
Description
Technical field
The invention belongs to membrane material modified technical field, be specifically related to a kind of interfacial polymerization and prepare composite nanometer filter
Film.
Background technology
NF membrane is a kind of pressure between ultrafilter membrane and reverse osmosis membrane grown up after the eighties in 20th century
Power is tended to act film, and its operation pressure ratio reverse osmosis membrane is low.Nanofiltration membrane separation is carried out at normal temperatures, without chemical reaction,
Without phase transformation, do not destroy biological activity, can effectively retain bivalence and high price salt and hundreds of organic little point of molecular weight
Son, and make major part inorganic monovalent salt pass through, separable similar amino acid and protein, it is achieved high molecular and
The separating organic matters of low-molecular-weight, and cost is lower than traditional handicraft, is therefore widely used in water softening, work
The fields such as the process of industry use water, waste water, compound separation.
Nanofiltration-membrane technique is the study hotspot in membrance separation field, at present the scientific research institution of the state such as Japan, the U.S. and enterprise
The exploitation of NF membrane is attached great importance to by industry.In after proposing " nanofiltration " concept 20 years, the U.S., Japan
The NF membrane of the tens kinds of brands that released one after another, as Nitto Denko company of Japan NTR7450,
NTR-7250, NTR7410 etc., NF45, NF270 etc. of DOW company of the U.S..The NF membrane research of China
Starting from the nineties in 20th century, the unit being devoted to NF membrane research is the most more, but all in laboratory research rank
Section, the NF membrane of current domestic use is the most still external imported product.Therefore, grinding of NF membrane is actively developed
Study carefully the development that may advantageously facilitate China's NF membrane industry.
Currently, the NF membrane product the most sold or the NF membrane product of development stage, all there is operation pressure
Power higher (general operation pressure is at 0.7-2.0MPa) and cause the problem that energy consumption is big, such as NTR-7250 series
The operation pressure of NF membrane product at 2MPa.Therefore, by rationally the selecting of material and method, technique
Optimizing makes membrane structure be controlled, thus prepares the NF membrane product of low operation pressure (≤0.7MPa), with fall
Low energy consumption is one of research direction of current NF membrane.
It is known that the structure of top layer stratum disjunctum has a very big impact for the performance of NF membrane with composition.Structure
Build a loose ultra-thin stratum disjunctum and advantageously reduce the operation pressure of NF membrane undoubtedly, improve separating property.Mesh
Before, the preparation technology of NF membrane mainly has interfacial polymerization, immersion precipitation, weak solution coating, thermal induction
Phase inversion, chemic modified method, plasma polymerization and prepare the sol-gel process etc. used by inoranic membrane.Its
In, interfacial polymerization is that industrialization NF membrane in the world produces the common method used at present, and the method utilizes
(Chang Weishui and another kind are organic at two kinds of immiscible solvents for the high monomer (or prepolymer) of two kinds of reactivities
Solvent) interface generation polyreaction, thus on porous support layer, form a tunic select thin layer.Affect boundary
The principal element of face polymerization preparation NF membrane has monomer structure, monomer concentration, reaction temperature, response time, pH
Value, post-processing temperature etc., conventional research focuses mostly in the optimization of technique, and for monomer structure to nanofiltration
The research of film impact is the most relatively fewer.Aqueous phase list conventional in the method for NF membrane is prepared at present by interfacial polymerization
Body is m-diaminobenzene., piperazine etc., and oil phase monomer is pyromellitic trimethylsilyl chloride, m-phthaloyl chloride etc..But, right
Interface polymerization reaction result of study containing porous support layer shows, the polymerization rate of the monomer of different structure
And differ.
Summary of the invention
The technology of the present invention purpose is to operate, for above-mentioned NF membrane, the problem that pressure is higher, energy consumption is big, it is provided that a kind of
Use the method that interfacial polymerization prepares NF membrane, structure can be formed on porous support layer by the method and dredge
The film of pine selects layer, thus advantageously reduces the operation pressure of NF membrane.
