CN106582315A - Polyamide composite membrane and preparation method thereof - Google Patents
Polyamide composite membrane and preparation method thereof Download PDFInfo
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- CN106582315A CN106582315A CN201611074835.7A CN201611074835A CN106582315A CN 106582315 A CN106582315 A CN 106582315A CN 201611074835 A CN201611074835 A CN 201611074835A CN 106582315 A CN106582315 A CN 106582315A
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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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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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
- B01D71/56—Polyamides, e.g. polyester-amides
Abstract
The invention relates to a polyamide composite membrane and a preparation method thereof, and belongs to the field of membrane separation. The composite membrane comprises a polymer support layer and a polyamide active layer composited on the polymer support layer; the polyamide active layer is obtained by carrying out a reaction of a polyamine aqueous solution containing a tertiary amine additive with a polyacyl chloride solution; in the preparation process, the polyamine aqueous solution containing the tertiary amine additive and the polyacyl chloride solution undergo interfacial polymerization, and the body modified polyamide active layer is obtained, so that the membrane preparation process is greatly simplified. The composite membrane has high water flux, low reverse salt flux, good anti-pollution performance and good membrane separation performance.
Description
Technical field
The invention belongs to membrance separation field, more particularly, to a kind of polyamide composite film and its system for water process
Preparation Method.
Background technology
Polyamide composite film is a kind of polymeric film commonly used in membrane separating process, and polyamide composite film is poly- by interface
The method of conjunction is prepared by water phase polyamine or alcohol (phenol) and the polynary acyl chlorides of oil phase or isocyanates reaction, in porous support layer
Surface forms the ultra-thin active layer with peak to valley asperities pattern of hundreds of nanometer thickness of one layer of densification.Traditional polyamide is combined
Film is the aromatic polyamides structure of a kind of high crosslinking obtained by water phase m-diaminobenzene. and the reaction of oil phase pyromellitic trimethylsilyl chloride, on boundary
During face is polymerized, due to the high reaction activity of two kinds of monomers, in reaction the cortex resistance of one layer of densification can be initially formed
That what is only reacted is further carried out, and the polyamide structure for obtaining has high anisotropy, is limited by regulating and controlling polyamide microcosmic
Structure optimizes the purpose of separating property, and the polyamide relative hydrophobic of this aromatic structure to reach, and its water flux is relatively low,
And be inclined to higher pollution, i.e., the easily absorption of various pollutant is on film surface.In addition, current filming technology post processing is more
It is loaded down with trivial details, in addition to needing using heat treatment, generally require to carry out soaking post processing etc. using sodium sulfite and liquor natrii hypochloritises.Cause
How this, prepare in a simple way that a kind of surface is smooth, hydrophilic is high, select the little polyamide film of thickness degree
Composite membrane is to suffer from a problem that at present realizing high water flux and more preferably antifouling property.
The content of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of polyamide composite film and preparation method thereof, by containing
The polynary amine aqueous solution of tertiary amine additive reacts with polynary solution of acid chloride, has obtained the modified polyamide active layer of body, from
And solve subject matter present in polyamide composite film traditional at present.
For achieving the above object, according to one aspect of the present invention, there is provided a kind of polyamide composite film.
The composite membrane includes polymeric support layer, also including the polyamide active layer being compounded on polymeric support layer, gathers
Amide active layer is obtained by the polynary amine aqueous solution containing tertiary amine additive with the reaction of polynary solution of acid chloride.
Preferably, the polyamine in the polynary amine aqueous solution containing tertiary amine additive is selected from p-phenylenediamine, m-diaminobenzene., adjacent benzene
Diamidogen, to one or more in cyclohexanediamine, hexamethylene diamine, polyethyleneimine and piperazidine.
