CN109589804A - A kind of hydrophilic polyolefin substrate composite nanometer filtering film and preparation method thereof - Google Patents
A kind of hydrophilic polyolefin substrate composite nanometer filtering film and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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Abstract
The present invention relates to a kind of hydrophilic polyolefin substrate composite nanometer filtering films, it is characterized in that, MIcroporous polyolefin film obtains the polyolefin film of hydrophilic modifying after immersing hydrophilic agent processing, then forms polyamide selectivity cortex by polyamine aqueous phase monomers and polynary acyl chlorides oil phase monomer interfacial polymerization on the polyolefin film of hydrophilic modifying.The application uses polyolefins film as substrate, compared with traditional ultrafiltration substrate, water flux with higher, and the flux retention time is long, performance is stablized；The hydrophilic modifying technique to polyolefin film of the application, operation is simple, and controllability is strong, and modified caudacoria can realize permanent hydrophilic, has the ability for carrying out continuous large-scale industrial production；The composite nanometer filtering film that the application is prepared with polyolefin-based bottom, water flux is higher, and retention NaCl is lower, retains Na2SO4It is higher, have good charged separating capacity.
Description
Technical field
The present invention relates to filter film technology fields, are a kind of hydrophilic polyolefin substrate composite nanometer filtering film and its system specifically
Preparation Method.
Background technique
Membrane Separation for Water Treatment is enriched with using having the film selectively penetrated to separate each component in solvent, pure
The advantages that method of change has efficiently, energy conservation, simple process, is the core process of current water treatment technology.Not according to aperture
Together, film is divided into microfiltration membranes, ultrafiltration membrane, nanofiltration membrane and reverse osmosis membrane.Wherein, the aperture of nanofiltration membrane between ultrafiltration membrane with it is reverse osmosis
It is 1nm or so between film, molecular cut off is 300~500 dalton.It has been generally acknowledged that the nanofiltration membrane mechanism of action is sieving actoion
With the synergistic effect of road south effect, it is ensured that it is relatively high have simultaneously through ability it is high cut salt performance, thus by
The extensive concern of domestic and foreign scholars and research develop very rapidly in recent years.
Currently, common composite nanometer filtering film is mainly prepared by interfacial polymerization, by loose perforated substrate film and it is thin and
Fine and close cortex composition.Basilar memebrane is used to provide the mechanical strength of film entirety as supporting layer, and cortex is used to provide the choosing of film
Select separating capacity.The performance of base material is particularly significant for nanofiltration membrane, and the stabilized soil pavement of substrate determines the use of film
Environment and service life, and the large aperture of substrate and high porosity then provide precondition for the high throughput of film.Traditional substrate material
Material such as cellulose acetate, polyacrylonitrile, polyarylsulfone (PAS), polyether sulfone etc., the substrate prepared is mostly ultrafiltration size, itself flux is inclined
It is low, and resistance to acid and alkali, inoxidizability and solvent resistance are poor, and use condition is restricted very big.
And polyolefin based materials such as polyethylene, the thermoplastic resins such as polypropylene, with excellent mechanical strength and physics and chemistry
Can, there are many advantages on preparing microporous film material, if film thickness is relatively thin, medium is small through resistance；Membrane aperture is larger, can
It is bigger to modify space；Resistance to acid and alkali and anti-oxidant strong with resistance to corrosion, long-time stability are good etc..But the low table of polyolefin material
Face energy, high hydrophobicity, so that surface wettability is poor, liquid is difficult to nature transmission；Hydrophobicity is but also film table in filter process
Face trapped substance bulk deposition, fouling membrane is serious, and water flux is caused to reduce, separating capacity decline.Thus for hydrophobic polyolefin material
The modification of material is particularly important.Have in the prior art using the method being co-deposited, passes through polyamines and deposition of the polyphenol solution on film
Polyolefin-based counterdie is modified, dyne value of hydrophobic interfaces is improved, it is anti-so as to carry out interfacial polymerization in substrate
It answers.