In order to realize above-mentioned technical purpose, the present inventor attempts using Cyanuric Chloride or six after a large amount of investigations
Chlorine ring three phosphonitrile prepares the reaction monomers during NF membrane as interfacial polymerization, found that Cyanuric Chloride or
In hexachlorocyclotriph,sphazene, chlorine atomic reaction activity is higher, nucleophilic substitution easily occurs, and response speed is relatively
Hurry up.But, owing to the active degree of group each in both reaction monomers is different, the most how activating reaction list
Each group in body, optimization obtains the film of short texture and selects layer to be the problem needing further exploratory development.This
Inventor obtains after a large amount of experiments repeatedly, and in both reaction monomers, different chlorine atoms can be in different temperature
Under the conditions of be activated, therefore in interface polymerization reaction, by control reaction temperature, can introduce different step by step
Active nucleophilic agent, connects specific group such that it is able to synthesis has the film selection layer optimizing structure.
Specifically, the technical solution adopted in the present invention is: a kind of employing interfacial polymerization prepares composite nanometer filter
The method of film, comprises the steps:
Step 1: with ultrafilter membrane as porous support layer, introduces aqueous phase solution, after standing on porous support layer surface
Remove unnecessary solution；
Step 2: normal pressure, temperature be 10 DEG C～50 DEG C, under the conditions of relative humidity is 30%～90%, will step
Porous support layer surface after rapid 1 process introduces oil-phase solution, makes in the monomer in aqueous phase solution and oil-phase solution
Monomer at this two-phase interface polyreaction 30s～500s；
The described solute in oil-phase solution is Cyanuric Chloride or/and hexachlorocyclotriph,sphazene；
Step 3: the porous support layer after step 2 being processed carries out two-step thermal processing, first step heat treatment temperature
Being 20 DEG C～100 DEG C, heat treatment time is 0.1h～180h；Second step heat treatment temperature is 100 DEG C～150 DEG C,
Heat treatment time is 0.1h～180h；
Step 4: after being cooled to room temperature, rinses with deionized water, obtains composite nanometer filtering film.
In described step 1, ultrafilter membrane includes but not limited to by polysulfones, polyether sulfone, polyarylsulfone (PAS), polyvinylidene fluoride
Alkene (PVDF), polyvinylidene fluoride-hexafluoropropene (PVDF-HFP) prepare；Ultrafilter membrane form is not
Limit, can be Flat Membrane or hollow-fibre membrane；Wherein, hollow-fibre membrane include single hole hollow-fibre membrane or
Person's porous hollow fiber membrane, its intensity need to meet NF membrane operating condition.
In described step 1, aqueous phase solution includes but not limited to piperazine, m-diaminobenzene., triethanolamine, adjacent benzene
Diamidogen, p-phenylenediamine, hexamethylene diamine, Putriscine, 4,4-diaminodiphenyl ether, 4,4-diaminourea hexichol
Methane neighbour's biphenyl methylamine, dimethylamine, o-phenylenediamine, 1,2-propane diamine, 1,3-propane diamine, 2,4-diamino
Base toluene, 3-diethyl amino propylamine, 1,2-cyclohexanediamine, 4,5-dichloro o-phenylenediamine, and aforementioned each thing
A kind of monomer in the derivant of matter or the aqueous solution of several monomer；As preferably, the most various monomers are at aqueous phase
Mass percentage concentration in solution is 0.05%～1%.
In described step 1, porous support layer surface introduce aqueous phase solution mode do not limit, can use by
Porous support layer surface is immersed in aqueous phase solution, takes out after standing a period of time, many to remove with rubber rollers rolling
Remaining aqueous phase solution；Can also use uniformly coat on porous support layer surface, spray or soak fall aqueous phase solution,
With rubber rollers rolling to remove the methods such as unnecessary aqueous phase solution after standing a period of time.Described time of repose is excellent
Elect 1min～100min as.
