CN110394073A - It is a kind of using crown ether preparation polyamide composite film, its preparation and application - Google Patents
It is a kind of using crown ether preparation polyamide composite film, its preparation and application Download PDFInfo
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- CN110394073A CN110394073A CN201810377657.8A CN201810377657A CN110394073A CN 110394073 A CN110394073 A CN 110394073A CN 201810377657 A CN201810377657 A CN 201810377657A CN 110394073 A CN110394073 A CN 110394073A
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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
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
Abstract
The invention belongs to UF membrane fields, more particularly, to a kind of polyamide composite film, preparation method and application prepared using crown ether for water process.The composite membrane includes polymeric support layer and polyamide active layer, polyamide active layer is reacted to obtain by the polynary amine aqueous solution of the additive containing crown ether with polynary solution of acid chloride, during the preparation process, interfacial polymerization occurs for the polynary amine aqueous solution of the additive containing crown ether and polynary solution of acid chloride, this modifies polyamide active layer is prepared, to greatly simplifie filming technology.Composite membrane water flux with higher, lower reversed flux salt.
Description
Technical field
The invention belongs to UF membrane fields, more particularly, to a kind of polyamides prepared using crown ether for water process
Amine composite membrane, preparation method and application.
Background technique
Polyamide composite film is common a kind of polymer film 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) with the mutually polynary acyl chlorides of oil or isocyanates reaction, in porous support layer
Surface forms the ultra-thin active layer with peak to valley asperities pattern of one layer of fine and close several hundred nanometer thickness.
Traditional polyamide composite film is to react a kind of high by water phase m-phenylene diamine (MPD) and oily phase pyromellitic trimethylsilyl chloride
The aromatic polyamides structure of crosslinking.This polyamide composite film is usually relatively hydrophobic, and water flux is lower, and water flux and direction salt are logical
There is the relationship of a kind of shifting (trade-off) between amount.In addition, during interfacial polymerization, due to m-phenylene diamine (MPD)
The slightly soluble in organic phase solvent, pyromellitic trimethylsilyl chloride is insoluble in water phase, causes two activated monomer reaction efficiencies very low.Meanwhile by
In the high reaction activity of two kinds of monomers, initially will form one layer of fine and close cortex in reaction can inhibit m-phenylene diamine (MPD) to organic
The migration of phase hinders the further progress of reaction, and obtained polyamide structure has high anisotropy, limits and passes through tune
Control polyamide microstructure optimizes the purpose of separating property to reach.Furthermore current filming technology post-processing is more loaded down with trivial details, removes
It needs outside using heat treatment, often requires to use sodium sulfite and liquor natrii hypochloritis carries out impregnating post-processing etc..
Therefore, the composite membrane that a kind of water flux is high, reversed flux salt is low how to be prepared in a simple way, is
It suffers from a problem that at present.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides it is a kind of using crown ether additive preparation
Polyamide composite film, preparation method and application, its object is to by that will contain the polynary amine aqueous solution of crown ether additive and more
First solution of acid chloride reaction, has obtained the modified polyamide active layer of ontology, so that it is compound to solve polyamide traditional at present
The technical issues of water flux present in film is not high enough, reversed flux salt height etc..
To achieve the above object, according to one aspect of the present invention, a kind of polyamide composite film, the composite membrane are provided
Including polymeric support layer, the composite membrane further includes polyamide active layer, and the polyamide active layer is by additive containing crown ether
Polynary amine aqueous solution and polynary solution of acid chloride interfacial reaction occur obtain.
Preferably, the mass ratio of the crown ether additive and the polyamine is (1-10): (1-5), the crown ether addition
Agent molecule formula general formula is x- crown- y and its derivative, and wherein x is the sum of the carbon atom and oxygen atom on crown ether cycle, and y is crown ether
Oxygen atomicity on ring.
Preferably, the crown ether additive is 18- crown- 6,12-crown-4,15- crown- 5,21- crown- 7, dibenzo -18- crown-
6, one of Benzo15crown5 derivatives, 30- crown- 10 or 1- azepine -18- crown- 6 or a variety of.