Preferably, tertiary amine additive and the mass ratio of polyamine are (1-5):(1-5), tertiary amine additive is changed selected from formula (I)
One or more in compound,
Wherein, R, R ' and R " is separately in hydrogen atom, methylene, the straight chained alkyl and straight chain alkyl amine of C2-C6
One kind,
Preferably, tertiary amine additive is three (2- aminoethyls) amine, and structural formula is
Preferably, the polynary acyl chlorides in polynary solution of acid chloride is selected from the formyl chloride of equal benzene four, pyromellitic trimethylsilyl chloride, terephthaldehyde
One or more in acyl chlorides, o-phthaloyl chloride and Adipoyl Chloride, the mass-volume concentration of polynary acyl chlorides is 0.05%-
0.5%, the solvent of polynary solution of acid chloride is selected from one or more in normal hexane, normal heptane, hexamethylene and toluene.
Preferably, polymeric support layer is micro-filtration membrane or ultrafilter membrane, and the material of polymeric support layer is selected from polyacrylonitrile, gathers
Ether sulfone, polysulfones, polyimides, polyamide, Polyetherimide, polyamidoimide, cellulose acetate, Triafol T or poly-
Vinylidene.
According to another aspect of the present invention, there is provided a kind of preparation method of polyamide composite film, including following three
Step：
(1) the polynary amine aqueous solution containing tertiary amine additive is prepared, polymeric support layer is immersed in into this and contains tertiary amine additive
Polynary amine aqueous solution in, fully take out after immersion；
(2) by a surface of the polymer support layer after step (1) process and polynary solution of acid chloride haptoreaction, answered
Close film；
(3) composite membrane that step (2) is obtained is transferred in hot water carries out post processing.
In interfacial polymerization process, the tertiary amine additive that the present invention is selected can absorb polyamine as a kind of proton absorbent
The byproduct hydrogen chloride formed with polynary acyl chloride reaction, promotes further carrying out for reaction, a kind of highly cross-linked so as to obtain
Aromatic polyamides structure, highly cross-linked molecular structure can not only improve salt-stopping rate, and can reduce polyamide active layer
Thickness, so as to reduce the transport resistance of hydrone to reach the purpose for improving water flux.The addition of tertiary amine additive not only can be with
This highly cross-linked aromatic polyamides structure is obtained, and it is poly- to form the semiaromatic containing aliphatic chain with polyamine competitive reaction
Amide structure, this polyamide has a preferable hydrophilic, and can reduce the peak to valley asperities pattern of aramid layer, obtains phase
To smooth film surface, the hydrophilic of improvement and the film surface roughness for reducing can reduce the pollution tendency on film surface.
Preferably, the polyamine in the polynary amine aqueous solution containing tertiary amine additive is selected from p-phenylenediamine, m-diaminobenzene., adjacent benzene
Diamidogen, to one or more in cyclohexanediamine, hexamethylene diamine, polyethyleneimine and piperazidine.
Preferably, the mass fraction of tertiary amine additive is 1%-5%, and the mass fraction of polyamine is 1%-5%, and tertiary amine adds
Plus agent is selected from one or more in formula (I) compound,
Wherein, R, R ' and R " is separately in hydrogen atom, methylene, the straight chained alkyl and straight chain alkyl amine of C2-C6
One kind.
The too low polyamide active layer that interfacial polymerization can be caused to be formed of polyamine concentration is not fine and close enough, composite membrane selectivity
Low, concentration is too high to make the polyamide active layer to be formed too fine and close, cause water flux to reduce.The concentration of tertiary amine additive is too low
When modified effect it is unobvious, when concentration is too high, the polyamide active layer of formation is so dense, and water flux significantly declines.
Preferably, tertiary amine additive is three (2- aminoethyls) amine, and structural formula is
Preferably, soak time is 1-10min in step (1), and normally, 1-2min can reach the mesh of abundant immersion
's.Time fully needed for immersion is related to the concentration of polynary amine aqueous solution, and usual 1-10min can cause the absorption of polyamine to reach
To saturation.
Preferably, the pH of the polynary amine aqueous solution containing tertiary amine additive prepared by step (1) is 5-13, polynary to adjust
The compound of the pH value of amine aqueous solution includes dodecyl sodium sulfate, sodium lauryl sulphate, dodecylbenzene sodium sulfonate, Camphora
Sulfonic acid, polyoxyethylenated alcohol sodium sulfate, AESA, hydrochloric acid, sulphuric acid, sodium hydroxide, sodium carbonate,
Sodium bicarbonate, triethylamine, dipotassium hydrogen phosphate, one or more of potassium dihydrogen phosphate.Polyamine pH value of water solution is too low, and tertiary amine adds
Plus the most of amine groups in agent are all protonated, reactivity is lost, polyamine pH value of water solution is too high, tertiary amine additive
On all amine groups it is active, this modified polyamide active layer for obtaining of Jing is very fine and close, and polyamine pH value of water solution
The too high hydrolysis that can cause polynary acyl chlorides, obtains the low polyamide active layer of the extent of reaction, so as to cause compound membrane flux
Reduce.