As preferably, in described step 1, aqueous phase solution adds triethylamine, pyridine, 4-dimethylamino
Pyridine, DIPEA, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate,
One or more in potassium bicarbonate etc. are as acid binding agent；
As preferably, in described step 1, add in aqueous phase solution a certain amount of sodium lauryl sulphate,
Dodecyl sodium sulfate, octadecyl trimethyl ammonium chloride, cetalkonium chloride, benzyl three
Ethyl ammonium chloride, tetrabutylammonium chloride, tetradecyl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride, three
One or more in methyl dodecyl bromination ammonium etc. are as surfactant；Surfactant is at aqueous phase solution
In mass percentage concentration be preferably 0.05%～0.5%.
In described step 2, the solvent in oil-phase solution includes but not limited to toluene, normal hexane, benzene, acetic acid
The mixture of one or more in ethyl ester etc.；In described oil-phase solution, the mass percentage concentration of solute is preferably
0.05%～1%.
As preferably, the described solute in oil-phase solution with the amount ratio of the material of the solute in aqueous phase solution is
1:1～2:3.
As preferably, described acid binding agent and the ratio of the amount of the material of solute in oil-phase solution be preferably 5:1～
2:1。
In described step 2, the interface polymerization reaction time is preferably 90s～300s.
In described step 3, heat treatment mode does not limits, and can be to carry out in vacuum drying oven, it is also possible to be
Purge with hot-air.
In described step 3, as preferably, first step heat treatment temperature is 50 DEG C～90 DEG C, during heat treatment
Between be 0.5h～10h；Second step heat treatment temperature is 100 DEG C～150 DEG C, and heat treatment time is 0.5h～10h.
In sum, the present invention uses interfacial polymerization, with ultrafilter membrane as porous support layer, selects Cyanuric Chloride
And/or hexachlorocyclotriph,sphazene is as oil phase solute, with aqueous solutes in two-phase interface generation polyreaction, and then
By controlling reaction temperature, each group in activating reaction monomer, substep introduces different active nucleophilic agent even
Upper specific group, thus the film having synthesized short texture on porous support layer surface selects layer.It is experimentally confirmed that
The composite hyperfiltration membrane utilizing the method for the present invention to prepare can be used in low-molecular-weight organic matter, inorganic salt, Yi Jiyi,
The separation of divalent ion etc., and there is low operation pressure, it is possible to effectively save energy consumption, therefore there is good answering
Use prospect.
Accompanying drawing explanation
Fig. 1 is the XPS figure of pvdf membrane before and after the polyreaction of the embodiment of the present invention 1 median surface.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail, it should be pointed out that the following stated
Embodiment is intended to be easy to the understanding of the present invention, and it does not play any restriction effect.
Embodiment 1:
In the present embodiment, with PVDF ultrafiltration membrane as porous support layer, do aqueous phase solution with the aqueous solution of piperazine,
The toluene solution of Cyanuric Chloride does oil-phase solution, prepares composite nanometer filtering film by interfacial polymerization.Concrete steps are such as
Under:
Step 1: with PVDF flat plate ultrafiltration membrane as porous support layer；
Step 2: configuration aqueous phase solution, in aqueous phase solution, the mass percentage concentration of piperazine is 1.0%, aqueous phase solution
In also include triethylamine and sodium lauryl sulphate, wherein, the mass percent concentration of sodium lauryl sulphate is
0.1%；
Configuration oil-phase solution, in oil-phase solution, the mass percentage concentration of Cyanuric Chloride is 1.0%；
Triethylamine in aqueous phase solution is 3:1 with the ratio of the amount of the material of the Cyanuric Chloride in oil-phase solution.