But co-electrodeposition method has the drawback that significantly: (1) needing the time longer, it is raw to be unfavorable for industrial serialization scale
It produces；(2) complex for operation step, control condition is relatively harsh, and temperature and humidity variation influence very greatly deposition rate；(3) it deposits
Bulky grain is formed after object autohemagglutination, causes film homogeneity poor, Pore Blocking is serious.It thus needs to find a kind of simple and direct efficient modification
Method is particularly important.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of hydrophilic polyolefin substrate composite nanometer filtering film and
Preparation method.The application by load hydrophilic agent in the way of to polyolefins basement membrane carry out hydrophilic modifying, make film surface and
It is easily flooded profit containing hydroxyl in fenestra, film tension significantly reduces；It is poly- that interface is then carried out on hydrophilic polyolefin film
Reaction is closed, highly selective polyamide cortex is generated.
The purpose of the present invention is achieved through the following technical solutions:
A kind of hydrophilic polyolefin substrate composite nanometer filtering film obtains hydrophilic after the immersion hydrophilic agent processing of polyolefin micropore basement membrane
Polyolefin base membrane then passes through polyamine aqueous phase monomers and polynary acyl chlorides oil phase monomer interfacial polymerization on hydrophilic polyolefin basement membrane
Form polyamide selectivity cortex.
A kind of hydrophilic polyolefin substrate composite nanometer filtering film and preparation method thereof
(1) polyolefin micropore basement membrane is cleaned with isopropanol, is immersed in hydrophilic agent after drying at room temperature；
The material of the polyolefin micropore basement membrane is selected from polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and one in Kynoar
Kind；
The porosity of the polyolefin micropore basement membrane is between 30~50%, and average pore size is between 0.02~0.4 micron
Between, average thickness is between 5~60 microns；
Hydrophilic agent includes polyvinyl alcohol, crosslinking agent, surfactant and solvent,
The alcoholysis degree of PVAC polyvinylalcohol is 80.0~99.8mol%, and molecular size range is 80000~180000.
Crosslinking agent be glyoxal, glutaraldehyde, to toluene dialdehyde, crotonaldehyde, oxalic acid, malonic acid, citric acid, maleic anhydride,
One of which in glycidyl methacrylate, trishydroxymethylaminomethane.
Surfactant is neopelex, lauryl sodium sulfate, kayexalate, glycerol, poly- second
Glycol, the one of which in nonylphenol polyoxyethylene ether.
Solvent is water；
Polyvinyl alcohol mass fraction in hydrophilic agent is 0.5~10%；Crosslinking agent is 0.1 in mass fraction in hydrophilic agent
~0.5%, mass fraction of the surfactant in hydrophilic agent is 1~10%.
The time for immersing hydrophilic agent is 1~10 minute.
(2) polyolefin base membrane that step (1) obtains load hydrophilic agent is taken out, and squeezes out redundant solution with silica gel roller, set
Heat cross-linking is carried out in baking oven；
The crosslinking temperature of heat cross-linking is 50~80 DEG C, and crosslinking time is 1~20min.
(3) polyolefin film of load polyvinyl alcohol that step (2) obtains is immersed in coagulation bath and carries out inversion of phases, after spend
Ionized water is cleaned, and hydrophilic polyolefin basement membrane is obtained；
Coagulation bath group becomes deionized water or ethanol/water solution, and wherein mass fraction of the ethyl alcohol in ethanol water is 1
~50%.
(4) it configures aqueous phase solution: polyamine is dissolved in high purity water, rear addition additive and sour accepting agent, ultrasound 10 minutes,
Set aside for use；
The polyamine is selected from piperazine, m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, one of equal benzene triamine；
Mass fraction of the polyamine in aqueous phase solution is 1~3%, and mass fraction of the sour accepting agent in aqueous phase solution is
0.5~2%, mass fraction of the additive in aqueous phase solution is 0.01~0.05%；
Additive therefor is precipitated silica；
Sour accepting agent is ethylenediamine.
It configures polynary acyl chlorides oil-phase solution: polynary acyl chlorides being taken to be dissolved in n-hexane, ultrasound 10 minutes, set aside for use；
The polynary acyl chlorides oil-phase solution is selected from pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, m-phthaloyl chloride and neighbour
One of phthalyl chloride；
Mass fraction of the polynary acyl chlorides in polynary solution of acid chloride is 0.1~0.5%.
(5) the hydrophilic polyolefin basement membrane for obtaining step (3) immerses in the aqueous phase solution containing polyamine, after standing five minutes
It takes out, removes excess surface solution；Then hydrophilic polyolefin film is immersed containing in polynary acyl chlorides oil-phase solution, carries out interfacial polymerization
Process, it is rear to take out, surplus liquid is removed, and be put into baking oven and be heat-treated；Obtain composite nanometer filter primary membrane；
The interface polymerization reaction time is 15~180 seconds, and reaction temperature is 10~30 DEG C.