Preferably, the polynary acyl chlorides in step (2) selected from the formyl chloride of equal benzene four, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride,
One or more in o-phthaloyl chloride and Adipoyl Chloride, the mass-volume concentration (w/v) of polynary acyl chlorides is 0.05%-
0.5%, the solvent of polynary solution of acid chloride is selected from one or more in normal hexane, normal heptane, hexamethylene and toluene.In the step
In, there is interface polymerization reaction in the upper surface of polymeric support layer with polyamine and tertiary amine additive in polynary acyl chlorides.
Preferably, polymeric support layer is micro-filtration membrane or ultrafilter membrane, and the material of polymeric support layer is selected from polyacrylonitrile, gathers
Ether sulfone, polysulfones, polyimides, polyamide, Polyetherimide, polyamidoimide cellulose acetate, Triafol T or poly-
Vinylidene.
Preferably, the haptoreaction time is 1-10min in step (2).Polynary amine aqueous solution containing tertiary amine additive with it is many
The time of first solution of acid chloride contact is 1-10min, and the time of contact is too short, polynary acyl chlorides and polyamine and tertiary amine additive it is poly-
Reaction is closed incomplete, the time of contact is oversize, then the polyamide active layer for reacting formation is too thick, so as to the water for reducing composite membrane leads to
Amount.
Post-processing operation in step (3) is to allow polynary acyl chlorides more to fill with the reaction of polyamine and tertiary amine additive
Point.
Preferably, hot water temperature is 40-100 DEG C in step (3), and finishing time is 1-60min.Hot water temperature it is too low or
Person's process time is too short, post processing DeGrain；Hot water temperature is too high or process time is oversize, the polyamide activity for obtaining
Layer it is so dense, water flux decline, and temperature too it is high be also possible to destroy membrane structure.
In general, by the contemplated above technical scheme of the present invention compared with prior art, can obtain down and show
Beneficial effect：
1st, tertiary amine additive is added directly in polynary amine aqueous solution and interfacial polymerization occurs with polynary acyl chlorides by the present invention,
This modifies polyamide active layer is prepared, so as to greatly simplifie filming technology.
2nd, the composite membrane by adding tertiary amine additive to prepare has finer and close polyamide molecule structure, obtains more
Low reverse flux salt, empirical tests, reverse flux salt is down to 12gMH.Simultaneously as thinner active layer thickness, reduces water
The transport resistance of molecule so as to higher water flux.Also, because the higher tertiary amine additive of nitrogen content is embedded into polyamides
In amine molecule chain, the hydrophilic of film is improved.Empirical tests, the water flux of composite membrane is improved to 58LMH.Due to more preferable
Hydrophilic and more smooth film surface, empirical tests, the present invention prepare polyamide composite film for common pollutant Sargassum
Sour sodium has good antifouling property, and the water flux after pollution reduces being less than 30%.
Description of the drawings
Fig. 1 is comparative example and embodiment 1-5 composite film surface topography scan electron microscope.
Fig. 2 is comparative example and embodiment 1-5 composite membrane contact angle test result.
Fig. 3 is comparative example and embodiment 1-5 composite membrane forward osmosis the performance test results.
Fig. 4 is comparative example and the reverse flux salt test result of embodiment 1-5 composite membrane.
Fig. 5 is comparative example and embodiment 1-5 composite membrane antipollution test result.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, and
It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each embodiment
Not constituting conflict each other just can be mutually combined.