Step 3: immersed on porous support layer surface in aqueous phase solution, takes out after standing 10min, uses rubber rollers
Rolling, removes unnecessary solution；
Step 4: be 84% time at normal temperature and pressure, relative humidity, the porous support layer table after step 3 processes
Face introduces oil-phase solution, makes aqueous phase solution and is polymerized monomer on the boundary of these two kinds of solution in oil-phase solution
Polyreaction occurs, and the interfacial polymerization time is 180s；
Step 5: the porous support layer after step 4 being processed is put into vacuum drying oven and carried out heat treatment, first exists
80 DEG C of heat treatment 1min, then at 120 DEG C of heat treatment 2min；
Step 6: after being cooled to room temperature, rinses with deionized water, obtains PVDF composite nanometer filtering film.
Characterize the pure PVDF ultrafiltration membrane before above-mentioned reaction by XPS, and carry out above-mentioned interface polymerization reaction
After the composite nanometer filtering film that obtains, as it is shown in figure 1, PVDF composite nanometer filtering film can successfully be obtained.
Carry out above-mentioned prepared PVDF composite nanometer filtering film separating test, be under 0.6MPa at operation pressure,
This PVDF composite nanometer filtering film is more than 90% to the rejection of 1g/L Adlerika.
Embodiment 2:
In the present embodiment, with PVDF hollow fiber ultrafiltration membrane as porous support layer, with the aqueous solution of m-diaminobenzene.
Doing aqueous phase solution, the benzole soln of Cyanuric Chloride does oil-phase solution, prepares composite nanometer filtering film by interfacial polymerization.
Specifically comprise the following steps that
Step 1: with PVDF hollow fiber ultrafiltration membrane as porous support layer；
Step 2: configuration aqueous phase solution, in aqueous phase solution, the mass percentage concentration of m-diaminobenzene. is 1.0%, water
Phase solution also includes potassium hydroxide and dodecyl sodium sulfate, wherein, the percent mass of dodecyl sodium sulfate
Specific concentration is 0.1%；
Configuration oil-phase solution, in oil-phase solution, the mass percentage concentration of Cyanuric Chloride is 0.8%；
Potassium hydroxide in aqueous phase solution is 3:1 with the ratio of the amount of the material of the Cyanuric Chloride in oil-phase solution.
Step 3: immersed on porous support layer surface in aqueous phase solution, takes out after standing 15min, rolls by rubber rollers
Pressure, removes unnecessary solution；
Step 4: 50 DEG C, normal pressure, relative humidity be 83% time, the porous support layer table after step 3 processes
Face introduces oil-phase solution, makes aqueous phase solution and is polymerized monomer in oil-phase solution on the boundary of these two kinds of solution
Raw polyreaction, the interfacial polymerization time is 120s；
Step 5: the porous support layer after step 4 being processed is put into vacuum drying oven and carried out two-step thermal processing, first
At 90 DEG C of heat treatment 1min, then at 100 DEG C of heat treatment 1min.
Step 5: after being cooled to room temperature, rinses with deionized water, obtains PVDF composite nanometer filtering film.
Characterize the pure PVDF hollow fiber ultrafiltration membrane before above-mentioned reaction by XPS, and carry out above-mentioned interface
The composite nanometer filtering film obtained after polyreaction, similar to Figure 1, can successfully obtain PVDF doughnut multiple
Close NF membrane.
Carry out above-mentioned prepared PVDF composite nanometer filtering film separating test, be under 0.6MPa at operation pressure,
This PVDF hollow fiber compound nanofiltration membrane is more than 90% to the rejection of 1g/L Adlerika.