Heat treatment temperature is 60~80 DEG C, and the processing time is 1~10min.
(6) the composite nanometer filter primary membrane obtained step (5) immerses organic solvent, after rinsed and save with deionization；It obtains
Polyolefin-based bottom composite nanometer filtering film.
The organic solvent is n-hexane or acetone.
Compared with prior art, the positive effect of the present invention is:
The application using polyolefins membrane aperture it is big, thickness is low, the high advantage of flux, solve current nanofiltration membrane flux compared with
It is low, and the defect that tolerance range is relatively narrow.
The technical process provided by the present application that hydrophilic modifying is carried out to hydrophobic microporous membrane, has greatly widened polyolefins
The application range of film, the application for polyolefins film in nanofiltration and reverse osmosis field provide strong reference.
The application uses polyolefins film as substrate, compared with traditional ultrafiltration substrate, water flux with higher, and it is logical
The amount retention time is long, and performance is stablized.
The hydrophilic modifying technique to polyolefin film of the application, operation is simple, and controllability is strong, and modified caudacoria can be realized
Permanent hydrophilic has the ability for carrying out continuous large-scale industrial production.
The composite nanometer filtering film that the application is prepared with polyolefin-based bottom, water flux is higher, and retention NaCl is lower, retains Na2SO4
It is higher, have good charged separating capacity.
Specific embodiment
The specific embodiment of hydrophilic polyolefin substrate composite nanometer filtering film of the present invention presented below and preparation method thereof.
Film properties test is carried out in embodiment and comparative example, and the specific method is as follows with characterization:
Thickness: using Marl, Germany THICKNESS GAUGE FOR THE MEASUREMENT OF THIN FOILS C1216 according to GB/T6672-2001 plastic film and sheet thickness
Measuring method measurement, same sample are tested 5 times, are averaged as average thickness.
Pure water flux: it is measured using nanofiltration test machine (self-control).
Rejection: it is measured using conductivity meter (DDS-307A, Lei Ci, Shanghai).
Flux and rejection: pure water flux is the important parameter for characterizing seperation film water permeable ability, under 0.8MPa pressure, is used
Film precompressed 1h is made stable water outlet as feed liquid by deionized water；Then pure water flux test, test device are carried out at 0.6MPa
Effective membrane area be 50cm2.Calculation formula is as follows:
Wherein, Q is the volume (L) through pure water, and Δ t is through the time (h), and A is through film effective area (cm2)。
Cutoff performance: rejection (R) two indices.After film precompressed, the NaCl and 1000mg/L of 1000mg/L are used instead
Na2SO4Prepare liquid, adjusting pressure are 0.6MPa, are tested at 25 DEG C of room temperature.Calculation formula is as follows:
CPAnd CFRespectively penetrating fluid and concentration of raw material (mg/L), it is generally recognized that be linear between conductivity and salinity
Correlation, thus can replace concentration with conductivity and carry out that salt-stopping rate R is calculated.
Comparative example 1
By polyethylene (Mn=5 × 106) microporous barrier (0.1 μm of average pore size, porosity 42%, 12 μm of thickness) cleaning, drying
2wt% polyvinyl alcohol (alcoholysis degree 98%, molecular weight 110000) solution is immersed afterwards, with 0.2wt% glutaraldehyde cross-linking, in hydrophilic agent
Surfactant SDBS content is 5wt%, is transferred to baking oven heat after standing 5min, is crosslinked 10min at 70 DEG C.It takes out and puts after the completion
Enter after 40wt% ethanol water removes extra hydrophilic agent and obtains hydrophilic polyethylene microporous barrier.
The aqueous phase solution of the 2wt% containing PIP is poured into hydrophilic polyethylene diaphragm plate frame, ethylenediamine content is in solution
It is taken out after 1wt%, 5min, with being dried with nitrogen surface liquid；The n-hexane containing pyromellitic trimethylsilyl chloride (TMC) 0.2wt% is poured into afterwards
In sheet frame, interface polymerization reaction is carried out at 26 DEG C, is taken out after 30s, is put into baking oven and is heat-treated 10min at 80 DEG C.
It takes the film out to be placed in acetone after having handled and impregnate, take out after 12h, saved in deionized water, obtain composite nanometer filter
Film.