Preferably, the polyamine in the polynary amine aqueous solution of the additive containing crown ether be selected from p-phenylenediamine, m-phenylene diamine (MPD),
O-phenylenediamine, to one of cyclohexanediamine, hexamethylene diamine, polyethyleneimine and piperazidine or a variety of.
Preferably, the polynary acyl chlorides in the polynary solution of acid chloride is selected from equal four formyl chloride of benzene, pyromellitic trimethylsilyl chloride, to benzene
One of dimethyl chloride, o-phthaloyl chloride and Adipoyl Chloride are a variety of, and the mass-volume concentration of the polynary acyl chlorides is
0.05%-0.75%.
Preferably, the solvent of the polynary solution of acid chloride be selected from one of n-hexane, normal heptane, hexamethylene and toluene or
It is a variety of.
Other side according to the invention provides the preparation method of polyamide composite film described in one kind, including such as
Lower step:
(1) polymeric support layer is immersed in the polynary amine aqueous solution of the additive containing crown ether, is taken after sufficiently impregnating
Out；The mass ratio of the crown ether additive and the polyamine is (1-10): (1-5), the crown ether additive molecule formula general formula
For x- crown- y and its derivative, wherein x is the sum of the carbon atom and oxygen atom on crown ether cycle, and y is the oxygen atom on crown ether cycle
Number；Polyamine in the polynary amine aqueous solution of the additive containing crown ether is selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, right
One of cyclohexanediamine, hexamethylene diamine, polyethyleneimine and piperazidine are a variety of；
(2) by the surface of step (1) treated polymeric support layer and polynary solution of acid chloride haptoreaction, polyamides is obtained
Amine composite membrane；
Preferably, the crown ether additive is 18- crown- 6,12-crown-4,15- crown- 5,21- crown- 7, dibenzo -18- crown-
6, one of Benzo15crown5 derivatives, 30- crown- 10 or 1- azepine -18- crown- 6 or a variety of.
Preferably, the polynary acyl chlorides in the polynary solution of acid chloride is selected from equal four formyl chloride of benzene, pyromellitic trimethylsilyl chloride, to benzene
One of dimethyl chloride, o-phthaloyl chloride and Adipoyl Chloride are a variety of, and the mass-volume concentration of the polynary acyl chlorides is
0.05%-0.75%；The solvent of the polynary solution of acid chloride be selected from one of n-hexane, normal heptane, hexamethylene and toluene or
It is a variety of.
Preferably, the catalytic time described in step (2) is 1-10min.
Other side according to the invention provides the application of polyamide composite film described in one kind, is used for UF membrane.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
1, crown ether additive is added directly into polynary amine aqueous solution by the present invention occurs interfacial polymerization, system with polynary acyl chlorides
It is standby to obtain this modifies polyamide active layer, to greatly simplifie filming technology.
2, have rougher, more hydrophilic and free volume bigger by the way that the composite membrane that crown ether additive is prepared is added
Aramid layer obtains higher water flux.Verified, the water flux of composite membrane can be promoted to 74.6LMH.Simultaneously as crown ether
Addition can be complexed reversely diffuse through come the alkali metal ion for drawing matter, then further repel then diffuses through come draw
Matter is taken, so that reversed flux salt is substantially reduced.Verified, reversed flux salt can be down to 10.4gMH.In addition, due to different hats
Ether has different complexing powers to alkali metal ion, suitably draws matter by selection, high water flux, low reversed salt may be implemented
Flux.
Detailed description of the invention
Fig. 1 is comparative example and embodiment 1-4 composite film surface topography scan electron microscope.
Fig. 2 is comparative example and embodiment 1-4 composite membrane contact angle test result.
Fig. 3 is comparative example and embodiment 1-3 composite membrane forward osmosis performance test water flux result.
Fig. 4 is comparative example and the reversed flux salt result of embodiment 1-3 composite membrane forward osmosis performance test.
Fig. 5 is that comparative example with embodiment 2,4 composite membrane difference of embodiment draws liquid forward osmosis performance test water flux knot
Fruit.