Embodiment 3:
In the present embodiment, with polysulfone hollow fibre ultrafilter membrane as porous support layer, do with the aqueous solution of triethanolamine
Aqueous phase solution, the ethyl acetate solution of hexachlorocyclotriph,sphazene does oil-phase solution, compound by interfacial polymerization preparation
NF membrane.Specifically comprise the following steps that
Step 1: with polysulfone hollow fibre ultrafilter membrane as porous support layer；
Step 2: configuration aqueous phase solution, in aqueous phase solution, the mass percentage concentration of triethanolamine is 0.1%, aqueous phase
Solution also includes potassium hydroxide and cetalkonium chloride, wherein, hexadecyldimethyl benzyl ammonium benzyl
Ammonium chloride mass percentage concentration is 0.05%；
Configuration oil-phase solution, in oil-phase solution, the mass percentage concentration of hexachlorocyclotriph,sphazene is 0.3%.
Potassium hydroxide in aqueous phase solution with the ratio of the amount of the material of the hexachlorocyclotriph,sphazene in oil-phase solution is
3:1；
Step 3: immersed on porous support layer surface in aqueous phase solution, takes out after standing 15min, uses rubber rollers
Rolling, removes unnecessary solution；
Step 4: be 80% time at normal temperature and pressure, relative humidity, the porous support layer table after step 3 processes
Face introduces oil-phase solution, makes aqueous phase solution and is polymerized monomer on the boundary of these two kinds of solution in oil-phase solution
Polyreaction occurs, and the interfacial polymerization time is 140s；
Step 5: the porous support layer after step 4 being processed, by 80 DEG C of hot air treatment 1min, is used the most again
100 DEG C of hot air treatment 1min；
Step 6: after being cooled to room temperature, rinses with deionized water, obtains polysulfone hollow fibre composite nanometer filtering film.
Characterize the pure polysulfone hollow fibre ultrafilter membrane before above-mentioned reaction by XPS, and it is poly-to carry out above-mentioned interface
Close the composite nanometer filtering film that obtains after reaction, similar to Figure 1, can successfully obtain that polysulfone hollow fibre is compound to be received
Filter membrane.
Carry out above-mentioned prepared polysulfone hollow fibre composite nanometer filtering film separating test, at operation pressure be
Under 0.6MPa, this polysulfone hollow fibre composite nanometer filtering film to the rejection of 1g/L Adlerika be 90% with
On.
Embodiment 4:
In the present embodiment, with polyether sulfone flat plate ultrafiltration membrane as porous support layer, do water with the aqueous solution of o-phenylenediamine
Phase solution, the hexane solution of Cyanuric Chloride does oil-phase solution, prepares composite nanometer filtering film by interfacial polymerization.
Specifically comprise the following steps that
Step 1: with PES as porous support layer；
Step 2: configuration aqueous phase solution, the mass percentage concentration of o-phenylenediamine is 0.3%, also wraps in aqueous phase solution
Including triethanolamine and octadecyl trimethyl ammonium chloride, wherein, octadecyl trimethyl ammonium chloride percent mass is dense
Degree is 0.1%；
Configuration oil-phase solution, in oil-phase solution, the mass percentage concentration of Cyanuric Chloride is 0.3%；
Step 3: immersed on porous support layer surface in aqueous phase solution, takes out after standing 20min, uses rubber rollers
Rolling, removes unnecessary solution；
Step 4: be 87% time at normal temperature and pressure, relative humidity, the porous support layer table after step 3 processes
Face introduces oil-phase solution, makes aqueous phase solution and is polymerized monomer on the boundary of these two kinds of solution in oil-phase solution
Polyreaction occurs, and the interfacial polymerization time is 120s；
Step 5: the porous support layer after step 4 being processed is put into vacuum drying oven and carried out heat treatment, first exists
80 DEG C of heat treatment 1min, then at 100 DEG C of heat treatment 2min；
Step 5: after being cooled to room temperature, rinses with deionized water, obtains Polyethersulfone Hollow Fiber Plasma composite nanometer filtering film.
Characterize the pure PVDF flat board fiber ultrafiltration membrane before above-mentioned reaction by XPS, and carry out above-mentioned interface
The composite nanometer filtering film of polyreaction, similar to Figure 1, can successfully obtain polyether sulfone plate compounding NF membrane.