Embodiment 1
By polyethylene (Mn=3 × 106) (0.058 micron of average pore size, porosity 47%, 20 microns of thickness) of microporous barrier use
Isopropanol cleaning, drying, it is rear to immerse 2wt% polyvinyl alcohol (alcoholysis degree 98%, molecular weight 110000) solution, with 0.5wt% penta 2
Aldehyde is crosslinked, and surfactant SDBS content is 10wt% in hydrophilic agent, is transferred to baking oven heat after standing 10min, is crosslinked at 70 DEG C
10min.It takes out to be put into after 40wt% ethanol water removes extra hydrophilic agent after the completion and obtains hydrophilic polyethylene microporous barrier.
The aqueous phase solution of the 2wt% containing piperazine is poured into hydrophilic polyethylene diaphragm plate frame, ethylenediamine content is in solution
It is taken out after 1wt%, precipitated silica silicone content 0.5wt%, 5min, with polyurethane pressure roller expression surface surplus liquid；After pour into
The n-hexane of the 0.2wt% containing pyromellitic trimethylsilyl chloride carries out interface polymerization reaction at room temperature, takes out after 30s, be put into baking in sheet frame
10min is heat-treated at 80 DEG C in case.
It takes the film out to be placed in acetone after having handled and impregnates 12h, rear taking-up, which is placed in deionized water, to be saved, and compound receive is obtained
Filter membrane 1.
The performance test results are shown, effectively increase the pure water of composite membrane through ability, film 1 after precipitated silica is added
Pure water flux reach 138.5L/m2.h per bar, improve 20% than being not added with example；In terms of retaining power, sodium chloride is cut
It is left 35.5%, and 96.8% is reached to sodium sulphate retention, there is superior divalent salts separating capacity.
Embodiment 2
By polyethylene (Mn=6 × 106) microporous barrier (0.043 micron of average pore size, porosity 35.4%, 16 microns of thickness)
It is rear to immerse 8wt% polyvinyl alcohol (alcoholysis degree 98%, molecular weight 110000) solution with isopropanol cleaning, drying, with 0.5wt% horse
Carry out acid anhydrides crosslinking, surfactant kayexalate content is 10wt% in hydrophilic agent, is transferred to baking oven after standing 10min
Heat is crosslinked 20min at 70 DEG C.It takes out to be put into after 40wt% ethanol water removes extra hydrophilic agent after the completion and obtains hydrophilic gather
Ethylene microporous barrier.
The aqueous phase solution of the 2wt% containing piperazine is poured into hydrophilic polyethylene diaphragm plate frame, ethylenediamine content is in solution
It is taken out after 1wt%, precipitated silica silicone content 0.5wt%, 5min, with polyurethane pressure roller expression surface surplus liquid；After pour into
The n-hexane of the 0.2wt% containing pyromellitic trimethylsilyl chloride carries out interface polymerization reaction at room temperature, takes out after 30s, be put into baking in sheet frame
10min is heat-treated at 80 DEG C in case.
It takes the film out to be placed in acetone after having handled and impregnates 12h, rear taking-up, which is placed in deionized water, to be saved, and compound receive is obtained
Filter membrane 2.
Performance test shows that the pure water flux 112.7L/m2.h per bar of composite nanometer filtering film is to sodium chloride retention
51.3%, 97.7% is reached to sodium sulphate retention, the decline of 1 flux of embodiment is compared obviously, shows to use the lower counterdie in aperture instead,
And under conditions of high-content polyvinyl alcohol hydrophilic modifying, fenestra can be further decreased, and flux is caused to reduce；To monovalent salt chlorine
The rejection for changing sodium is 51.3%, compares example 1 and is significantly improved, and divalent salts raising is not very obvious, also shows apparent
Molecular sieving effect.
Embodiment 3
Precipitated silica dosage is adjusted, increases its content to 5wt%, ultrasonic 10min, increasing the interfacial polymerization time is
120s, other conditions are the same as example 2.
Embodiment 3 is tested, pure water flux reaches 126.8L/m2.h per bar, shows to increase precipitated silica
The dosage of silicon has certain effect to flux is improved, but sodium chloride rejection is reduced to 36.6%, and sodium sulphate is reduced to 87.2%, table
The polyamide cortex aperture of bright formation is bigger than normal, and forms defect, and rejection is caused generally to reduce.