Fig. 6 is comparative example with embodiment 2,4 composite membrane difference of embodiment, and to draw the reversed salt of liquid forward osmosis performance test logical
Measure result.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The present invention provides a kind of polyamide composite film, the composite membrane includes polymeric support layer, and the composite membrane is also
Including polyamide active layer, the polyamide active layer is anti-by the polynary amine aqueous solution of the additive containing crown ether and polynary solution of acid chloride
It should obtain.Wherein the mass ratio of crown ether additive and the polyamine is (1-10): (1-5), the crown ether additive molecule formula
General formula is x- crown- y and its derivative, and wherein x is the sum of the carbon atom and oxygen atom on crown ether cycle, and y is the oxygen on crown ether cycle
Atomicity, the crown ether additive are preferably 18- crown- 6,12-crown-4,15- crown- 5,21- crown- 7, dibenzo-18 crown-6, benzene
And one of -15- crown- 5,30- crown- 10 or 1- azepine -18- crown- 6 or a variety of, further preferably 18- crown- 6 or 15-
Crown- 5.Polyamine in the polynary amine aqueous solution of the additive containing crown ether be selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, to ring
One of hexamethylene diamine, hexamethylene diamine, polyethyleneimine and piperazidine are a variety of.Polynary acyl chlorides choosing in polynary solution of acid chloride
From one of equal four formyl chloride of benzene, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, o-phthaloyl chloride and Adipoyl Chloride or more
Kind, the mass-volume concentration (unit are as follows: g/100 milliliters) of the polynary acyl chlorides is 0.05%-0.75%.Polynary solution of acid chloride
Solvent is selected from one of n-hexane, normal heptane, hexamethylene and toluene or a variety of.Polymeric support layer is microfiltration membranes or ultrafiltration
The material of film, polymeric support layer is selected from polyacrylonitrile, polyether sulfone, polysulfones, polyimides, polyamide, polyetherimide, polyamides
Amine acid imide, cellulose acetate, Triafol T or Kynoar.
The preparation method of polyamide composite film of the invention, includes the following steps:
(1) polymeric support layer is immersed in described containing crown ether addition by the polynary amine aqueous solution for preparing the additive containing crown ether
In the polynary amine aqueous solution of agent, taken out after sufficiently impregnating；Normally, 1-2min can reach the purpose sufficiently impregnated.Sufficiently leaching
Time needed for bubble is related to the concentration of polynary amine aqueous solution, and usual 1-10min may make the absorption of polyamine to reach saturation.Hat
The mass ratio of ether additive and polyamine is (1-10): (1-5), and crown ether additive molecule formula general formula is x- crown- y and its derivative
Object, wherein x is the sum of the carbon atom and oxygen atom on crown ether cycle, and y is the oxygen atomicity on crown ether cycle；Preferred crown ether addition
Agent such as 18- crown- 6,12-crown-4,15- crown- 5,21- crown- 7, dibenzo-18 crown-6, phendioxin 5- crown- 5,30- crown- 10 or
One of 1- azepine -18- crown- 6 is a variety of.Polyamine in the polynary amine aqueous solution of the additive containing crown ether is selected to benzene two
Amine, m-phenylene diamine (MPD), o-phenylenediamine, to one of cyclohexanediamine, hexamethylene diamine, polyethyleneimine and piperazidine or a variety of.
(2) by the surface of step (1) treated polymeric support layer and polynary solution of acid chloride haptoreaction 1-10min,
Obtain polyamide composite film；In this step, polynary acyl chlorides and polyamine are poly- at the upper surface of polymeric support layer generation interface
Close reaction.Polynary acyl chlorides in polynary solution of acid chloride is selected from equal four formyl chloride of benzene, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, neighbour
One of phthalyl chloride and Adipoyl Chloride are a variety of, and the mass-volume concentration of the polynary acyl chlorides is 0.05%-0.75%；
The solvent of the polynary solution of acid chloride is selected from one of n-hexane, normal heptane, hexamethylene and toluene or a variety of.Polynary amine concentration
The too low polyamide active layer that will lead to interfacial polymerization formation is not fine and close enough, and composite membrane is selectively low, and concentration is too high to be made to be formed
Polyamide active layer it is too fine and close, cause water flux to reduce.Modified effect is unobvious when the concentration of crown ether additive is too low, dense
When Du Taigao, the polyamide active layer of formation is so dense, water flux decline.The polynary amine aqueous solution of the additive containing crown ether with it is polynary
The time of solution of acid chloride contact is 1-10min, and the time of contact is too short, and polynary acyl chlorides and polyamine and tertiary amine additive polymerize
Not exclusively, the time of contact is too long, then the polyamide active layer for reacting formation is too thick for reaction, so that the water for reducing composite membrane is logical
Amount.