Tertiary amine additive of the present invention is a kind of tertiary amine for carrying three amine groups, due to its molecular structure itself
The feature having, it is easy to the byproduct hydrogen chloride produced in absorption interface polymerization process, therefore on the one hand it can be used as catalysis
Agent promotes the carrying out of interface polymerization reaction, accelerates forward reaction speed, obtains the densification activity that the degree of cross linking is higher, thickness is thinner
Layer.On the other hand, it obtains the half of the higher fatty chain of hydrophilic as a kind of active amine monomer and polynary acyl chloride reaction
The smooth active layer of armaticity polyamide.It is higher that the dual function of tertiary amine additive causes modified polyamide composite film to have
Water flux, lower reverse flux salt, more preferable antifouling property.
It is below specific embodiment
Comparative example
The polymeric support layer of the composite membrane of comparative example is polysulfones micro-filtration membrane.The preparation process of the composite membrane includes following step
(1) the m-diaminobenzene. aqueous solution that mass fraction is 3.4% is prepared, polysulfones base micro-filtration membrane is fully immersed in into the isophthalic
Take out after 2min in two amine aqueous solutions, catch up with except the aqueous solution on the polysulfones base micro-filtration membrane surface；
(2) hexane solution of the pyromellitic trimethylsilyl chloride that mass/volume fraction is 0.15% is prepared, the solution is poured on wet
One surface of the polysulfones base micro-filtration membrane that the Jing steps (1) of profit are processed, after contacting 1 minute, outwells unnecessary solution；
(3) polyamide composite film formed in step (2) is transferred to 5 minutes in 80 DEG C of hot water, in being subsequently placed in pure water
Preservation is used.
Embodiment 1
Tertiary amine additive is three (2- aminoethyls) amine in embodiment 1, and structural formula isComposite membrane it is poly-
Compound supporting layer is polysulfones micro-filtration membrane.The preparation process of the composite membrane includes following step
(1) the m-diaminobenzene. aqueous solution that mass fraction is 3.4% is prepared, quality point is added with the m-diaminobenzene. aqueous solution
Number is 1% three (2- aminoethyls) amine, and the pH camphorsulfonic acids of the m-diaminobenzene. aqueous solution are adjusted to 9, by polysulfones base micro-filtration membrane
It is fully immersed in the m-diaminobenzene. aqueous solution after 2min and takes out, catches up with except the aqueous solution on the polysulfones base micro-filtration membrane surface；
(2) hexane solution of the pyromellitic trimethylsilyl chloride that mass/volume fraction is 0.15% is prepared, the solution is poured on wet
The upper surface of the polysulfones base micro-filtration membrane that the Jing steps (1) of profit are processed, after contacting 1 minute, outwells unnecessary solution；
(3) polyamide composite film formed in step (2) is transferred to into heat treatment 5 minutes in 80 DEG C of hot water, is subsequently placed in
Preserve in pure water and use.
Embodiment 2
Experimental implementation is with embodiment 1, difference, in step (1), (2- aminoethyls) amine three in m-diaminobenzene. aqueous solution
Mass fraction be 2%.
Embodiment 3
Experimental implementation is with embodiment 1, difference, in step (1), (2- aminoethyls) amine three in m-diaminobenzene. aqueous solution
Mass fraction be 3%.
Embodiment 4
Experimental implementation is with embodiment 1, difference, and in step (1), m-diaminobenzene. aqueous solution pH is adjusted with camphorsulfonic acid
To 8.
Embodiment 5
Experimental implementation is with embodiment 1, difference, and in step (1), m-diaminobenzene. aqueous solution pH is adjusted with camphorsulfonic acid
To 11.
In order to simplify description, therefore list the preparation parameter of embodiment 6- embodiment 11 in table 1, not listed parameter and reality in table
Apply example 1 identical.