Embodiment 4
Polyamine piperazine (PIP) in above-described embodiment is changed to m-phenylene diamine (MPD) (MPD), dosage is still 2wt%, adjustment interface
Polymerization time is 60 seconds, other steps are constant, obtain composite nanometer filtering film 4.
Embodiment 4 is tested, the results show that after piperazine is changed to m-phenylene diamine (MPD), pure water flux drastically reduce to
71.5L/m2.h per bar, and sodium chloride rejection is significantly improved to 87%, the variation of sodium sulphate rejection less, shows to work as
When m-phenylene diamine (MPD) makees polynary amine component, the polyamide cortex of formation is excessively fine and close, and pure water flux is low at this time, and is unfavorable for monovalent salt
With the separation of divalent salts.
Embodiment 5
By polytetrafluoroethylene (PTFE) (Mn=6 × 106) after microporous barrier (0.5 micron of average pore size, 58 microns of thickness) cleaning, drying
4wt% polyvinyl alcohol (alcoholysis degree 98%, molecular weight 110000) solution is immersed, with 0.2wt% glutaraldehyde cross-linking, adds 5wt%
Surfactant SDBS is transferred to baking oven heat after standing 5min, is crosslinked 10min at 80 DEG C.It is rinsed after the completion in deionized water
1h is impregnated, hydrophilic polytetrafluoroethylmicroporous microporous barrier is obtained.
The aqueous phase solution of the 2wt% containing PIP is poured into hydrophilic polyethylene diaphragm plate frame, ethylenediamine content is in solution
It is taken out after 1wt%, 5min, excess surface liquid is squeezed out；The n-hexane containing pyromellitic trimethylsilyl chloride (TMC) 0.4wt% is poured into afterwards
In sheet frame, interface polymerization reaction is carried out at room temperature, is taken out after 80s, is put into baking oven and is heat-treated 10min at 80 DEG C.
It takes the film out to be placed in acetone after having handled and impregnate, take out after 12h, saved in deionized water, obtain composite nanometer filter
Film 5.
The performance test of embodiment 5 shows, pure water flux 159.2L/m2.h per bar is greatly improved compared with precedent,
But 30.8% is reduced to sodium chloride retention, sodium sulphate rejection is reduced to 90.2%；When doing basilar memebrane with polytetrafluoroethylene (PTFE), hole
Diameter is bigger than normal compared with polyethylene film, thus pure water flux is higher, but the polyamide cortex formed at this time is not fine and close enough, to the retention power of salt
It is insufficient.
The transmission and cutoff performance of the composite nanometer filtering film of 1. embodiment of table.
By table 1: precipitated silica silicon face is rich in hydroxyl, and the hydrophilic of polyamide cortex can be effectively improved after addition
Property, and polyamide cortex is made to become loose, the water of film is improved through ability.
The addition of hydroxyl group simultaneously improves nanofiltration process road south effect so that film surface charge density further increases
The sieving capacity for coping with monovalence and divalent salts, to improve to Na2SO4Interception capacity.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.
Claims (10)
1. a kind of hydrophilic polyolefin substrate composite nanometer filtering film, which is characterized in that polyolefin micropore basement membrane immerse hydrophilic agent processing with
After obtain hydrophilic polyolefin basement membrane, then on hydrophilic polyolefin basement membrane by polyamine aqueous phase monomers and polynary acyl chlorides oil mutually singly
Body interface polymerize to form polyamide selectivity cortex.