Carry out above-mentioned prepared polyether sulfone plate compounding NF membrane separating test, be 0.5MPa at operation pressure
Under, this polyether sulfone plate compounding NF membrane is more than 90% to the rejection of 1g/L Adlerika.
Embodiment 5:
In the present embodiment, with polyarylsulfone (PAS) flat plate ultrafiltration membrane as porous support layer, do aqueous phase with the aqueous solution of hexamethylene diamine
Solution, the toluene solution of hexachlorocyclotriph,sphazene does oil-phase solution, prepares composite nanometer filtering film by interfacial polymerization.Tool
Body step is as follows:
Step 1: with polyarylsulfone (PAS) flat plate ultrafiltration membrane as porous support layer；
Step 2: configuration aqueous phase solution, in aqueous phase solution, the mass percentage concentration of m-diaminobenzene. is 0.5%, aqueous phase
Solution also includes sodium hydroxide and tetradecyl trimethyl ammonium chloride, wherein, tetradecyl trimethyl ammonium chloride
Mass percent concentration be 0.2%；
Configuration oil-phase solution, in oil-phase solution, the mass percentage concentration of hexachlorocyclotriph,sphazene is 0.4%；
Sodium hydroxide in aqueous phase solution with the ratio of the amount of the material of the hexachlorocyclotriph,sphazene in oil-phase solution is
3:1；
Step 3: introduced on porous support layer surface in aqueous phase solution, rolls by rubber rollers after standing 15min,
Remove unnecessary solution；
Step 4: be 86% time at normal temperature and pressure, relative humidity, the porous support layer table after step 3 processes
Face introducing oil-phase solution, makes aqueous phase solution and is polymerized monomer in oil-phase solution on the boundary of these two kinds of solution
Polyreaction occurs, and the interfacial polymerization time is 130s；
Step 5: the porous support layer after step 4 being processed is by 90 DEG C of hot air treatment 1min, then very
110 DEG C of heat treatment 2min in empty drying baker；
Step 5: after being cooled to room temperature, rinses with deionized water, obtains polyarylsulfone (PAS) plate compounding NF membrane.
Characterize the pure polyarylsulfone (PAS) ultrafilter membrane before above-mentioned reaction by XPS, and carry out answering of above-mentioned interfacial polymerization
Close NF membrane, similar to Figure 1, can successfully obtain polyarylsulfone (PAS) plate compounding NF membrane.
Carry out above-mentioned prepared polyarylsulfone (PAS) plate compounding NF membrane separating test, be 0.6MPa at operation pressure
Under, this polyarylsulfone (PAS) plate compounding NF membrane is more than 90% to the rejection of 1g/L Adlerika.
Embodiment 6:
In the present embodiment, with PVDF-HFP hollow fiber ultrafiltration membrane as porous support layer, water-soluble with piperazine
Liquid does aqueous phase solution, and the benzole soln of hexachlorocyclotriph,sphazene does oil-phase solution, receives by interfacial polymerization preparation is compound
Filter membrane.Specifically comprise the following steps that
Step 1: with PVDF-HFP hollow fiber ultrafiltration membrane as porous support layer；
Step 2: configuration aqueous phase solution, in aqueous phase solution, the mass percentage concentration of piperazine is 0.7%, aqueous phase solution
In also include potassium carbonate and benzyltriethylammoinium chloride, wherein, the mass percent of benzyltriethylammoinium chloride is dense
Degree is 0.2%；
Configuration oil-phase solution, in oil-phase solution, the mass percentage concentration of hexachlorocyclotriph,sphazene is 0.4%；
The amount of the potassium carbonate in aqueous phase solution and the material of the hexachlorocyclotriph,sphazene in oil-phase solution is than for 3:1；
Step 3: introduce aqueous phase solution on porous support layer surface, rolls by rubber rollers after standing 18min, goes
Except unnecessary solution；
Step 4: 30 DEG C, atmospheric pressure, relative humidity be 90% time, the porous after step 3 processes is propped up
Support layer surface introduces oil-phase solution, makes aqueous phase solution and is polymerized the monomer phase at these two kinds of solution in oil-phase solution
Polyreaction occurs on interface, and the interfacial polymerization time is 200s；
Step 5: the porous support layer after step 4 being processed is by 90 DEG C of hot air treatment 5min, then in vacuum
130 DEG C of heat treatment 10min in drying baker；
Step 6: after being cooled to room temperature, rinses with deionized water, obtains that PVDF-HFP doughnut is compound to be received
Filter membrane.