Polyamide composite film provided by the invention can be applied to UF membrane, such as water process, including underwater gold category ion
Removing, sewage treatment or saline-water reclamation processing.
In interfacial polymerization process, the crown ether that the present invention selects can be organic with water phase aqueous solvent and organic phase n-hexane etc.
Solvent dissolves each other, and just can increase the mixed area of two phase reaction object in this way, so that more amine monomers is moved to organic phase and participates in interface
Polymerization reaction promotes the progress of interface polymerization reaction.In addition, crown ether can also migrate into aramid layer therewith, it is deposited
Hydrogen bond can be formed through the hydrone of membrane matrix with transmitting on the one hand, attract hydrone and promote hydrone in aramid layer
Interior transmitting；Itself existing hole cave structure also can provide additional express passway for the transmitting of hydrone simultaneously, increase
Free volume in aramid layer.On the other hand, crown ether hole can be complexed reversely diffuse through come draw alkali metal ion in matter,
Such as the Na in NaCl and KCl+And K+Ion, and the alkali metal ion being complexed can further repel subsequently reverse direction and diffuse through
Matter molecule is drawn, so that the reversed flux salt of composite membrane be effectively reduced.
The following are embodiments:
Comparative example
The polymeric support layer of the composite membrane of comparative example is polysulfones microfiltration membranes.The preparation process of the composite membrane includes following step
It is rapid:
(1) the m-phenylene diamine (MPD) aqueous solution that mass fraction is 3.4% is prepared, polysulfones base microfiltration membranes are fully immersed in the isophthalic
It is taken out after 2min in two amine aqueous solutions, catches up with the aqueous solution except the polysulfones base micro-filtration film surface；
(2) hexane solution for preparing the pyromellitic trimethylsilyl chloride that mass/volume score is 0.15%, which is poured on wet
Extra solution is outwelled, is obtained compound after contact 1 minute in one surface of the polysulfones base microfiltration membranes through step (1) processing of profit
Film is stored in pure water.
Embodiment 1
Crown ether additive is 15- crown- 5 in embodiment 1.The polymeric support layer of composite membrane is polysulfones microfiltration membranes.This is compound
The preparation process of film the following steps are included:
(1) the m-phenylene diamine (MPD) aqueous solution that mass fraction is 3.4% is prepared, is divided in the m-phenylene diamine (MPD) aqueous solution added with quality
The 15- crown- 5 that number is 1%, polysulfones base microfiltration membranes are fully immersed in the m-phenylene diamine (MPD) aqueous solution after 2min and are taken out, and are caught up with to remove and are somebody's turn to do
The aqueous solution of polysulfones base micro-filtration film surface；
(2) hexane solution for preparing the pyromellitic trimethylsilyl chloride that mass/volume score is 0.15%, which is poured on wet
The upper surface of the polysulfones base microfiltration membranes through step (1) processing of profit outwells extra solution and obtains composite membrane after contact 1 minute,
It is stored in pure water.
Embodiment 2
With embodiment 1, difference is experimental implementation, in step (1), the quality of 15- crown- 5 in m-phenylene diamine (MPD) aqueous solution
Score is 3%.
Embodiment 3
With embodiment 1, difference is experimental implementation, in step (1), the quality of 15- crown- 5 in m-phenylene diamine (MPD) aqueous solution
Score is 5%.
Embodiment 4
With embodiment 1, difference is experimental implementation, and in step (1), mass fraction is added in m-phenylene diamine (MPD) aqueous solution
For 3% 18- crown- 6.
To simplify the description, therefore the preparation parameter of embodiment 5- embodiment 10 is included in table 1, unlisted parameter and reality in table
It is identical to apply example 1.