It is below interpretation
Fig. 1 shows the scanning electron microscope (SEM) photograph of composite membrane prepared by comparative example and embodiment 1-5, composite membrane prepared by comparative example
Show typical foliaceous peak-to-valley polyamide structure, and composite membrane prepared by embodiment 1-5 show it is more fine and close smooth
Warty peak-to-valley polyamide structure.The formation of peak-to-valley polyamide structure mainly includes two steps.For comparative example, first, when
Two phase liquid contact when, the polyamine in aqueous phase solution can be migrated to organic faciess, and at two-phase interface with polynary acyl chlorides
Reaction forms initial warty peak-to-valley polyamide structure, the structure relative smooth；Then, due to interfacial tension at two-phase interface
Presence, polyamine accelerates to be gone forward side by side single step reaction to organic faciess migration so that originally warty peak-to-valley polyamide structure expands and distorts
More obvious foliaceous peak-to-valley polyamide structure is obtained, the structure relative coarseness.Due between this polyamine and polynary acyl chlorides
Reactivity is all very high, and response speed is very fast, and the aramid layer for originally being formed can to a certain extent suppress this polyamine
To the further migration of organic faciess, for embodiment 1-5, in the presence of tertiary amine additive, due to urging for tertiary amine structure
Change is acted on, and can further speed up the generation of reaction, increases the degree of cross linking of polyamide molecule, obtains more fine and close aramid layer,
In addition it also more inhibits migration of the polyamine to organic faciess, prevents and becomes apparent from foliaceous peak-to-valley polyamide structure
Formation.And the formation of semi-aromatic polyamide molecule can also obtain the aramid layer of relative smooth therefore modified is poly-
Amide active layer is more fine and close smooth.The film surface of warty peak-to-valley structure is more smooth, and roughness is little；Foliaceous peak and valley structure
Film rough surface, roughness is big.Roughness is bigger, surface relative hydropathic, but easily contaminated.As a result it will be appreciated that, embodiment
The composite membrane that 1-5 is prepared is difficult to be contaminated.
Fig. 2 shows the contact angle of the composite membrane that comparative example and embodiment 1-5 are prepared, and composite membrane connects in comparative example
Feeler is 56.2 ± 1.0 °, in embodiment 1-5, except embodiment 3 and embodiment 5, the contact of the composite membrane of remaining embodiment
Angle is respectively less than the contact angle of the composite membrane in control experiment comparative example.All composite membranes of comparative example and embodiment 1-5 are respectively provided with
There is preferable hydrophilic, embodiment 1,2 and 4 more preferable hydrophilic to be because that tertiary amine additive take part in interface polymerization reaction
Afterwards, a kind of semi-aromatic polyamide active layer is obtained, because tertiary amine additive contains many amine groups, the introducing of amine groups is improved
The hydrophilic of film.And for embodiment 3 and 5, although semi-aromatic polyamide active layer is defined, but due to there is more amine
Group take part in reaction, obtain finer and close aramid layer, and in addition the less warty peak-to-valley structure of its surface roughness, leads
Cause its hydrophilic decline.
The water flux and reverse salt of the composite membrane prepared with forward osmosis test device test comparison example and embodiment 1-5 is logical
Amount, specific experiment condition：It is 2M sodium-chloride water solutions to draw liquid, and feed liquid is deionized water, and feed liquid is with the flow velocity for drawing liquid
0.3L/min, the testing time is 1h.Every kind of composite films retest three times, results averaged is measured as reality to three times
Test result.
As shown in figure 3, water flux of the composite membrane of comparative example preparation in the case where positive penetration modes and pressure delay penetration modes
Respectively 22.7 ± 1.3LMH and 43.4 ± 2.2LMH, and its water flux is obviously improved for the modified composite membrane of embodiment 1-5, most
32.0 ± 1.3LMH and 63.0 ± 1.3LMH can be promoted to greatly.It is modified, the water flux of composite membrane is not only improved, and one
Determine to reduce reverse flux salt in degree.
As shown in figure 4, reverse salt of the composite membrane of comparative example preparation in the case where positive penetration modes and pressure delay penetration modes
Flux is 12.1 ± 1.0gMH and 19.6 ± 1.2gMH, in embodiment 1-5, although its reverse flux salt of embodiment 1 and 4 is more right
Ratio is high, but its water flux lifts amplitude and becomes apparent from, and considers water flux and reverse flux salt, and its separating property is relatively contrasted
Example still has a certain upgrade.And for the reverse flux salt of the composite membrane of remaining embodiment preparation is substantially reduced, especially
Embodiment 3, its reverse flux salt can be reduced to 6.8 ± 0.4gMH and 14.8 ± 1.1gMH.And it is most relative to what is reported
Under identical testing conditions, its water flux is obviously improved number polyamide composite film, and reverse flux salt significantly declines.