Characterize the pure PVDF-HFP hollow fiber ultrafiltration membrane before above-mentioned reaction by XPS, and carry out above-mentioned
The composite nanometer filtering film obtained after interface polymerization reaction, similar to Figure 1, can successfully obtain PVDF-HFP
Hollow fiber nanofiltration membrane composite nanometer filtering film.
Carry out above-mentioned prepared PVDF-HFP hollow fiber compound nanofiltration membrane separating test, at operation pressure
For under 0.5MPa, this PVDF-HFP hollow fiber compound nanofiltration membrane rejection to 1g/L Adlerika
It is more than 90%.
Embodiment 7:
In the present embodiment, with PVDF flat board fiber ultrafiltration membrane as porous support layer, with the aqueous solution of p-phenylenediamine
Doing aqueous phase solution, the hexane solution of Cyanuric Chloride does oil-phase solution, prepares composite nanometer filter by interfacial polymerization
Film.Specifically comprise the following steps that
Step 1: with PVDF flat plate ultrafiltration membrane as porous support layer；
Step 2: configuration aqueous phase solution, in aqueous phase solution, the mass percentage concentration of p-phenylenediamine is 1.0%, aqueous phase
Solution also includes sodium hydroxide and tetradecyl trimethyl ammonium chloride, wherein, tetradecyl trimethyl ammonium chloride
Mass percent concentration be 0.1%；
Configuration oil-phase solution, in oil-phase solution, the mass percentage concentration of Cyanuric Chloride is 0.8%.
The amount of the sodium hydroxide in aqueous phase solution and the material of the Cyanuric Chloride in oil-phase solution is than for 3:1；
Step 3: introduce aqueous phase solution on porous support layer surface, rolls by rubber rollers after standing 15min, goes
Except unnecessary solution；
Step 4: be 84% time at normal temperature and pressure, relative humidity, the porous support layer table after step 3 processes
Face introduces oil-phase solution, makes aqueous phase solution and is polymerized monomer on the boundary of these two kinds of solution in oil-phase solution
Polyreaction occurs, and the interfacial polymerization time is 120s；
Step 5: the porous support layer after step 4 being processed is put into vacuum drying oven and carried out two-step thermal processing, first
First at 60 DEG C of heat treatment 1.5min, then 140 DEG C of heat treatment 2min in vacuum drying oven；
Step 6: after being cooled to room temperature, rinses with deionized water, prepares PVDF plate compounding NF membrane.
Characterize the pure PVDF flat plate ultrafiltration membrane before not carrying out above-mentioned reaction by XPS, and carry out above-mentioned boundary
The composite nanometer filtering film obtained after the polyreaction of face, similar to Figure 1, can successfully obtain PVDF plate compounding
NF membrane.
Carry out above-mentioned prepared PVDF plate compounding NF membrane separating test, be 0.6MPa at operation pressure
Under, this PVDF plate compounding NF membrane is more than 90% to the rejection of 1g/L Adlerika.