The following are analysis of experimental results:
Fig. 1 shows the scanning electron microscope (SEM) photograph of the composite membrane of comparative example and embodiment 1-4 preparation, comparative example and embodiment 1-4
The composite membrane of preparation all shows typical foliaceous peak-to-valley pattern.What comparative example was mainly presented is nodular texture, and surface is opposite
It is smooth.And the composite membrane of embodiment 1-4 preparation shows warty and foliated mixed structure, film surface is relatively more coarse.
In general, film surface is more coarse, hydrophily is better, and water flux is bigger.
Fig. 2 shows the contact angle for the composite membrane that comparative example and embodiment 1-4 are prepared, and composite membrane connects in comparative example
Feeler is 81.9 ± 1.4 °, and in embodiment 1-4, the contact angle of composite membrane is respectively less than the composite membrane in control experiment comparative example
Contact angle.In general, the membrane flux of good hydrophilic property is higher, it is more difficult contaminated.
It is logical with the water flux and reversed salt of forward osmosis test device test comparison example and embodiment the 1-4 composite membrane prepared
Amount, specific experiment condition: drawing liquid is 2M sodium chloride or potassium chloride solution, and feed liquid is deionized water, feed liquid and draws liquid
Flow velocity is 0.3L/min, testing time 1h.Every kind of composite films retest three times, is averaged to result is measured three times
Value is used as experimental 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 15.7 ± 0.9LMH and 33.8 ± 2.2LMH, and its water flux of composite membrane modified for embodiment 1-3 is obviously improved, most
It can be promoted to 39.2 ± 3.1LMH and 73.4 ± 3.0 LMH greatly.It is modified, not only improve the water flux of composite membrane, and
Reversed flux salt is reduced to a certain extent.
As shown in figure 4, reversed salt of the composite membrane of comparative example preparation in the case where positive penetration modes and pressure delay penetration modes
Flux is 13.0 ± 1.3gMH and 23.3 ± 1.5gMH, and in embodiment 1-3, the reversed flux salt of composite membrane is substantially reduced,
Especially embodiment 3 and embodiment 4, reversed flux salt can be reduced to 6.3 ± 1.1/5.9 ± 1.0gMH and 10.8 ± 0.1/
10.4±0.7gMH.And under identical testing conditions relative to the most of polyamide composite films reported, water flux
It is obviously improved, reversed flux salt sharp fall.
In view of different crown ethers have different size of hole, different alkali metal can be complexed, therefore difference has been selected to draw
Matter (being 2M) is tested.As shown in figure 5, being used since the permeable pressure head that 2M NaCl and 2M KCl are generated is few
When difference draws matter, the water flux difference of film is little.In addition, since the hole of 18- crown- 6 is greater than 15- crown- 5, it is real
The water flux for applying example 4 is higher than embodiment 2, can reach 40.3 ± 2.5LMH and 74.6 ± 2.9LMH.
As shown in fig. 6, since 15- crown- 5 is to Na+There is strong complexing power, and to K+Complexing power is relatively weak, and because
KCl hydrated ionic radius is less than NaCl hydrated ionic radius, therefore the reversed flux salt of NaCl of embodiment 2 will be lower than KCl
's.And since 18- crown- 6 is to K+There is strong complexing power, and to Na+Complexing power is relatively weak, therefore the KCl of embodiment 4 is anti-
It instead will be lower than NaCl's to flux salt.
Above-mentioned test is carried out to remaining embodiment, also can get similar result.
By the above test result it is found that the present invention is not necessarily to other modified methods, directly using crown ether additive to polyamide
Layer is modified, and a kind of high performance composite membrane has been prepared, has greatly simplified filming technology.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of polyamide composite film, the composite membrane includes polymeric support layer, which is characterized in that the composite membrane further includes
By the polynary amine aqueous solution of the additive containing crown ether and polynary solution of acid chloride circle occurs for polyamide active layer, the polyamide active layer
It reacts to obtain in face.