2. a kind of preparation method of hydrophilic polyolefin substrate composite nanometer filtering film, which is characterized in that the specific steps are that:
(1) polyolefin micropore basement membrane is cleaned with isopropanol, is immersed in hydrophilic agent after drying at room temperature；Immerse the time of hydrophilic agent
It is 1~10 minute；
(2) polyolefin base membrane that step (1) obtains load hydrophilic agent is taken out, and squeezes out redundant solution with silica gel roller, be placed in baking
Heat cross-linking is carried out in case；The crosslinking temperature of heat cross-linking is 50~80 DEG C, and crosslinking time is 1~20min；
(3) polyolefin film of load polyvinyl alcohol that step (2) obtains is immersed in coagulation bath and carries out inversion of phases, after use deionization
Water is cleaned, and hydrophilic polyolefin basement membrane is obtained；
(4) it configures aqueous phase solution: polyamine is dissolved in high purity water, rear that additive and sour accepting agent is added, ultrasound 10 minutes is stood
For use；
It configures polynary acyl chlorides oil-phase solution: polynary acyl chlorides being taken to be dissolved in n-hexane, ultrasound 10 minutes, set aside for use；
(5) the hydrophilic polyolefin basement membrane for obtaining step (3) immerses in the aqueous phase solution containing polyamine, and standing is taken out after five minutes,
Remove excess surface solution；Then hydrophilic polyolefin film is immersed containing in polynary acyl chlorides oil-phase solution, carries out interfacial polymerization process,
After take out, remove surplus liquid, and be put into baking oven and be heat-treated；Obtain composite nanometer filter primary membrane；
The interface polymerization reaction time is 15~180 seconds, and reaction temperature is 10~30 DEG C；
Heat treatment temperature is 60~80 DEG C, and the processing time is 1~10min；
(6) the composite nanometer filter primary membrane obtained step (5) immerses organic solvent, after rinsed and save with deionization；Obtain polyene
Alkyl bottom composite nanometer filtering film.
3. a kind of preparation method of hydrophilic polyolefin substrate composite nanometer filtering film as described in claim 1, which is characterized in that described
The material of polyolefin micropore basement membrane is selected from polyethylene, polypropylene, polytetrafluoroethylene (PTFE), one of Kynoar；
The porosity of the polyolefin micropore basement membrane between 30~50%, average pore size between 0.02~0.4 micron,
Average thickness is between 5~60 microns.
4. a kind of preparation method of hydrophilic polyolefin substrate composite nanometer filtering film as described in claim 1, which is characterized in that hydrophilic
Agent includes polyvinyl alcohol, crosslinking agent, surfactant and solvent,
The alcoholysis degree of PVAC polyvinylalcohol is 80.0~99.8mol%, and molecular size range is 80000~180000；
Crosslinking agent is glyoxal, glutaraldehyde, to toluene dialdehyde, crotonaldehyde, oxalic acid, malonic acid, citric acid, maleic anhydride, methyl
One of which in glycidyl acrylate, trishydroxymethylaminomethane；
Surfactant is neopelex, lauryl sodium sulfate, kayexalate, glycerol, polyethylene glycol,
One of which in nonylphenol polyoxyethylene ether；
Solvent is water.
5. a kind of preparation method of hydrophilic polyolefin substrate composite nanometer filtering film as claimed in claim 4, which is characterized in that poly- second
Enol mass fraction in hydrophilic agent is 0.5~10%；Crosslinking agent is 0.1~0.5% in mass fraction in hydrophilic agent, surface
Mass fraction of the activating agent in hydrophilic agent is 1~10%.
6. a kind of preparation method of hydrophilic polyolefin substrate composite nanometer filtering film as claimed in claim 2, which is characterized in that gel
Bath group becomes deionized water or ethanol/water solution, and wherein mass fraction of the ethyl alcohol in ethanol water is 1~50%.
7. a kind of preparation method of hydrophilic polyolefin substrate composite nanometer filtering film as claimed in claim 2, which is characterized in that described
Polyamine be selected from piperazine, m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, one of equal benzene triamine；
Mass fraction of the polyamine in aqueous phase solution is 1~3%, and mass fraction of the sour accepting agent in aqueous phase solution is 0.5
~2%, mass fraction of the additive in aqueous phase solution is 0.01~0.05%.
8. a kind of preparation method of hydrophilic polyolefin substrate composite nanometer filtering film as claimed in claim 2, which is characterized in that described
Polynary acyl chlorides oil-phase solution be selected from pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, in m-phthaloyl chloride and o-phthaloyl chloride
One kind；
Additive therefor is precipitated silica；
Sour accepting agent is ethylenediamine.
9. a kind of preparation method of hydrophilic polyolefin substrate composite nanometer filtering film as claimed in claim 2, which is characterized in that polynary
Mass fraction of the acyl chlorides in polynary solution of acid chloride is 0.1~0.5%.
10. a kind of preparation method of hydrophilic polyolefin substrate composite nanometer filtering film as claimed in claim 2, which is characterized in that institute
The organic solvent stated is n-hexane or acetone.
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| CN110302686A (en) * | 2019-06-13 | 2019-10-08 | 浙江特分环境技术有限公司 | A kind of high performance nanofiltration membrane preparation method based on building Multi-network |
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