Antifouling property test is carried out to composite membrane prepared by comparative example and embodiment 1-5 with positive penetration equipment.It is concrete real
Test condition：With the synthetic wastewater containing 250mg/L sodium alginates as pollutant feed liquid, the sodium-chloride water solution using 2M is used as drawing
Liquid is taken, pollutant feed liquid is 0.3L/min, carries out the seriality Contamination measurement of 18 hours, real time record with the flow velocity for drawing liquid
Water flux change of the composite membrane in test process.Test terminate after, deionized water as feed liquid plus be twice flow velocity
Under the conditions of backwash 20min is carried out to film, then measure water flux recovery situation in real time as feed liquid with pure water.
As shown in figure 5, water flux significantly declines after the compound fouling membrane of comparative example, and flux recovery rate after backwash
Less than 60%.The composite membrane of embodiment 1-5 shows outstanding antifouling property, and after polluting 18 hours, water flux rate of descent is all
Less than 30%, and flux recovery rate all up to more than 94.3% after backwash.
Above-mentioned test is carried out to remaining embodiment, similar result can be also obtained.
From above test result, the present invention directly utilizes tertiary amine additive to polyamide without the need for other modified methods
Layer is modified, and has prepared a kind of high performance composite membrane, greatly simplifies filming technology.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, not to
The present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc. are limited, all should be included
Within protection scope of the present invention.
Claims (10)
1. a kind of polyamide composite film, the composite membrane includes polymeric support layer, it is characterised in that the composite membrane also includes
The polyamide active layer being compounded on the polymeric support layer, the polyamide active layer is by the polyamine containing tertiary amine additive
Aqueous solution is obtained with the reaction of polynary solution of acid chloride.
2. a kind of polyamide composite film as claimed in claim 1, it is characterised in that the polynary aqueous amine containing tertiary amine additive
Polyamine in solution selected from p-phenylenediamine, m-diaminobenzene., o-phenylenediamine, to cyclohexanediamine, hexamethylene diamine, polyethyleneimine and right
One or more in two piperazines；The tertiary amine additive is (1-5) with the mass ratio of the polyamine:(1-5), the uncle
Amine additive is selected from one or more in formula (I) compound,
Wherein, R, R ' and R " is separately in hydrogen atom, methylene, the straight chained alkyl and straight chain alkyl amine of C2-C6
Kind.
3. a kind of polyamide composite film as claimed in claim 1, it is characterised in that the tertiary amine additive is three (2- ammonia second
Base) amine.
4. a kind of polyamide composite film as claimed in claim 1, it is characterised in that the polynary acyl in the polynary solution of acid chloride
One kind in the formyl chloride of equal benzene four, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, o-phthaloyl chloride and the Adipoyl Chloride of chlorine or
Various, the mass-volume concentration of the polynary acyl chlorides is 0.05%-0.5%, the solvent of the polynary solution of acid chloride selected from just oneself
One or more in alkane, normal heptane, hexamethylene and toluene.
5. a kind of preparation method of polyamide composite film, it is characterised in that the preparation method comprises the steps：
(1) prepare the polynary amine aqueous solution containing tertiary amine additive, polymeric support layer is immersed in described containing tertiary amine additive
Take out after polynary amine aqueous solution, fully immersion；
(2) by a surface of the polymeric support layer after step (1) process and polynary solution of acid chloride haptoreaction, obtain one and be combined
Film；
(3) composite membrane that step (2) is obtained is transferred in hot water carries out post processing.
6. a kind of preparation method of polyamide composite film as claimed in claim 5, it is characterised in that described containing tertiary amine additive
Polynary amine aqueous solution in polyamine selected from p-phenylenediamine, m-diaminobenzene., o-phenylenediamine, to cyclohexanediamine, hexamethylene diamine, poly- second
One or more in alkene imines and piperazidine；In the polynary amine aqueous solution containing tertiary amine additive, the tertiary amine
The mass fraction of additive is 1%-5%, and the mass fraction of the polyamine is 1%-5%, and the tertiary amine additive is selected from formula
(I) one or more in compound,
Wherein, R, R ' and R " is separately in hydrogen atom, methylene, the straight chained alkyl and straight chain alkyl amine of C2-C6
Kind.