2. polyamide composite film as described in claim 1, which is characterized in that the matter of the crown ether additive and the polyamine
Amount is than being (1-10): (1-5), and the crown ether additive molecule formula general formula is x- crown- y and its derivative, and wherein x is on crown ether cycle
Carbon atom and oxygen atom sum, y be crown ether cycle on oxygen atomicity, the crown ether additive is preferably 18- crown- 6,12-
In crown- 4,15- crown- 5,21- crown- 7, dibenzo-18 crown-6, Benzo15crown5 derivatives, 30- crown- 10 and 1- azepine -18- crown- 6
It is one or more.
3. polyamide composite film as described in claim 1, which is characterized in that the polynary amine aqueous solution of the additive containing crown ether
In polyamine be selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, to cyclohexanediamine, hexamethylene diamine, polyethyleneimine and to phenodiazine
One of own ring is a variety of.
4. polyamide composite film as described in claim 1, which is characterized in that the polynary acyl chlorides choosing in the polynary solution of acid chloride
From one of equal four formyl chloride of benzene, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, o-phthaloyl chloride and Adipoyl Chloride or more
Kind, the mass-volume concentration of the polynary acyl chlorides is 0.05%-0.75%.
5. polyamide composite film as described in claim 1, which is characterized in that the solvent of the polynary solution of acid chloride be selected from just oneself
One of alkane, normal heptane, hexamethylene and toluene are a variety of.
6. the preparation method of the polyamide composite film as described in claim 1 to 5 any one, which is characterized in that including as follows
Step:
(1) polymeric support layer is immersed in the polynary amine aqueous solution of the additive containing crown ether, is taken out after sufficiently impregnating；The hat
The mass ratio of ether additive and the polyamine is (1-10): (1-5), the crown ether additive molecule formula general formula be x- crown- y and
Its derivative, wherein x is the sum of the carbon atom and oxygen atom on crown ether cycle, and y is the oxygen atomicity on crown ether cycle；It is described to contain hat
Polyamine in the polynary amine aqueous solution of ether additive be selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, to cyclohexanediamine, oneself
One of diamines, polyethyleneimine and piperazidine are a variety of；
(2) by the surface of step (1) treated polymeric support layer and polynary solution of acid chloride haptoreaction, it is multiple to obtain polyamide
Close film.
7. preparation method as claimed in claim 6, which is characterized in that the crown ether additive be 18- crown- 6,12-crown-4,
One of 15- crown- 5,21- crown- 7, dibenzo-18 crown-6, Benzo15crown5 derivatives, 30- crown- 10 and 1- azepine -18- crown- 6
Or it is a variety of.
8. preparation method as claimed in claim 6, which is characterized in that the polynary acyl chlorides in the polynary solution of acid chloride is selected from equal
One of four formyl chloride of benzene, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, o-phthaloyl chloride and Adipoyl Chloride are a variety of, institute
The mass-volume concentration for stating polynary acyl chlorides is 0.05%-0.75%；The solvent of the polynary solution of acid chloride is selected from n-hexane, positive heptan
One of alkane, hexamethylene and toluene are a variety of.
9. preparation method as claimed in claim 6, which is characterized in that the haptoreaction time described in step (2) is 1-
10min。
10. the application of the polyamide composite film as described in claim 1 to 5 any one, which is characterized in that be used for UF membrane.
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| CN110790843A (en) * | 2019-11-19 | 2020-02-14 | 浙江肯特催化材料科技有限公司 | Hyperbranched cellulose crown ether and preparation method thereof |
| CN113893713A (en) * | 2021-12-13 | 2022-01-07 | 天津大学 | Preparation method of high-selectivity lithium-magnesium separation membrane |
| CN114642974A (en) * | 2020-12-17 | 2022-06-21 | 沃顿科技股份有限公司 | Composite reverse osmosis membrane and preparation method thereof |
| CN114749025A (en) * | 2022-01-07 | 2022-07-15 | 天津工业大学 | Method for separating magnesium and lithium by electric field coupling crown ether functionalized nanofiltration membrane |
| CN116478396A (en) * | 2022-01-14 | 2023-07-25 | 天津工业大学 | Preparation method of dibenzo-14-crown-4 polyamide for extracting lithium from salt lake |
| CN117181019A (en) * | 2023-11-07 | 2023-12-08 | 天津大学 | Nitrogen-containing hybrid macrocyclic cycloparaffin polyamide composite membrane, and preparation method and application thereof |
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