Claims (9)
1. the method using interfacial polymerization to prepare composite nanometer filtering film, is characterized in that: comprise the steps:
Step 1: with ultrafilter membrane as porous support layer, introduces aqueous phase solution, removes unnecessary solution after standing on porous support layer surface；
Step 2: normal pressure, temperature be 10 DEG C～50 DEG C, under the conditions of relative humidity is 30%～90%, porous support layer surface after step 1 being processed introduces oil-phase solution, makes the monomer in aqueous phase solution with the monomer in oil-phase solution in this two-phase interface polyreaction 30～500s；
The described solute in oil-phase solution is hexachlorocyclotriph,sphazene；
Step 3: the porous support layer after step 2 being processed carries out two-step thermal processing, first step heat treatment temperature is 20 DEG C～100 DEG C, and heat treatment time is 0.1h～180h；Second step heat treatment temperature is 100 DEG C～150 DEG C, and heat treatment time is 0.1h～180h；
Step 4: after being cooled to room temperature, rinses with deionized water, obtains composite nanometer filtering film.
The method that employing interfacial polymerization the most according to claim 1 prepares composite nanometer filtering film, is characterized in that: described ultrafilter membrane is to be prepared by polysulfones, polyether sulfone, polyarylsulfone (PAS), Kynoar, polyvinylidene fluoride-hexafluoropropene.
The method that employing interfacial polymerization the most according to claim 1 prepares composite nanometer filtering film, it is characterized in that: described aqueous phase solution be piperazine, m-diaminobenzene., triethanolamine, o-phenylenediamine, p-phenylenediamine, hexamethylene diamine, 1,4-butanediamine, 4,4-diaminodiphenyl ether, 4,4-MDA neighbour's biphenyl methylamine, dimethylamine, 1,2-propane diamine, 1,3-propane diamine, 2,4-diaminotoluene, 3-diethyl amino propylamine, 1,2-cyclohexanediamine, 4, the aqueous solution of one or more in 5-dichloro o-phenylenediamine, and the derivant of aforementioned each material.
The method that employing interfacial polymerization the most according to claim 1 prepares composite nanometer filtering film, is characterized in that: the described solvent in oil-phase solution includes the mixture of one or more in toluene, normal hexane, benzene, ethyl acetate.
The method that employing interfacial polymerization the most according to claim 1 prepares composite nanometer filtering film, is characterized in that: in described aqueous phase solution, the mass percent concentration of solute is 0.05%-1%.
The method that employing interfacial polymerization the most according to claim 1 prepares composite nanometer filtering film, is characterized in that: in described oil-phase solution, the mass percent concentration of solute is 0.05%～1%.
The method that employing interfacial polymerization the most according to claim 1 prepares composite nanometer filtering film, is characterized in that: the described solute in oil-phase solution is 1:1～2:3 with the ratio of the amount of the material of the solute in aqueous phase solution.
The method that employing interfacial polymerization the most according to claim 1 prepares composite nanometer filtering film, it is characterized in that: in described aqueous phase solution, one or more in addition sodium lauryl sulphate, dodecyl sodium sulfate, octadecyl trimethyl ammonium chloride, cetalkonium chloride, benzyltriethylammoinium chloride, tetrabutylammonium chloride, tetradecyl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride, trimethyldodecane base ammonium bromide are as surfactant, and described surfactant qualities accounts for the 0.05%～0.5% of aqueous phase solution quality.
The method that employing interfacial polymerization the most according to claim 1 prepares composite nanometer filtering film, it is characterized in that: described aqueous phase solution adds triethylamine, pyridine, DMAP, N, one or more in N-diisopropylethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate are 5:1～2:1 as acid binding agent, described acid binding agent with the ratio of the amount of the material of solute in oil-phase solution.
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| CN106040015A (en) * | 2016-06-29 | 2016-10-26 | 浙江大学 | High-throughput multilayer composite nano-filtration membrane and preparation method thereof |
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| CN115318110B (en) * | 2022-08-04 | 2023-08-11 | 哈尔滨工业大学 | Method for preparing high-selectivity nanofiltration membrane based on regulation and control of weak-polarity organic solvent |
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