7. a kind of preparation method of polyamide composite film as claimed in claim 5, it is characterised in that the tertiary amine additive is
Three (2- aminoethyls) amine.
8. a kind of preparation method of polyamide composite film as claimed in claim 5, it is characterised in that prepared by the step (1)
The pH of the polynary amine aqueous solution containing tertiary amine additive be 5-13, to adjust the polynary aqueous amine containing tertiary amine additive
The compound of the pH value of solution includes dodecyl sodium sulfate, sodium lauryl sulphate, dodecylbenzene sodium sulfonate, Camphora sulphur
Acid, polyoxyethylenated alcohol sodium sulfate, AESA, hydrochloric acid, sulphuric acid, sodium hydroxide, sodium carbonate, carbon
Sour hydrogen sodium, triethylamine, dipotassium hydrogen phosphate, one or more of potassium dihydrogen phosphate.
9. a kind of preparation method of polyamide composite film as claimed in claim 5, it is characterised in that in the step (2)
Polynary acyl chlorides is in the formyl chloride of equal benzene four, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, o-phthaloyl chloride and Adipoyl Chloride
One or more, the mass-volume concentration of the polynary acyl chlorides is 0.05%-0.5%, and the solvent of the polynary solution of acid chloride is selected
From one or more of normal hexane, normal heptane, hexamethylene and toluene.
10. a kind of preparation method of polyamide composite film as claimed in claim 5, it is characterised in that connect in the step (2)
The tactile response time is 1-10min, and hot water temperature is 40-100 DEG C in the step (3), and finishing time is 1-60min.
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| CN108126536A (en) * | 2017-12-29 | 2018-06-08 | 湖南澳维环保科技有限公司 | A kind of polyamide composite film and preparation method thereof |
| CN108187511A (en) * | 2017-12-27 | 2018-06-22 | 东华大学 | High flux and high retention ratio polyamide composite reverse osmosis membrane and preparation method thereof |
| CN109200836A (en) * | 2017-07-01 | 2019-01-15 | 华中科技大学 | A kind of polyamide composite film, preparation method and application |
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| EP3702020A4 (en) * | 2018-07-09 | 2021-02-17 | Lg Chem, Ltd. | Water treatment separation membrane, water treatment module comprising same, and manufacturing method therefor |
| CN112535957A (en) * | 2020-11-10 | 2021-03-23 | 同济大学 | Composite membrane with intermediate layer for forward osmosis of organic solvent and preparation method and application thereof |
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| EP3702020A4 (en) * | 2018-07-09 | 2021-02-17 | Lg Chem, Ltd. | Water treatment separation membrane, water treatment module comprising same, and manufacturing method therefor |
| CN112535957A (en) * | 2020-11-10 | 2021-03-23 | 同济大学 | Composite membrane with intermediate layer for forward osmosis of organic solvent and preparation method and application thereof |
| CN112535957B (en) * | 2020-11-10 | 2021-12-07 | 同济大学 | Composite membrane with intermediate layer for forward osmosis of organic solvent and preparation method and application thereof |
| CN113083032A (en) * | 2021-04-26 | 2021-07-09 | 贵州省材料产业技术研究院 | Positively charged blended ultrafiltration membrane and preparation method thereof |
| CN113230913A (en) * | 2021-05-11 | 2021-08-10 | 燕山大学 | Preparation method and application of nitrate-trapped polyethersulfone nanofiltration membrane |
| WO2023040336A1 (en) * | 2021-09-18 | 2023-03-23 | 宁波大学 | Solvent-resistant forward osmosis composite membrane, preparation method therefor, and application thereof |
| CN115007003A (en) * | 2022-05-13 | 2022-09-06 | 天津工业大学 | High-flux positively-charged composite nanofiltration membrane, preparation method and application |
| CN115007003B (en) * | 2022-05-13 | 2023-12-22 | 天津工业大学 | High-flux positively charged composite nanofiltration membrane, preparation method and application |
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